11DOE Kick-off Meeting Washington DC September 28 2010

Fuel Cell Projects Kick-off Meeting Washington DC ndash September 28 2010

Advanced Materials and Concepts for Portable Power Fuel Cellsfor Portable Power Fuel Cells

Piotr Zelenay

Los Alamos National LaboratoryLos Alamos National Laboratory Los Alamos New Mexico 87545

This presentation does not contain any proprietary confidential or otherwise restricted information ndash

t t

Overview

Timeline

bull Start date September 2010 bull End date Four-year duration

BudgetBudget

bull Total funding estimate ndash DOE share $3825K

Contractor share $342K$342Kndash Contractor share bull FY10 funding received $250K bull FY11 funding estimate $1000K

Barriers

bull A Durability (catalyst electrode)(catalyst electrode)

bull B Cost (catalyst membrane MEA) bull C Electrode Performance

(f(fuell oxidatiion kikinetiics)id )

Partners ndash Principal Investigators

Brookhaven National Laboratory

ndash Radoslav Adzic

University of California RiversideUniversity of California Riverside

ndash Yushan Yan

Virginia TechVirginia Tech

ndash James McGrath

Johnson Mattheyy Fuel Cells ndash Nadia Permogorov

Smart Fuel Cell Energy

ndash Verena Graf

Oak Ridge National Laboratory

ndash Karren More

DOE Kick-off Meeting Washington DC ndash September 28 2010 22

t t

t

= 1 = -

Relevance Objective amp Targets

Objective Develop advanced materials (catalysts membranes electrode structures b l d bli ) d f l ll ti bl f f lfillimembrane-electrode assemblies) and fuel cell operating concepts capable of fulfilling

cost performance and durability requirements established by DOE for portable fuel cell systems assure path to large-scale fabrication of successful materials

Project technical targets bull System cost target $3W bull Performance target Overall fuel conversion efficiency (ηΣ) of 20-25 kWhL

F h l f lFor methanol fuel (1) 20-25 kWhL rarr ηΣ = 042-052 (16-20times improvement over the state of the art ~ 1250 kWhL) (2) If ηfuel = 096 ηBOP= 090 Vth=121 (at 25degC)

V = V [ηΣ ((ηη η ] 06 07 V The ultimate project goalVcell Vth [η fuel ηBOP ))-1] = 0 6-0 7 V The ultimate project goal

DOE Kick-off Meeting Washington DC ndash September 28 2010 33

t t

Overview

Timeline

bull Start date September 2010 bull End date Four-year duration

BudgetBudget

bull Total funding estimate ndash DOE share $3825K

Contractor share $342K$342Kndash Contractor share bull FY10 funding received $250K bull FY11 funding estimate $1000K

Barriers

bull A Durability (catalyst electrode)(catalyst electrode)

bull B Cost (catalyst membrane MEA) bull C Electrode Performance

(f(fuell oxidatiion kikinetiics)id )

Partners ndash Principal Investigators

Brookhaven National Laboratory

ndash Radoslav Adzic

University of California RiversideUniversity of California Riverside

ndash Yushan Yan

Virginia TechVirginia Tech

ndash James McGrath

Johnson Mattheyy Fuel Cells ndash Nadia Permogorov

Smart Fuel Cell Energy

ndash Verena Graf

Oak Ridge National Laboratory

ndash Karren More

DOE Kick-off Meeting Washington DC ndash September 28 2010 22

t t

t

= 1 = -

Relevance Objective amp Targets

Objective Develop advanced materials (catalysts membranes electrode structures b l d bli ) d f l ll ti bl f f lfillimembrane-electrode assemblies) and fuel cell operating concepts capable of fulfilling

cost performance and durability requirements established by DOE for portable fuel cell systems assure path to large-scale fabrication of successful materials

Project technical targets bull System cost target $3W bull Performance target Overall fuel conversion efficiency (ηΣ) of 20-25 kWhL

F h l f lFor methanol fuel (1) 20-25 kWhL rarr ηΣ = 042-052 (16-20times improvement over the state of the art ~ 1250 kWhL) (2) If ηfuel = 096 ηBOP= 090 Vth=121 (at 25degC)

V = V [ηΣ ((ηη η ] 06 07 V The ultimate project goalVcell Vth [η fuel ηBOP ))-1] = 0 6-0 7 V The ultimate project goal

DOE Kick-off Meeting Washington DC ndash September 28 2010 33

t t

t

= 1 = -

Relevance Objective amp Targets

Objective Develop advanced materials (catalysts membranes electrode structures b l d bli ) d f l ll ti bl f f lfillimembrane-electrode assemblies) and fuel cell operating concepts capable of fulfilling

cost performance and durability requirements established by DOE for portable fuel cell systems assure path to large-scale fabrication of successful materials

Project technical targets bull System cost target $3W bull Performance target Overall fuel conversion efficiency (ηΣ) of 20-25 kWhL

F h l f lFor methanol fuel (1) 20-25 kWhL rarr ηΣ = 042-052 (16-20times improvement over the state of the art ~ 1250 kWhL) (2) If ηfuel = 096 ηBOP= 090 Vth=121 (at 25degC)

V = V [ηΣ ((ηη η ] 06 07 V The ultimate project goalVcell Vth [η fuel ηBOP ))-1] = 0 6-0 7 V The ultimate project goal

DOE Kick-off Meeting Washington DC ndash September 28 2010 33

Approach Focus Areas

bull DMFC anode research minus cattallysts with iith improvedd ac titivitity andd reducedd cost (BNL JMFCJMFC LANL)t d t (BNL LANL) minus development of catalysts with improved durability (LANL JMFC)

bull Alternative fuels for portable fuel cells minus ethanol oxidation electrocatalysis (BNL LANL) minus dimethyl ether research (LANL)

bull Innovative electrode structures for better activityy and durabilit yy ((UCR)) bull Hydrocarbon membranes for lower MEA cost and enhanced fuel cell

performance (VT LANL) minus block copolymersblock copolymers

minus copolymers with cross-linkable end-groups

bull Characterization performance and durability testing multi-cell device minus advanced materials characterization (ORNL BNL LANL) minus MEA performance testing (LANL JMFC SFC) minus durability evaluation (LANL JMFC SFC) minus five-cell stack (SFC)

DOE Kick-off Meeting Washington DC ndash September 28 2010 44

- deg deg

05 M MeOH in 01 M HClO4

PtRuC (commercial)) 10 nmol Pt + 10 nmol Ru

mA

μg Pt

)

4

6

8

55

DMFC Anode Research Activity

bull DMFC Vth=121 V (at 25degC) fuel specific energy 61 kWhkg

bull CH OH + 2H O rarr CO + 6H+ + 6e- E cong 002 V (at 25 C)CH3OH + 2H2O rarr CO2 + 6H+ + 6e Edeg cong 0 02 V (at 25degC)

bull Reduction of methanol-oxidation overpotential through atomic-level control of PtRu nanoparticle synthesis minus optimal Pt atom ensembles for MeOH adsorption and abstraction of H atomsoptimal Pt-atom ensembles for MeOH adsorption and abstraction of H atoms minus adequate Ru coverage for providing OH and O species for CO oxidation minus submonolayer of Pt on Ru nanoparticles through galvanic replacement of Cu adlayers

bull Catalysts on oxide supportsCatalysts on oxide supports (e g(eg NbONbO2 SnOSnO2 MagneacuteliMagneacuteli phases)phases)bull

minus cation-adsorptionreductiongalvanic-displacement method minus significant reduction in Pt loading expected

10

adsorption

Electrochemicalor chemical reductionadsorption

Electrochemicalor chemical reductionadsorption

Electrochemical or chemical reduction

PtRuC (BNL) 033 nmol Pt + 045 nmol Ru

j (m

0

2

4

-04 -02 00 02 04 06 08 10 12C ti d ti d ti l i di l t th d

Immersion in Pt solution

Further Ptdeposition by electrochemical or chemical methodsreplacement

Immersion in Pt solution

Further Pt deposition by electrochemical or chemical methodsreplacementreplacement

Cation-adsorptionreductiongalvanic-displacement method of metal deposition on oxide surfaces EAgAgCl (V)

DOE Kick-off Meeting Washington DC ndash September 28 2010

- deg deg

05 M MeOH in 01 M HClO4

PtRuC (commercial)) 10 nmol Pt + 10 nmol Ru

mA

μg Pt

)

4

6

8

55

DMFC Anode Research Activity

bull DMFC Vth=121 V (at 25degC) fuel specific energy 61 kWhkg

bull CH OH + 2H O rarr CO + 6H+ + 6e- E cong 002 V (at 25 C)CH3OH + 2H2O rarr CO2 + 6H+ + 6e Edeg cong 0 02 V (at 25degC)

bull Reduction of methanol-oxidation overpotential through atomic-level control of PtRu nanoparticle synthesis minus optimal Pt atom ensembles for MeOH adsorption and abstraction of H atomsoptimal Pt-atom ensembles for MeOH adsorption and abstraction of H atoms minus adequate Ru coverage for providing OH and O species for CO oxidation minus submonolayer of Pt on Ru nanoparticles through galvanic replacement of Cu adlayers

bull Catalysts on oxide supportsCatalysts on oxide supports (e g(eg NbONbO2 SnOSnO2 MagneacuteliMagneacuteli phases)phases)bull

minus cation-adsorptionreductiongalvanic-displacement method minus significant reduction in Pt loading expected

10

adsorption

Electrochemicalor chemical reductionadsorption

Electrochemicalor chemical reductionadsorption

Electrochemical or chemical reduction

PtRuC (BNL) 033 nmol Pt + 045 nmol Ru

j (m

0

2

4

-04 -02 00 02 04 06 08 10 12C ti d ti d ti l i di l t th d

Immersion in Pt solution

Further Ptdeposition by electrochemical or chemical methodsreplacement

Immersion in Pt solution

Further Pt deposition by electrochemical or chemical methodsreplacementreplacement

Cation-adsorptionreductiongalvanic-displacement method of metal deposition on oxide surfaces EAgAgCl (V)

DOE Kick-off Meeting Washington DC ndash September 28 2010

0 00

66

DMFC Anode Research Activity

bull New PtRu catalysts for further thrifting of the Pt content minus new formulations minus different supports minus performance referenced to Johnson Mattheyrsquos HiSPECreg 12100 catalyst

0400

HiSPEC6000 - PtRu Black HiSPEC6000 PtRu Black

HiSPEC12100 - PtRuC

Experimental PdRu

Development PtRu Catalyst

150300

0600

0500

20

25

20

W

g Pt

Potte

ntia

lE v

s R

HE

iR fr

ee

0200

5 0000

0 100 200 300 400 500 600 700

Mass ActivityymAmgg-1 Pt or Pd

Anode polarization plots (iR-corrected) with various 0 Gen 1 Gen 2 Gen 3 Gen 4 Gen 5 JMFCrsquos catalysts (10 M MeOH 80degC) Evolution of JMFCrsquos DMFC MEA

10

0100

DOE Kick-off Meeting Washington DC ndash September 28 2010

77

DMFC Anode Research Activity

bull PtSn catalysts minus PtSn catalysts showing lower onset potential for MeOH oxidation than PtRu however

performing below PtRu at high current densities minus model indicating OH formation on PtSn at lower potentials than on PtRu but slow

decrease in CO coverage with potential (PtRu a better catalyst at higher potentials)decrease in CO coverage with potential (PtRu a better catalyst at higher potentials) minus assess scope for exploiting the lower onset potentials of PtSn for methanol oxidation

0 4

05

06

07

0 6

07

08

09

1

erag

e

PtRu OH

01

02

03

04

E V PtRu

PtSn

01

02

03

04

05

06

Frac

tiona

l Cov

e

PtRu CO PtSn OH PtSn CO

0 0 10 20 30 40 50

J mA cm-2

0 0 01 02 03 04 05 06

E V

Anode polarization plots OH and CO coverage modelling

DOE Kick-off Meeting Washington DC ndash September 28 2010

88

DMFC Anode Research Innovative Nanostructures

(A) ECSA loss of PtC (E-TEK) Pt black (E-TEK) and PtNT under cycling from 0 to 13 V (vs RHE) at 50 mVs in Ar-purged 05 M H2SO4 at 60degC 50 mVs scans between (B) ORR polarization plots of PtC Pt black PtNT and PdPtNT in O2-saturated 05 M H2SO4 Inset Mass activity and

SEM image of SEM image of supportlesssupportless Pt nanotubes (Pt nanotubes (PtNTPtNT)) specific activity of PtC Pt lack PtNT and PtPdNT catalysts at 0 85 Vspecific activity of PtC Pt lack PtNT and PtPdNT catalysts at 085 V

bull Supportless Pt nanotubes already synthesized bull Pt nanotubes showing improved cycling durability compared to nanoparticle

catalysts and possibly higher activity bull Approach also applicable to the cathode bull Initial focus on PtRu catalysts

DOE Kick-off Meeting Washington DC ndash September 28 2010

99

DMFC Anode Research Innovative Nanostructures

bull PtRu nanotubes Complete displacement of Ag with Pt Ruminus Complete displacement of Ag with Pt Ru

minus Displacement reactions PtCl62- (aq) + 4 Ag (s) rarr Pt (s) + 2 Cl- (aq) + 4 AgCl (s) Ru3+ (aq) + 3 Cl- (aq) + 3 Ag (s) rarr Ru (s) + 3 AgCl (s)

Silver NW PtRu NT

+ PtCl62- (aq)

+ RuCl3 (aq)

Synthesis of PtRu nanotubes

bull Metal nanotube substrate minus Inexpensive metal source used as template Inexpensive metal source used as template minus Partial displacement of metal with Pt Ru minus Form PtRu alloy on the entire metal nanotube substrate

Silver NW

Metal Fill

Metal NT

+ PtCl62- (aq)

+ RuCl3 (aq)

Metal Fill PtRu Shell

DOE Kick-off Meeting Washington DC ndash September 28 2010

Synthesis of PtRu nanotubes with the aid of a metal nanotube substrate

DMFC Anode Research Durability

bull Limiting Ru crossover as a major cause of DMFC performance loss (mitigation methods to be applied to viable Ru containing anode catalysts developed in the project)methods to be applied to viable Ru-containing anode catalysts developed in the project) minus high temperature cure of anode catalyst minus pre-leach of unstable Ru phase(s) minus use of low permeability membranesuse of low-permeability membranes

minus electrochemical method of limiting ruthenium ndash main focus

09 D

MMFC

Vol

tage

(VV)

Initial After 115 h After 330 h

0 50 100 150 200 250 300 350

08

07

06

0 505

04 02

01

00

Current Density (mAcm2)

Performance of an electrochemically-treated MEA after different times of DMFC operation 80degC

HFR

( Ω c

m2 )

DOE Kick-off Meeting Washington DC ndash September 28 2010 1010

Alternative Fuels Dimethyl Ether and Ethanol

Dimethyl ether bull DME fDME fuell cellll VVth=11 1515 VV ((at 25t 25degdegC)C) ffuell specifiific energy 8 0 kWhk80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull High fuel vapor pressure (59 atm at 25degC) conducive to passive fuel delivery bull Oxidation kinetics strongly dependent on temperature making DME a more attractive

fuel at high temperatures than methanol bull Research

minus enhancement of DME oxidation through acceleration of the dissociative DME adsorption minus effect of Pt-to-Ru ratio on the rate of DME oxidation to CO2 (from 101 to 13) minus the role of a third metal or non-metallic component (eg SnO2)

gono go decision after Q5minus gono-go decision after Q5

Ethanol bull DEFC Vth=115 V (at 25degC) fuel specific energy 80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull Advantages High energy content renewable non-toxic easy to handle and distribute

bull Main challenge Slow incomplete oxidation ndash electrocatalytic scission of the C-C bond very difficult to accomplish at low temperatures

DOE Kick-off Meeting Washington DC ndash September 28 2010 1111

77

DMFC Anode Research Activity

bull PtSn catalysts minus PtSn catalysts showing lower onset potential for MeOH oxidation than PtRu however

performing below PtRu at high current densities minus model indicating OH formation on PtSn at lower potentials than on PtRu but slow

decrease in CO coverage with potential (PtRu a better catalyst at higher potentials)decrease in CO coverage with potential (PtRu a better catalyst at higher potentials) minus assess scope for exploiting the lower onset potentials of PtSn for methanol oxidation

0 4

05

06

07

0 6

07

08

09

1

erag

e

PtRu OH

01

02

03

04

E V PtRu

PtSn

01

02

03

04

05

06

Frac

tiona

l Cov

e

PtRu CO PtSn OH PtSn CO

0 0 10 20 30 40 50

J mA cm-2

0 0 01 02 03 04 05 06

E V

Anode polarization plots OH and CO coverage modelling

DOE Kick-off Meeting Washington DC ndash September 28 2010

88

DMFC Anode Research Innovative Nanostructures

(A) ECSA loss of PtC (E-TEK) Pt black (E-TEK) and PtNT under cycling from 0 to 13 V (vs RHE) at 50 mVs in Ar-purged 05 M H2SO4 at 60degC 50 mVs scans between (B) ORR polarization plots of PtC Pt black PtNT and PdPtNT in O2-saturated 05 M H2SO4 Inset Mass activity and

SEM image of SEM image of supportlesssupportless Pt nanotubes (Pt nanotubes (PtNTPtNT)) specific activity of PtC Pt lack PtNT and PtPdNT catalysts at 0 85 Vspecific activity of PtC Pt lack PtNT and PtPdNT catalysts at 085 V

bull Supportless Pt nanotubes already synthesized bull Pt nanotubes showing improved cycling durability compared to nanoparticle

catalysts and possibly higher activity bull Approach also applicable to the cathode bull Initial focus on PtRu catalysts

DOE Kick-off Meeting Washington DC ndash September 28 2010

99

DMFC Anode Research Innovative Nanostructures

bull PtRu nanotubes Complete displacement of Ag with Pt Ruminus Complete displacement of Ag with Pt Ru

minus Displacement reactions PtCl62- (aq) + 4 Ag (s) rarr Pt (s) + 2 Cl- (aq) + 4 AgCl (s) Ru3+ (aq) + 3 Cl- (aq) + 3 Ag (s) rarr Ru (s) + 3 AgCl (s)

Silver NW PtRu NT

+ PtCl62- (aq)

+ RuCl3 (aq)

Synthesis of PtRu nanotubes

bull Metal nanotube substrate minus Inexpensive metal source used as template Inexpensive metal source used as template minus Partial displacement of metal with Pt Ru minus Form PtRu alloy on the entire metal nanotube substrate

Silver NW

Metal Fill

Metal NT

+ PtCl62- (aq)

+ RuCl3 (aq)

Metal Fill PtRu Shell

DOE Kick-off Meeting Washington DC ndash September 28 2010

Synthesis of PtRu nanotubes with the aid of a metal nanotube substrate

DMFC Anode Research Durability

bull Limiting Ru crossover as a major cause of DMFC performance loss (mitigation methods to be applied to viable Ru containing anode catalysts developed in the project)methods to be applied to viable Ru-containing anode catalysts developed in the project) minus high temperature cure of anode catalyst minus pre-leach of unstable Ru phase(s) minus use of low permeability membranesuse of low-permeability membranes

minus electrochemical method of limiting ruthenium ndash main focus

09 D

MMFC

Vol

tage

(VV)

Initial After 115 h After 330 h

0 50 100 150 200 250 300 350

08

07

06

0 505

04 02

01

00

Current Density (mAcm2)

Performance of an electrochemically-treated MEA after different times of DMFC operation 80degC

HFR

( Ω c

m2 )

DOE Kick-off Meeting Washington DC ndash September 28 2010 1010

Alternative Fuels Dimethyl Ether and Ethanol

Dimethyl ether bull DME fDME fuell cellll VVth=11 1515 VV ((at 25t 25degdegC)C) ffuell specifiific energy 8 0 kWhk80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull High fuel vapor pressure (59 atm at 25degC) conducive to passive fuel delivery bull Oxidation kinetics strongly dependent on temperature making DME a more attractive

fuel at high temperatures than methanol bull Research

minus enhancement of DME oxidation through acceleration of the dissociative DME adsorption minus effect of Pt-to-Ru ratio on the rate of DME oxidation to CO2 (from 101 to 13) minus the role of a third metal or non-metallic component (eg SnO2)

gono go decision after Q5minus gono-go decision after Q5

Ethanol bull DEFC Vth=115 V (at 25degC) fuel specific energy 80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull Advantages High energy content renewable non-toxic easy to handle and distribute

bull Main challenge Slow incomplete oxidation ndash electrocatalytic scission of the C-C bond very difficult to accomplish at low temperatures

DOE Kick-off Meeting Washington DC ndash September 28 2010 1111

88

DMFC Anode Research Innovative Nanostructures

(A) ECSA loss of PtC (E-TEK) Pt black (E-TEK) and PtNT under cycling from 0 to 13 V (vs RHE) at 50 mVs in Ar-purged 05 M H2SO4 at 60degC 50 mVs scans between (B) ORR polarization plots of PtC Pt black PtNT and PdPtNT in O2-saturated 05 M H2SO4 Inset Mass activity and

SEM image of SEM image of supportlesssupportless Pt nanotubes (Pt nanotubes (PtNTPtNT)) specific activity of PtC Pt lack PtNT and PtPdNT catalysts at 0 85 Vspecific activity of PtC Pt lack PtNT and PtPdNT catalysts at 085 V

bull Supportless Pt nanotubes already synthesized bull Pt nanotubes showing improved cycling durability compared to nanoparticle

catalysts and possibly higher activity bull Approach also applicable to the cathode bull Initial focus on PtRu catalysts

DOE Kick-off Meeting Washington DC ndash September 28 2010

99

DMFC Anode Research Innovative Nanostructures

bull PtRu nanotubes Complete displacement of Ag with Pt Ruminus Complete displacement of Ag with Pt Ru

minus Displacement reactions PtCl62- (aq) + 4 Ag (s) rarr Pt (s) + 2 Cl- (aq) + 4 AgCl (s) Ru3+ (aq) + 3 Cl- (aq) + 3 Ag (s) rarr Ru (s) + 3 AgCl (s)

Silver NW PtRu NT

+ PtCl62- (aq)

+ RuCl3 (aq)

Synthesis of PtRu nanotubes

bull Metal nanotube substrate minus Inexpensive metal source used as template Inexpensive metal source used as template minus Partial displacement of metal with Pt Ru minus Form PtRu alloy on the entire metal nanotube substrate

Silver NW

Metal Fill

Metal NT

+ PtCl62- (aq)

+ RuCl3 (aq)

Metal Fill PtRu Shell

DOE Kick-off Meeting Washington DC ndash September 28 2010

Synthesis of PtRu nanotubes with the aid of a metal nanotube substrate

DMFC Anode Research Durability

bull Limiting Ru crossover as a major cause of DMFC performance loss (mitigation methods to be applied to viable Ru containing anode catalysts developed in the project)methods to be applied to viable Ru-containing anode catalysts developed in the project) minus high temperature cure of anode catalyst minus pre-leach of unstable Ru phase(s) minus use of low permeability membranesuse of low-permeability membranes

minus electrochemical method of limiting ruthenium ndash main focus

09 D

MMFC

Vol

tage

(VV)

Initial After 115 h After 330 h

0 50 100 150 200 250 300 350

08

07

06

0 505

04 02

01

00

Current Density (mAcm2)

Performance of an electrochemically-treated MEA after different times of DMFC operation 80degC

HFR

( Ω c

m2 )

DOE Kick-off Meeting Washington DC ndash September 28 2010 1010

Alternative Fuels Dimethyl Ether and Ethanol

Dimethyl ether bull DME fDME fuell cellll VVth=11 1515 VV ((at 25t 25degdegC)C) ffuell specifiific energy 8 0 kWhk80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull High fuel vapor pressure (59 atm at 25degC) conducive to passive fuel delivery bull Oxidation kinetics strongly dependent on temperature making DME a more attractive

fuel at high temperatures than methanol bull Research

minus enhancement of DME oxidation through acceleration of the dissociative DME adsorption minus effect of Pt-to-Ru ratio on the rate of DME oxidation to CO2 (from 101 to 13) minus the role of a third metal or non-metallic component (eg SnO2)

gono go decision after Q5minus gono-go decision after Q5

Ethanol bull DEFC Vth=115 V (at 25degC) fuel specific energy 80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull Advantages High energy content renewable non-toxic easy to handle and distribute

bull Main challenge Slow incomplete oxidation ndash electrocatalytic scission of the C-C bond very difficult to accomplish at low temperatures

DOE Kick-off Meeting Washington DC ndash September 28 2010 1111

99

DMFC Anode Research Innovative Nanostructures

bull PtRu nanotubes Complete displacement of Ag with Pt Ruminus Complete displacement of Ag with Pt Ru

minus Displacement reactions PtCl62- (aq) + 4 Ag (s) rarr Pt (s) + 2 Cl- (aq) + 4 AgCl (s) Ru3+ (aq) + 3 Cl- (aq) + 3 Ag (s) rarr Ru (s) + 3 AgCl (s)

Silver NW PtRu NT

+ PtCl62- (aq)

+ RuCl3 (aq)

Synthesis of PtRu nanotubes

bull Metal nanotube substrate minus Inexpensive metal source used as template Inexpensive metal source used as template minus Partial displacement of metal with Pt Ru minus Form PtRu alloy on the entire metal nanotube substrate

Silver NW

Metal Fill

Metal NT

+ PtCl62- (aq)

+ RuCl3 (aq)

Metal Fill PtRu Shell

DOE Kick-off Meeting Washington DC ndash September 28 2010

Synthesis of PtRu nanotubes with the aid of a metal nanotube substrate

DMFC Anode Research Durability

bull Limiting Ru crossover as a major cause of DMFC performance loss (mitigation methods to be applied to viable Ru containing anode catalysts developed in the project)methods to be applied to viable Ru-containing anode catalysts developed in the project) minus high temperature cure of anode catalyst minus pre-leach of unstable Ru phase(s) minus use of low permeability membranesuse of low-permeability membranes

minus electrochemical method of limiting ruthenium ndash main focus

09 D

MMFC

Vol

tage

(VV)

Initial After 115 h After 330 h

0 50 100 150 200 250 300 350

08

07

06

0 505

04 02

01

00

Current Density (mAcm2)

Performance of an electrochemically-treated MEA after different times of DMFC operation 80degC

HFR

( Ω c

m2 )

DOE Kick-off Meeting Washington DC ndash September 28 2010 1010

Alternative Fuels Dimethyl Ether and Ethanol

Dimethyl ether bull DME fDME fuell cellll VVth=11 1515 VV ((at 25t 25degdegC)C) ffuell specifiific energy 8 0 kWhk80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull High fuel vapor pressure (59 atm at 25degC) conducive to passive fuel delivery bull Oxidation kinetics strongly dependent on temperature making DME a more attractive

fuel at high temperatures than methanol bull Research

minus enhancement of DME oxidation through acceleration of the dissociative DME adsorption minus effect of Pt-to-Ru ratio on the rate of DME oxidation to CO2 (from 101 to 13) minus the role of a third metal or non-metallic component (eg SnO2)

gono go decision after Q5minus gono-go decision after Q5

Ethanol bull DEFC Vth=115 V (at 25degC) fuel specific energy 80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull Advantages High energy content renewable non-toxic easy to handle and distribute

bull Main challenge Slow incomplete oxidation ndash electrocatalytic scission of the C-C bond very difficult to accomplish at low temperatures

DOE Kick-off Meeting Washington DC ndash September 28 2010 1111

DMFC Anode Research Durability

bull Limiting Ru crossover as a major cause of DMFC performance loss (mitigation methods to be applied to viable Ru containing anode catalysts developed in the project)methods to be applied to viable Ru-containing anode catalysts developed in the project) minus high temperature cure of anode catalyst minus pre-leach of unstable Ru phase(s) minus use of low permeability membranesuse of low-permeability membranes

minus electrochemical method of limiting ruthenium ndash main focus

09 D

MMFC

Vol

tage

(VV)

Initial After 115 h After 330 h

0 50 100 150 200 250 300 350

08

07

06

0 505

04 02

01

00

Current Density (mAcm2)

Performance of an electrochemically-treated MEA after different times of DMFC operation 80degC

HFR

( Ω c

m2 )

DOE Kick-off Meeting Washington DC ndash September 28 2010 1010

Alternative Fuels Dimethyl Ether and Ethanol

Dimethyl ether bull DME fDME fuell cellll VVth=11 1515 VV ((at 25t 25degdegC)C) ffuell specifiific energy 8 0 kWhk80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull High fuel vapor pressure (59 atm at 25degC) conducive to passive fuel delivery bull Oxidation kinetics strongly dependent on temperature making DME a more attractive

fuel at high temperatures than methanol bull Research

minus enhancement of DME oxidation through acceleration of the dissociative DME adsorption minus effect of Pt-to-Ru ratio on the rate of DME oxidation to CO2 (from 101 to 13) minus the role of a third metal or non-metallic component (eg SnO2)

gono go decision after Q5minus gono-go decision after Q5

Ethanol bull DEFC Vth=115 V (at 25degC) fuel specific energy 80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull Advantages High energy content renewable non-toxic easy to handle and distribute

bull Main challenge Slow incomplete oxidation ndash electrocatalytic scission of the C-C bond very difficult to accomplish at low temperatures

DOE Kick-off Meeting Washington DC ndash September 28 2010 1111

Alternative Fuels Dimethyl Ether and Ethanol

Dimethyl ether bull DME fDME fuell cellll VVth=11 1515 VV ((at 25t 25degdegC)C) ffuell specifiific energy 8 0 kWhk80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull High fuel vapor pressure (59 atm at 25degC) conducive to passive fuel delivery bull Oxidation kinetics strongly dependent on temperature making DME a more attractive

fuel at high temperatures than methanol bull Research

minus enhancement of DME oxidation through acceleration of the dissociative DME adsorption minus effect of Pt-to-Ru ratio on the rate of DME oxidation to CO2 (from 101 to 13) minus the role of a third metal or non-metallic component (eg SnO2)

gono go decision after Q5minus gono-go decision after Q5

Ethanol bull DEFC Vth=115 V (at 25degC) fuel specific energy 80 kWhkg

bull C2H3OH + 3H2O rarr 2CO2 + 12H+ + 12e- Edeg cong 008 V (at 25degC)

bull Advantages High energy content renewable non-toxic easy to handle and distribute

bull Main challenge Slow incomplete oxidation ndash electrocatalytic scission of the C-C bond very difficult to accomplish at low temperatures

DOE Kick-off Meeting Washington DC ndash September 28 2010 1111

1212

Ethanol Oxidation Scheme amp Catalyst Concept

bull On Pt EtOH oxidation is slow and limited to acetaldehyde at existing catalysts ((followingg the α-C-H bond dissociation)) C2H5OH + Pt(H2O) rarr Pt(CH3CHO) + H2O + 2H+ + 2eshy

C-C bond splitting is difficult

bull Ternary PtRhSnO2 model catalyst capable of oxidizing EtOH to CO2 (at 25degC) minus Pt - abstraction and oxidation of H atoms minus SnO2 - source of OH for oxidation of strongly bound intermediates minus Rh - small amounts placed either on SbO2 or Pt to aid in C-C bond scission

PtPtRhSnO2C

Nanoparticles Rh 2ML SnO2 + 12ML Rh 2ML SnO2 + 1ML Pt

Pt(111) Rh(111) SnO2

Model Catalysts Real Catalyst

DOE Kick-off Meeting Washington DC ndash September 28 2010

- -

1313

Ethanol Improved Synthesis amp Catalyst Composition Optimization

bull A modified polyol method Pt-Rh-SnO nanopaticles H PtCl + RhCl + SnCl + NaOH + EG + H Ominus Pt Rh SnOx nanopaticles H2PtCl6 + RhCl3 + SnCl2+ NaOH + EG + H2O

minus Heat treatment 200ordmC Ar 1 hour

Pt

Rh Heat Treatment

Rh

Sn

SnO2

Pt-Rh-SnPt Rh Sn Pt Rh SnO Pt-Rh-SnOx

bull The effect of catalyst composition ie the PtRhSn ratio

15 08 Pt Rh S 3 1 2PtRhSn = 312 PtRhSn = 313 PtRhSn = 314 PtRhSn = 315 PtRhSn = 316

05M EtOH + 01M HClO4

Room Temperature Room Temperature 10mVs

04

06 045V vs RHE

PtRhSn = 312 PtRhSn = 313 PtRhSn = 314 PtRhSn = 315 PtRhSn = 316

05M EtOH + 01M HClO4

00

02

Room Temperature

0 10 20 30 40 50 60

-2j

Pt

mA

cmm

ug 10

05 -2

j

Pt

mA

cm

ug

00 01 02 03 04 05 06

DOE Kick-off Meeting Washington DC ndash September 28 2010

E V vs RHE Time min

Ethanol Oxidation Performance Ternary Catalyst vs PtC

HR-TEM PtRhSnO2C Room Temperature 60degC

2 525 10P tC ETEK Pt ETEK

20 Pt RhSnO CPtRhSnO C 22 8 05M EtOH + 01M HClO405M EtOH + 01M HClO4

j m

AAc

m-2

E

V v

s R

HE

15 1mVs

E V

vs

RHH

Ej

mAA

cm

-2 1mVs 6

104

05 2

0PtRhSn 314 00 01 02 03 04 05 06 07 01 02 03 04 05 06 07

E V vs RHE E V vs RHE

0606 PtC ETEKPtC Pt RhSnO CPtRhS nO C 20505 2

04

03

04

03

02 02

01 01-4 -3 -2 -1 0 -4 -3 -2 -1 0 1

Log j mA cm-2 Log j mAcm-2

bull ~ 03 V difference observed under voltammetric and steady-state conditions bull At 0 3 V Pt Rh S O C ff i t d f it d t d itAt 03 V Pt-Rh-SnO2C offering a two-order of magnitude current-density

advantage over a standard E-TEKC catalyst

DOE Kick-off Meeting Washington DC ndash September 28 2010 1414

1515

Ethanol Oxidation In situ IRRAS Quantification of Reaction Products

-2

Cha

rgge

Q μm

olc

m

Inte

graat

ed B

and

Inte

nnsity

CO22

CH3COOH

010

008

006

004

0 02 002

000

8

4

01

Pt-Rh-SnOxC

E vs RHE

2400 2000 1600 1200

082V 073V 064V 055V 046V 040V 035V 026V

00

Wavenumber cm-1 100

80

60

40

20

bull Product quantity Product quantity Q = A εQ = Ai εeff

Ai - integrated band intensity Εeff - effective absorption coefficient

bull Charge contribution Ci = 100 (nitimesQi) Σ(nitimesQi) 0 04 06 08 10

DOE Kick-off Meeting Washington DC ndash September 28 2010

E V vs RHE CO2 - 6e-molecule CH3COOH - 4e-molecule

Advanced Membranes for Portable Power Fuel Cells

Issue Objective

Selectivity High proton conductivity but low methanol permeability

Stability Chemicalmechanical stability of DMFCDEFC membranes

MEA processibilityMEA processibility Interfacial stability between membrane and PFSA-bonded electrodesInterfacial stability between membrane and PFSA bonded electrodes

Material Design Options

1616DOE Kick-off Meeting Washington DC ndash September 28 2010

Relative Selectivity of Various Sulfonated PEMs

Proton conductivity (mScm) 6 20 70 90 100 104 105

15 PFSA Partially fluorinated HC-based (random) F ti lFunctional HC-based (cross-linked)

00 01 02 03 04 05 06 07

δ

12

9

6

18λ

Fraction of conducting volume (FCV)

times R

elat

ivee

Sele

ctiv

ityprop conductivi ty 3FCV =

MVCMVC(wet) y

0MVC ndash molar volume per charge

Fraction of Conducting Volume (FCV)a tion of C t Volu e (F V)Fr c onduc ing m C

Functional Polymer moiety resulting in a specific interaction such as hydrogen bonding dipole-dipole or acid-base interactions Examples carboxylic acid group nitirile amide phosphine oxide imidazole

Kim and Pivovar Ann Rev Chem Biomol Eng 1 23-148 2010 Kim et al manuscript in preparation

DOE Kick-off Meeting Washington DC ndash September 28 2010 1717

μ

bull Membrane thickness 50 μm

bull Thickness 30 (supporter) 10 (selectiv la r)

bull Thickness 50 μm including submicron coating layer

Three Approaches to Advanced Membranes

Membrane thickness 50 μm bull Relative selectivity 2‐5 bull Advantage Simple processing bull Major Challenge PEMs with good balance of selectivity

1 Homogeneous thin membrane

(LANL VT) and conductivity

m m e yebull Thickness 30 μm (supporter) 10 μm (selective layer) bull Relative selectivity 5‐10 bull Advantage High selectivity bull Major Challenge Membrane processing

2 Multi‐layer membrane

(LANL) Major Challenge Membrane processing

bull Relative selectivity 2‐5 bull Advantage Good interfacial compatibility amp conductivity Major Challenge S rfa e treatment

3 Surface treated membrane

(VT)

1818DOE Kick-off Meeting Washington DC ndash September 28 2010

bull Major Challenge Surface treatment

ob c u b oc c u b oc

‐

PEM Structures for Homogeneous Thin Membranes

Fl i ti F tiFluorination Functionall group Cross-linking agent KO3SCN

OCF3

S O

m

O C O O O

n OCF3

SO3K

Hydyd oprophobic multi-block Hydrophilic multi-blockyd op

Component Role in PEM

Functional group Increasing selectivity

Fluorination Increasing phase separation and conductivity

Cross‐linking agent Increasing selectivityCross linking agent Increasing selectivity

Multi‐block structure Increasing flexibility phase separation and conductivity

DOE Kick-off Meeting Washington DC ndash September 28 2010 1919

2020

Polymer Processing for Homogeneous Thin Membranes

Block Copolymer Film (BisSF 17k12k) Random Copolymer Film (6F40)

Membranes with uniform thickness in the range 30-200 microm can be provided by Virginia Tech for MEA fabrication

DOE Kick-off Meeting Washington DC ndash September 28 2010

DMFC Performance of MEAs with Homogeneous Thin Membranes

05 M MeOH 20 M MeOH 09 09

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400 500 600

08

07

06

08

07

06

05 05

04 04

03 03

02

01

00

02

01

00

Current density (mAcm2) Current density (mAcm2)

bull PEM performance comparison carried out at a fixed methanol crossover limiting current (50 mAcm2 using 05 M MeOH feed)

bull Performance improvement with hydrocarbon membranes thanks to better selectivitymembranes thanks to better selectivity

Membrane Relative SelectivitySelectivity

M‐SPAEEN‐60 29

BPSH‐35 13

Nafionreg 1

Kim et al J Electrochem Soc 155 B21-B26 2008

Nafionreg 1

DOE Kick-off Meeting Washington DC ndash September 28 2010 2121

Coating layerProt

Anode catalystlayer

cathode catalystlayer

Protonexchangemembrane

ye

Multi-Layer Membranes

Two-Layer System Three-Layer System

Cathode CathodeAnode Anode g y catalyst la r catalystcatalyst catalyst oncatalyst P t Highly layer catal st Highly Proton HighlyProton Highly catalyst

layerlayer selectiveexchange layer selective exchange selective PEMmembrane PEM membrane PEM

Highly selective

Highly selective

Anode CathodePEM

PEMAnode Cathode PEM

PEM

MeOH concentration

profile

Highly selective PEM layers also improving interfacial compatibility

Kim and Pivovar US Patent Application LANL 2006

DOE Kick-off Meeting Washington DC ndash September 28 2010 2222

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

- -

1313

Ethanol Improved Synthesis amp Catalyst Composition Optimization

bull A modified polyol method Pt-Rh-SnO nanopaticles H PtCl + RhCl + SnCl + NaOH + EG + H Ominus Pt Rh SnOx nanopaticles H2PtCl6 + RhCl3 + SnCl2+ NaOH + EG + H2O

minus Heat treatment 200ordmC Ar 1 hour

Pt

Rh Heat Treatment

Rh

Sn

SnO2

Pt-Rh-SnPt Rh Sn Pt Rh SnO Pt-Rh-SnOx

bull The effect of catalyst composition ie the PtRhSn ratio

15 08 Pt Rh S 3 1 2PtRhSn = 312 PtRhSn = 313 PtRhSn = 314 PtRhSn = 315 PtRhSn = 316

05M EtOH + 01M HClO4

Room Temperature Room Temperature 10mVs

04

06 045V vs RHE

PtRhSn = 312 PtRhSn = 313 PtRhSn = 314 PtRhSn = 315 PtRhSn = 316

05M EtOH + 01M HClO4

00

02

Room Temperature

0 10 20 30 40 50 60

-2j

Pt

mA

cmm

ug 10

05 -2

j

Pt

mA

cm

ug

00 01 02 03 04 05 06

DOE Kick-off Meeting Washington DC ndash September 28 2010

E V vs RHE Time min

Ethanol Oxidation Performance Ternary Catalyst vs PtC

HR-TEM PtRhSnO2C Room Temperature 60degC

2 525 10P tC ETEK Pt ETEK

20 Pt RhSnO CPtRhSnO C 22 8 05M EtOH + 01M HClO405M EtOH + 01M HClO4

j m

AAc

m-2

E

V v

s R

HE

15 1mVs

E V

vs

RHH

Ej

mAA

cm

-2 1mVs 6

104

05 2

0PtRhSn 314 00 01 02 03 04 05 06 07 01 02 03 04 05 06 07

E V vs RHE E V vs RHE

0606 PtC ETEKPtC Pt RhSnO CPtRhS nO C 20505 2

04

03

04

03

02 02

01 01-4 -3 -2 -1 0 -4 -3 -2 -1 0 1

Log j mA cm-2 Log j mAcm-2

bull ~ 03 V difference observed under voltammetric and steady-state conditions bull At 0 3 V Pt Rh S O C ff i t d f it d t d itAt 03 V Pt-Rh-SnO2C offering a two-order of magnitude current-density

advantage over a standard E-TEKC catalyst

DOE Kick-off Meeting Washington DC ndash September 28 2010 1414

1515

Ethanol Oxidation In situ IRRAS Quantification of Reaction Products

-2

Cha

rgge

Q μm

olc

m

Inte

graat

ed B

and

Inte

nnsity

CO22

CH3COOH

010

008

006

004

0 02 002

000

8

4

01

Pt-Rh-SnOxC

E vs RHE

2400 2000 1600 1200

082V 073V 064V 055V 046V 040V 035V 026V

00

Wavenumber cm-1 100

80

60

40

20

bull Product quantity Product quantity Q = A εQ = Ai εeff

Ai - integrated band intensity Εeff - effective absorption coefficient

bull Charge contribution Ci = 100 (nitimesQi) Σ(nitimesQi) 0 04 06 08 10

DOE Kick-off Meeting Washington DC ndash September 28 2010

E V vs RHE CO2 - 6e-molecule CH3COOH - 4e-molecule

Advanced Membranes for Portable Power Fuel Cells

Issue Objective

Selectivity High proton conductivity but low methanol permeability

Stability Chemicalmechanical stability of DMFCDEFC membranes

MEA processibilityMEA processibility Interfacial stability between membrane and PFSA-bonded electrodesInterfacial stability between membrane and PFSA bonded electrodes

Material Design Options

1616DOE Kick-off Meeting Washington DC ndash September 28 2010

Relative Selectivity of Various Sulfonated PEMs

Proton conductivity (mScm) 6 20 70 90 100 104 105

15 PFSA Partially fluorinated HC-based (random) F ti lFunctional HC-based (cross-linked)

00 01 02 03 04 05 06 07

δ

12

9

6

18λ

Fraction of conducting volume (FCV)

times R

elat

ivee

Sele

ctiv

ityprop conductivi ty 3FCV =

MVCMVC(wet) y

0MVC ndash molar volume per charge

Fraction of Conducting Volume (FCV)a tion of C t Volu e (F V)Fr c onduc ing m C

Functional Polymer moiety resulting in a specific interaction such as hydrogen bonding dipole-dipole or acid-base interactions Examples carboxylic acid group nitirile amide phosphine oxide imidazole

Kim and Pivovar Ann Rev Chem Biomol Eng 1 23-148 2010 Kim et al manuscript in preparation

DOE Kick-off Meeting Washington DC ndash September 28 2010 1717

μ

bull Membrane thickness 50 μm

bull Thickness 30 (supporter) 10 (selectiv la r)

bull Thickness 50 μm including submicron coating layer

Three Approaches to Advanced Membranes

Membrane thickness 50 μm bull Relative selectivity 2‐5 bull Advantage Simple processing bull Major Challenge PEMs with good balance of selectivity

1 Homogeneous thin membrane

(LANL VT) and conductivity

m m e yebull Thickness 30 μm (supporter) 10 μm (selective layer) bull Relative selectivity 5‐10 bull Advantage High selectivity bull Major Challenge Membrane processing

2 Multi‐layer membrane

(LANL) Major Challenge Membrane processing

bull Relative selectivity 2‐5 bull Advantage Good interfacial compatibility amp conductivity Major Challenge S rfa e treatment

3 Surface treated membrane

(VT)

1818DOE Kick-off Meeting Washington DC ndash September 28 2010

bull Major Challenge Surface treatment

ob c u b oc c u b oc

‐

PEM Structures for Homogeneous Thin Membranes

Fl i ti F tiFluorination Functionall group Cross-linking agent KO3SCN

OCF3

S O

m

O C O O O

n OCF3

SO3K

Hydyd oprophobic multi-block Hydrophilic multi-blockyd op

Component Role in PEM

Functional group Increasing selectivity

Fluorination Increasing phase separation and conductivity

Cross‐linking agent Increasing selectivityCross linking agent Increasing selectivity

Multi‐block structure Increasing flexibility phase separation and conductivity

DOE Kick-off Meeting Washington DC ndash September 28 2010 1919

2020

Polymer Processing for Homogeneous Thin Membranes

Block Copolymer Film (BisSF 17k12k) Random Copolymer Film (6F40)

Membranes with uniform thickness in the range 30-200 microm can be provided by Virginia Tech for MEA fabrication

DOE Kick-off Meeting Washington DC ndash September 28 2010

DMFC Performance of MEAs with Homogeneous Thin Membranes

05 M MeOH 20 M MeOH 09 09

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400 500 600

08

07

06

08

07

06

05 05

04 04

03 03

02

01

00

02

01

00

Current density (mAcm2) Current density (mAcm2)

bull PEM performance comparison carried out at a fixed methanol crossover limiting current (50 mAcm2 using 05 M MeOH feed)

bull Performance improvement with hydrocarbon membranes thanks to better selectivitymembranes thanks to better selectivity

Membrane Relative SelectivitySelectivity

M‐SPAEEN‐60 29

BPSH‐35 13

Nafionreg 1

Kim et al J Electrochem Soc 155 B21-B26 2008

Nafionreg 1

DOE Kick-off Meeting Washington DC ndash September 28 2010 2121

Coating layerProt

Anode catalystlayer

cathode catalystlayer

Protonexchangemembrane

ye

Multi-Layer Membranes

Two-Layer System Three-Layer System

Cathode CathodeAnode Anode g y catalyst la r catalystcatalyst catalyst oncatalyst P t Highly layer catal st Highly Proton HighlyProton Highly catalyst

layerlayer selectiveexchange layer selective exchange selective PEMmembrane PEM membrane PEM

Highly selective

Highly selective

Anode CathodePEM

PEMAnode Cathode PEM

PEM

MeOH concentration

profile

Highly selective PEM layers also improving interfacial compatibility

Kim and Pivovar US Patent Application LANL 2006

DOE Kick-off Meeting Washington DC ndash September 28 2010 2222

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

Ethanol Oxidation Performance Ternary Catalyst vs PtC

HR-TEM PtRhSnO2C Room Temperature 60degC

2 525 10P tC ETEK Pt ETEK

20 Pt RhSnO CPtRhSnO C 22 8 05M EtOH + 01M HClO405M EtOH + 01M HClO4

j m

AAc

m-2

E

V v

s R

HE

15 1mVs

E V

vs

RHH

Ej

mAA

cm

-2 1mVs 6

104

05 2

0PtRhSn 314 00 01 02 03 04 05 06 07 01 02 03 04 05 06 07

E V vs RHE E V vs RHE

0606 PtC ETEKPtC Pt RhSnO CPtRhS nO C 20505 2

04

03

04

03

02 02

01 01-4 -3 -2 -1 0 -4 -3 -2 -1 0 1

Log j mA cm-2 Log j mAcm-2

bull ~ 03 V difference observed under voltammetric and steady-state conditions bull At 0 3 V Pt Rh S O C ff i t d f it d t d itAt 03 V Pt-Rh-SnO2C offering a two-order of magnitude current-density

advantage over a standard E-TEKC catalyst

DOE Kick-off Meeting Washington DC ndash September 28 2010 1414

1515

Ethanol Oxidation In situ IRRAS Quantification of Reaction Products

-2

Cha

rgge

Q μm

olc

m

Inte

graat

ed B

and

Inte

nnsity

CO22

CH3COOH

010

008

006

004

0 02 002

000

8

4

01

Pt-Rh-SnOxC

E vs RHE

2400 2000 1600 1200

082V 073V 064V 055V 046V 040V 035V 026V

00

Wavenumber cm-1 100

80

60

40

20

bull Product quantity Product quantity Q = A εQ = Ai εeff

Ai - integrated band intensity Εeff - effective absorption coefficient

bull Charge contribution Ci = 100 (nitimesQi) Σ(nitimesQi) 0 04 06 08 10

DOE Kick-off Meeting Washington DC ndash September 28 2010

E V vs RHE CO2 - 6e-molecule CH3COOH - 4e-molecule

Advanced Membranes for Portable Power Fuel Cells

Issue Objective

Selectivity High proton conductivity but low methanol permeability

Stability Chemicalmechanical stability of DMFCDEFC membranes

MEA processibilityMEA processibility Interfacial stability between membrane and PFSA-bonded electrodesInterfacial stability between membrane and PFSA bonded electrodes

Material Design Options

1616DOE Kick-off Meeting Washington DC ndash September 28 2010

Relative Selectivity of Various Sulfonated PEMs

Proton conductivity (mScm) 6 20 70 90 100 104 105

15 PFSA Partially fluorinated HC-based (random) F ti lFunctional HC-based (cross-linked)

00 01 02 03 04 05 06 07

δ

12

9

6

18λ

Fraction of conducting volume (FCV)

times R

elat

ivee

Sele

ctiv

ityprop conductivi ty 3FCV =

MVCMVC(wet) y

0MVC ndash molar volume per charge

Fraction of Conducting Volume (FCV)a tion of C t Volu e (F V)Fr c onduc ing m C

Functional Polymer moiety resulting in a specific interaction such as hydrogen bonding dipole-dipole or acid-base interactions Examples carboxylic acid group nitirile amide phosphine oxide imidazole

Kim and Pivovar Ann Rev Chem Biomol Eng 1 23-148 2010 Kim et al manuscript in preparation

DOE Kick-off Meeting Washington DC ndash September 28 2010 1717

μ

bull Membrane thickness 50 μm

bull Thickness 30 (supporter) 10 (selectiv la r)

bull Thickness 50 μm including submicron coating layer

Three Approaches to Advanced Membranes

Membrane thickness 50 μm bull Relative selectivity 2‐5 bull Advantage Simple processing bull Major Challenge PEMs with good balance of selectivity

1 Homogeneous thin membrane

(LANL VT) and conductivity

m m e yebull Thickness 30 μm (supporter) 10 μm (selective layer) bull Relative selectivity 5‐10 bull Advantage High selectivity bull Major Challenge Membrane processing

2 Multi‐layer membrane

(LANL) Major Challenge Membrane processing

bull Relative selectivity 2‐5 bull Advantage Good interfacial compatibility amp conductivity Major Challenge S rfa e treatment

3 Surface treated membrane

(VT)

1818DOE Kick-off Meeting Washington DC ndash September 28 2010

bull Major Challenge Surface treatment

ob c u b oc c u b oc

‐

PEM Structures for Homogeneous Thin Membranes

Fl i ti F tiFluorination Functionall group Cross-linking agent KO3SCN

OCF3

S O

m

O C O O O

n OCF3

SO3K

Hydyd oprophobic multi-block Hydrophilic multi-blockyd op

Component Role in PEM

Functional group Increasing selectivity

Fluorination Increasing phase separation and conductivity

Cross‐linking agent Increasing selectivityCross linking agent Increasing selectivity

Multi‐block structure Increasing flexibility phase separation and conductivity

DOE Kick-off Meeting Washington DC ndash September 28 2010 1919

2020

Polymer Processing for Homogeneous Thin Membranes

Block Copolymer Film (BisSF 17k12k) Random Copolymer Film (6F40)

Membranes with uniform thickness in the range 30-200 microm can be provided by Virginia Tech for MEA fabrication

DOE Kick-off Meeting Washington DC ndash September 28 2010

DMFC Performance of MEAs with Homogeneous Thin Membranes

05 M MeOH 20 M MeOH 09 09

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400 500 600

08

07

06

08

07

06

05 05

04 04

03 03

02

01

00

02

01

00

Current density (mAcm2) Current density (mAcm2)

bull PEM performance comparison carried out at a fixed methanol crossover limiting current (50 mAcm2 using 05 M MeOH feed)

bull Performance improvement with hydrocarbon membranes thanks to better selectivitymembranes thanks to better selectivity

Membrane Relative SelectivitySelectivity

M‐SPAEEN‐60 29

BPSH‐35 13

Nafionreg 1

Kim et al J Electrochem Soc 155 B21-B26 2008

Nafionreg 1

DOE Kick-off Meeting Washington DC ndash September 28 2010 2121

Coating layerProt

Anode catalystlayer

cathode catalystlayer

Protonexchangemembrane

ye

Multi-Layer Membranes

Two-Layer System Three-Layer System

Cathode CathodeAnode Anode g y catalyst la r catalystcatalyst catalyst oncatalyst P t Highly layer catal st Highly Proton HighlyProton Highly catalyst

layerlayer selectiveexchange layer selective exchange selective PEMmembrane PEM membrane PEM

Highly selective

Highly selective

Anode CathodePEM

PEMAnode Cathode PEM

PEM

MeOH concentration

profile

Highly selective PEM layers also improving interfacial compatibility

Kim and Pivovar US Patent Application LANL 2006

DOE Kick-off Meeting Washington DC ndash September 28 2010 2222

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

1515

Ethanol Oxidation In situ IRRAS Quantification of Reaction Products

-2

Cha

rgge

Q μm

olc

m

Inte

graat

ed B

and

Inte

nnsity

CO22

CH3COOH

010

008

006

004

0 02 002

000

8

4

01

Pt-Rh-SnOxC

E vs RHE

2400 2000 1600 1200

082V 073V 064V 055V 046V 040V 035V 026V

00

Wavenumber cm-1 100

80

60

40

20

bull Product quantity Product quantity Q = A εQ = Ai εeff

Ai - integrated band intensity Εeff - effective absorption coefficient

bull Charge contribution Ci = 100 (nitimesQi) Σ(nitimesQi) 0 04 06 08 10

DOE Kick-off Meeting Washington DC ndash September 28 2010

E V vs RHE CO2 - 6e-molecule CH3COOH - 4e-molecule

Advanced Membranes for Portable Power Fuel Cells

Issue Objective

Selectivity High proton conductivity but low methanol permeability

Stability Chemicalmechanical stability of DMFCDEFC membranes

MEA processibilityMEA processibility Interfacial stability between membrane and PFSA-bonded electrodesInterfacial stability between membrane and PFSA bonded electrodes

Material Design Options

1616DOE Kick-off Meeting Washington DC ndash September 28 2010

Relative Selectivity of Various Sulfonated PEMs

Proton conductivity (mScm) 6 20 70 90 100 104 105

15 PFSA Partially fluorinated HC-based (random) F ti lFunctional HC-based (cross-linked)

00 01 02 03 04 05 06 07

δ

12

9

6

18λ

Fraction of conducting volume (FCV)

times R

elat

ivee

Sele

ctiv

ityprop conductivi ty 3FCV =

MVCMVC(wet) y

0MVC ndash molar volume per charge

Fraction of Conducting Volume (FCV)a tion of C t Volu e (F V)Fr c onduc ing m C

Functional Polymer moiety resulting in a specific interaction such as hydrogen bonding dipole-dipole or acid-base interactions Examples carboxylic acid group nitirile amide phosphine oxide imidazole

Kim and Pivovar Ann Rev Chem Biomol Eng 1 23-148 2010 Kim et al manuscript in preparation

DOE Kick-off Meeting Washington DC ndash September 28 2010 1717

μ

bull Membrane thickness 50 μm

bull Thickness 30 (supporter) 10 (selectiv la r)

bull Thickness 50 μm including submicron coating layer

Three Approaches to Advanced Membranes

Membrane thickness 50 μm bull Relative selectivity 2‐5 bull Advantage Simple processing bull Major Challenge PEMs with good balance of selectivity

1 Homogeneous thin membrane

(LANL VT) and conductivity

m m e yebull Thickness 30 μm (supporter) 10 μm (selective layer) bull Relative selectivity 5‐10 bull Advantage High selectivity bull Major Challenge Membrane processing

2 Multi‐layer membrane

(LANL) Major Challenge Membrane processing

bull Relative selectivity 2‐5 bull Advantage Good interfacial compatibility amp conductivity Major Challenge S rfa e treatment

3 Surface treated membrane

(VT)

1818DOE Kick-off Meeting Washington DC ndash September 28 2010

bull Major Challenge Surface treatment

ob c u b oc c u b oc

‐

PEM Structures for Homogeneous Thin Membranes

Fl i ti F tiFluorination Functionall group Cross-linking agent KO3SCN

OCF3

S O

m

O C O O O

n OCF3

SO3K

Hydyd oprophobic multi-block Hydrophilic multi-blockyd op

Component Role in PEM

Functional group Increasing selectivity

Fluorination Increasing phase separation and conductivity

Cross‐linking agent Increasing selectivityCross linking agent Increasing selectivity

Multi‐block structure Increasing flexibility phase separation and conductivity

DOE Kick-off Meeting Washington DC ndash September 28 2010 1919

2020

Polymer Processing for Homogeneous Thin Membranes

Block Copolymer Film (BisSF 17k12k) Random Copolymer Film (6F40)

Membranes with uniform thickness in the range 30-200 microm can be provided by Virginia Tech for MEA fabrication

DOE Kick-off Meeting Washington DC ndash September 28 2010

DMFC Performance of MEAs with Homogeneous Thin Membranes

05 M MeOH 20 M MeOH 09 09

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400 500 600

08

07

06

08

07

06

05 05

04 04

03 03

02

01

00

02

01

00

Current density (mAcm2) Current density (mAcm2)

bull PEM performance comparison carried out at a fixed methanol crossover limiting current (50 mAcm2 using 05 M MeOH feed)

bull Performance improvement with hydrocarbon membranes thanks to better selectivitymembranes thanks to better selectivity

Membrane Relative SelectivitySelectivity

M‐SPAEEN‐60 29

BPSH‐35 13

Nafionreg 1

Kim et al J Electrochem Soc 155 B21-B26 2008

Nafionreg 1

DOE Kick-off Meeting Washington DC ndash September 28 2010 2121

Coating layerProt

Anode catalystlayer

cathode catalystlayer

Protonexchangemembrane

ye

Multi-Layer Membranes

Two-Layer System Three-Layer System

Cathode CathodeAnode Anode g y catalyst la r catalystcatalyst catalyst oncatalyst P t Highly layer catal st Highly Proton HighlyProton Highly catalyst

layerlayer selectiveexchange layer selective exchange selective PEMmembrane PEM membrane PEM

Highly selective

Highly selective

Anode CathodePEM

PEMAnode Cathode PEM

PEM

MeOH concentration

profile

Highly selective PEM layers also improving interfacial compatibility

Kim and Pivovar US Patent Application LANL 2006

DOE Kick-off Meeting Washington DC ndash September 28 2010 2222

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

Advanced Membranes for Portable Power Fuel Cells

Issue Objective

Selectivity High proton conductivity but low methanol permeability

Stability Chemicalmechanical stability of DMFCDEFC membranes

MEA processibilityMEA processibility Interfacial stability between membrane and PFSA-bonded electrodesInterfacial stability between membrane and PFSA bonded electrodes

Material Design Options

1616DOE Kick-off Meeting Washington DC ndash September 28 2010

Relative Selectivity of Various Sulfonated PEMs

Proton conductivity (mScm) 6 20 70 90 100 104 105

15 PFSA Partially fluorinated HC-based (random) F ti lFunctional HC-based (cross-linked)

00 01 02 03 04 05 06 07

δ

12

9

6

18λ

Fraction of conducting volume (FCV)

times R

elat

ivee

Sele

ctiv

ityprop conductivi ty 3FCV =

MVCMVC(wet) y

0MVC ndash molar volume per charge

Fraction of Conducting Volume (FCV)a tion of C t Volu e (F V)Fr c onduc ing m C

Functional Polymer moiety resulting in a specific interaction such as hydrogen bonding dipole-dipole or acid-base interactions Examples carboxylic acid group nitirile amide phosphine oxide imidazole

Kim and Pivovar Ann Rev Chem Biomol Eng 1 23-148 2010 Kim et al manuscript in preparation

DOE Kick-off Meeting Washington DC ndash September 28 2010 1717

μ

bull Membrane thickness 50 μm

bull Thickness 30 (supporter) 10 (selectiv la r)

bull Thickness 50 μm including submicron coating layer

Three Approaches to Advanced Membranes

Membrane thickness 50 μm bull Relative selectivity 2‐5 bull Advantage Simple processing bull Major Challenge PEMs with good balance of selectivity

1 Homogeneous thin membrane

(LANL VT) and conductivity

m m e yebull Thickness 30 μm (supporter) 10 μm (selective layer) bull Relative selectivity 5‐10 bull Advantage High selectivity bull Major Challenge Membrane processing

2 Multi‐layer membrane

(LANL) Major Challenge Membrane processing

bull Relative selectivity 2‐5 bull Advantage Good interfacial compatibility amp conductivity Major Challenge S rfa e treatment

3 Surface treated membrane

(VT)

1818DOE Kick-off Meeting Washington DC ndash September 28 2010

bull Major Challenge Surface treatment

ob c u b oc c u b oc

‐

PEM Structures for Homogeneous Thin Membranes

Fl i ti F tiFluorination Functionall group Cross-linking agent KO3SCN

OCF3

S O

m

O C O O O

n OCF3

SO3K

Hydyd oprophobic multi-block Hydrophilic multi-blockyd op

Component Role in PEM

Functional group Increasing selectivity

Fluorination Increasing phase separation and conductivity

Cross‐linking agent Increasing selectivityCross linking agent Increasing selectivity

Multi‐block structure Increasing flexibility phase separation and conductivity

DOE Kick-off Meeting Washington DC ndash September 28 2010 1919

2020

Polymer Processing for Homogeneous Thin Membranes

Block Copolymer Film (BisSF 17k12k) Random Copolymer Film (6F40)

Membranes with uniform thickness in the range 30-200 microm can be provided by Virginia Tech for MEA fabrication

DOE Kick-off Meeting Washington DC ndash September 28 2010

DMFC Performance of MEAs with Homogeneous Thin Membranes

05 M MeOH 20 M MeOH 09 09

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400 500 600

08

07

06

08

07

06

05 05

04 04

03 03

02

01

00

02

01

00

Current density (mAcm2) Current density (mAcm2)

bull PEM performance comparison carried out at a fixed methanol crossover limiting current (50 mAcm2 using 05 M MeOH feed)

bull Performance improvement with hydrocarbon membranes thanks to better selectivitymembranes thanks to better selectivity

Membrane Relative SelectivitySelectivity

M‐SPAEEN‐60 29

BPSH‐35 13

Nafionreg 1

Kim et al J Electrochem Soc 155 B21-B26 2008

Nafionreg 1

DOE Kick-off Meeting Washington DC ndash September 28 2010 2121

Coating layerProt

Anode catalystlayer

cathode catalystlayer

Protonexchangemembrane

ye

Multi-Layer Membranes

Two-Layer System Three-Layer System

Cathode CathodeAnode Anode g y catalyst la r catalystcatalyst catalyst oncatalyst P t Highly layer catal st Highly Proton HighlyProton Highly catalyst

layerlayer selectiveexchange layer selective exchange selective PEMmembrane PEM membrane PEM

Highly selective

Highly selective

Anode CathodePEM

PEMAnode Cathode PEM

PEM

MeOH concentration

profile

Highly selective PEM layers also improving interfacial compatibility

Kim and Pivovar US Patent Application LANL 2006

DOE Kick-off Meeting Washington DC ndash September 28 2010 2222

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

Relative Selectivity of Various Sulfonated PEMs

Proton conductivity (mScm) 6 20 70 90 100 104 105

15 PFSA Partially fluorinated HC-based (random) F ti lFunctional HC-based (cross-linked)

00 01 02 03 04 05 06 07

δ

12

9

6

18λ

Fraction of conducting volume (FCV)

times R

elat

ivee

Sele

ctiv

ityprop conductivi ty 3FCV =

MVCMVC(wet) y

0MVC ndash molar volume per charge

Fraction of Conducting Volume (FCV)a tion of C t Volu e (F V)Fr c onduc ing m C

Functional Polymer moiety resulting in a specific interaction such as hydrogen bonding dipole-dipole or acid-base interactions Examples carboxylic acid group nitirile amide phosphine oxide imidazole

Kim and Pivovar Ann Rev Chem Biomol Eng 1 23-148 2010 Kim et al manuscript in preparation

DOE Kick-off Meeting Washington DC ndash September 28 2010 1717

μ

bull Membrane thickness 50 μm

bull Thickness 30 (supporter) 10 (selectiv la r)

bull Thickness 50 μm including submicron coating layer

Three Approaches to Advanced Membranes

Membrane thickness 50 μm bull Relative selectivity 2‐5 bull Advantage Simple processing bull Major Challenge PEMs with good balance of selectivity

1 Homogeneous thin membrane

(LANL VT) and conductivity

m m e yebull Thickness 30 μm (supporter) 10 μm (selective layer) bull Relative selectivity 5‐10 bull Advantage High selectivity bull Major Challenge Membrane processing

2 Multi‐layer membrane

(LANL) Major Challenge Membrane processing

bull Relative selectivity 2‐5 bull Advantage Good interfacial compatibility amp conductivity Major Challenge S rfa e treatment

3 Surface treated membrane

(VT)

1818DOE Kick-off Meeting Washington DC ndash September 28 2010

bull Major Challenge Surface treatment

ob c u b oc c u b oc

‐

PEM Structures for Homogeneous Thin Membranes

Fl i ti F tiFluorination Functionall group Cross-linking agent KO3SCN

OCF3

S O

m

O C O O O

n OCF3

SO3K

Hydyd oprophobic multi-block Hydrophilic multi-blockyd op

Component Role in PEM

Functional group Increasing selectivity

Fluorination Increasing phase separation and conductivity

Cross‐linking agent Increasing selectivityCross linking agent Increasing selectivity

Multi‐block structure Increasing flexibility phase separation and conductivity

DOE Kick-off Meeting Washington DC ndash September 28 2010 1919

2020

Polymer Processing for Homogeneous Thin Membranes

Block Copolymer Film (BisSF 17k12k) Random Copolymer Film (6F40)

Membranes with uniform thickness in the range 30-200 microm can be provided by Virginia Tech for MEA fabrication

DOE Kick-off Meeting Washington DC ndash September 28 2010

DMFC Performance of MEAs with Homogeneous Thin Membranes

05 M MeOH 20 M MeOH 09 09

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400 500 600

08

07

06

08

07

06

05 05

04 04

03 03

02

01

00

02

01

00

Current density (mAcm2) Current density (mAcm2)

bull PEM performance comparison carried out at a fixed methanol crossover limiting current (50 mAcm2 using 05 M MeOH feed)

bull Performance improvement with hydrocarbon membranes thanks to better selectivitymembranes thanks to better selectivity

Membrane Relative SelectivitySelectivity

M‐SPAEEN‐60 29

BPSH‐35 13

Nafionreg 1

Kim et al J Electrochem Soc 155 B21-B26 2008

Nafionreg 1

DOE Kick-off Meeting Washington DC ndash September 28 2010 2121

Coating layerProt

Anode catalystlayer

cathode catalystlayer

Protonexchangemembrane

ye

Multi-Layer Membranes

Two-Layer System Three-Layer System

Cathode CathodeAnode Anode g y catalyst la r catalystcatalyst catalyst oncatalyst P t Highly layer catal st Highly Proton HighlyProton Highly catalyst

layerlayer selectiveexchange layer selective exchange selective PEMmembrane PEM membrane PEM

Highly selective

Highly selective

Anode CathodePEM

PEMAnode Cathode PEM

PEM

MeOH concentration

profile

Highly selective PEM layers also improving interfacial compatibility

Kim and Pivovar US Patent Application LANL 2006

DOE Kick-off Meeting Washington DC ndash September 28 2010 2222

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

μ

bull Membrane thickness 50 μm

bull Thickness 30 (supporter) 10 (selectiv la r)

bull Thickness 50 μm including submicron coating layer

Three Approaches to Advanced Membranes

Membrane thickness 50 μm bull Relative selectivity 2‐5 bull Advantage Simple processing bull Major Challenge PEMs with good balance of selectivity

1 Homogeneous thin membrane

(LANL VT) and conductivity

m m e yebull Thickness 30 μm (supporter) 10 μm (selective layer) bull Relative selectivity 5‐10 bull Advantage High selectivity bull Major Challenge Membrane processing

2 Multi‐layer membrane

(LANL) Major Challenge Membrane processing

bull Relative selectivity 2‐5 bull Advantage Good interfacial compatibility amp conductivity Major Challenge S rfa e treatment

3 Surface treated membrane

(VT)

1818DOE Kick-off Meeting Washington DC ndash September 28 2010

bull Major Challenge Surface treatment

ob c u b oc c u b oc

‐

PEM Structures for Homogeneous Thin Membranes

Fl i ti F tiFluorination Functionall group Cross-linking agent KO3SCN

OCF3

S O

m

O C O O O

n OCF3

SO3K

Hydyd oprophobic multi-block Hydrophilic multi-blockyd op

Component Role in PEM

Functional group Increasing selectivity

Fluorination Increasing phase separation and conductivity

Cross‐linking agent Increasing selectivityCross linking agent Increasing selectivity

Multi‐block structure Increasing flexibility phase separation and conductivity

DOE Kick-off Meeting Washington DC ndash September 28 2010 1919

2020

Polymer Processing for Homogeneous Thin Membranes

Block Copolymer Film (BisSF 17k12k) Random Copolymer Film (6F40)

Membranes with uniform thickness in the range 30-200 microm can be provided by Virginia Tech for MEA fabrication

DOE Kick-off Meeting Washington DC ndash September 28 2010

DMFC Performance of MEAs with Homogeneous Thin Membranes

05 M MeOH 20 M MeOH 09 09

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400 500 600

08

07

06

08

07

06

05 05

04 04

03 03

02

01

00

02

01

00

Current density (mAcm2) Current density (mAcm2)

bull PEM performance comparison carried out at a fixed methanol crossover limiting current (50 mAcm2 using 05 M MeOH feed)

bull Performance improvement with hydrocarbon membranes thanks to better selectivitymembranes thanks to better selectivity

Membrane Relative SelectivitySelectivity

M‐SPAEEN‐60 29

BPSH‐35 13

Nafionreg 1

Kim et al J Electrochem Soc 155 B21-B26 2008

Nafionreg 1

DOE Kick-off Meeting Washington DC ndash September 28 2010 2121

Coating layerProt

Anode catalystlayer

cathode catalystlayer

Protonexchangemembrane

ye

Multi-Layer Membranes

Two-Layer System Three-Layer System

Cathode CathodeAnode Anode g y catalyst la r catalystcatalyst catalyst oncatalyst P t Highly layer catal st Highly Proton HighlyProton Highly catalyst

layerlayer selectiveexchange layer selective exchange selective PEMmembrane PEM membrane PEM

Highly selective

Highly selective

Anode CathodePEM

PEMAnode Cathode PEM

PEM

MeOH concentration

profile

Highly selective PEM layers also improving interfacial compatibility

Kim and Pivovar US Patent Application LANL 2006

DOE Kick-off Meeting Washington DC ndash September 28 2010 2222

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

ob c u b oc c u b oc

‐

PEM Structures for Homogeneous Thin Membranes

Fl i ti F tiFluorination Functionall group Cross-linking agent KO3SCN

OCF3

S O

m

O C O O O

n OCF3

SO3K

Hydyd oprophobic multi-block Hydrophilic multi-blockyd op

Component Role in PEM

Functional group Increasing selectivity

Fluorination Increasing phase separation and conductivity

Cross‐linking agent Increasing selectivityCross linking agent Increasing selectivity

Multi‐block structure Increasing flexibility phase separation and conductivity

DOE Kick-off Meeting Washington DC ndash September 28 2010 1919

2020

Polymer Processing for Homogeneous Thin Membranes

Block Copolymer Film (BisSF 17k12k) Random Copolymer Film (6F40)

Membranes with uniform thickness in the range 30-200 microm can be provided by Virginia Tech for MEA fabrication

DOE Kick-off Meeting Washington DC ndash September 28 2010

DMFC Performance of MEAs with Homogeneous Thin Membranes

05 M MeOH 20 M MeOH 09 09

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400 500 600

08

07

06

08

07

06

05 05

04 04

03 03

02

01

00

02

01

00

Current density (mAcm2) Current density (mAcm2)

bull PEM performance comparison carried out at a fixed methanol crossover limiting current (50 mAcm2 using 05 M MeOH feed)

bull Performance improvement with hydrocarbon membranes thanks to better selectivitymembranes thanks to better selectivity

Membrane Relative SelectivitySelectivity

M‐SPAEEN‐60 29

BPSH‐35 13

Nafionreg 1

Kim et al J Electrochem Soc 155 B21-B26 2008

Nafionreg 1

DOE Kick-off Meeting Washington DC ndash September 28 2010 2121

Coating layerProt

Anode catalystlayer

cathode catalystlayer

Protonexchangemembrane

ye

Multi-Layer Membranes

Two-Layer System Three-Layer System

Cathode CathodeAnode Anode g y catalyst la r catalystcatalyst catalyst oncatalyst P t Highly layer catal st Highly Proton HighlyProton Highly catalyst

layerlayer selectiveexchange layer selective exchange selective PEMmembrane PEM membrane PEM

Highly selective

Highly selective

Anode CathodePEM

PEMAnode Cathode PEM

PEM

MeOH concentration

profile

Highly selective PEM layers also improving interfacial compatibility

Kim and Pivovar US Patent Application LANL 2006

DOE Kick-off Meeting Washington DC ndash September 28 2010 2222

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

2020

Polymer Processing for Homogeneous Thin Membranes

Block Copolymer Film (BisSF 17k12k) Random Copolymer Film (6F40)

Membranes with uniform thickness in the range 30-200 microm can be provided by Virginia Tech for MEA fabrication

DOE Kick-off Meeting Washington DC ndash September 28 2010

DMFC Performance of MEAs with Homogeneous Thin Membranes

05 M MeOH 20 M MeOH 09 09

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400 500 600

08

07

06

08

07

06

05 05

04 04

03 03

02

01

00

02

01

00

Current density (mAcm2) Current density (mAcm2)

bull PEM performance comparison carried out at a fixed methanol crossover limiting current (50 mAcm2 using 05 M MeOH feed)

bull Performance improvement with hydrocarbon membranes thanks to better selectivitymembranes thanks to better selectivity

Membrane Relative SelectivitySelectivity

M‐SPAEEN‐60 29

BPSH‐35 13

Nafionreg 1

Kim et al J Electrochem Soc 155 B21-B26 2008

Nafionreg 1

DOE Kick-off Meeting Washington DC ndash September 28 2010 2121

Coating layerProt

Anode catalystlayer

cathode catalystlayer

Protonexchangemembrane

ye

Multi-Layer Membranes

Two-Layer System Three-Layer System

Cathode CathodeAnode Anode g y catalyst la r catalystcatalyst catalyst oncatalyst P t Highly layer catal st Highly Proton HighlyProton Highly catalyst

layerlayer selectiveexchange layer selective exchange selective PEMmembrane PEM membrane PEM

Highly selective

Highly selective

Anode CathodePEM

PEMAnode Cathode PEM

PEM

MeOH concentration

profile

Highly selective PEM layers also improving interfacial compatibility

Kim and Pivovar US Patent Application LANL 2006

DOE Kick-off Meeting Washington DC ndash September 28 2010 2222

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

DMFC Performance of MEAs with Homogeneous Thin Membranes

05 M MeOH 20 M MeOH 09 09

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400

HFR

( Ω c

m2 )

Ceel

l pot

entia

l (VV)

m-SPAEEN-60 (53 μm) BPSH-35 (74 μm) Nafion (250 μm)

0 100 200 300 400 500 600

08

07

06

08

07

06

05 05

04 04

03 03

02

01

00

02

01

00

Current density (mAcm2) Current density (mAcm2)

bull PEM performance comparison carried out at a fixed methanol crossover limiting current (50 mAcm2 using 05 M MeOH feed)

bull Performance improvement with hydrocarbon membranes thanks to better selectivitymembranes thanks to better selectivity

Membrane Relative SelectivitySelectivity

M‐SPAEEN‐60 29

BPSH‐35 13

Nafionreg 1

Kim et al J Electrochem Soc 155 B21-B26 2008

Nafionreg 1

DOE Kick-off Meeting Washington DC ndash September 28 2010 2121

Coating layerProt

Anode catalystlayer

cathode catalystlayer

Protonexchangemembrane

ye

Multi-Layer Membranes

Two-Layer System Three-Layer System

Cathode CathodeAnode Anode g y catalyst la r catalystcatalyst catalyst oncatalyst P t Highly layer catal st Highly Proton HighlyProton Highly catalyst

layerlayer selectiveexchange layer selective exchange selective PEMmembrane PEM membrane PEM

Highly selective

Highly selective

Anode CathodePEM

PEMAnode Cathode PEM

PEM

MeOH concentration

profile

Highly selective PEM layers also improving interfacial compatibility

Kim and Pivovar US Patent Application LANL 2006

DOE Kick-off Meeting Washington DC ndash September 28 2010 2222

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

Coating layerProt

Anode catalystlayer

cathode catalystlayer

Protonexchangemembrane

ye

Multi-Layer Membranes

Two-Layer System Three-Layer System

Cathode CathodeAnode Anode g y catalyst la r catalystcatalyst catalyst oncatalyst P t Highly layer catal st Highly Proton HighlyProton Highly catalyst

layerlayer selectiveexchange layer selective exchange selective PEMmembrane PEM membrane PEM

Highly selective

Highly selective

Anode CathodePEM

PEMAnode Cathode PEM

PEM

MeOH concentration

profile

Highly selective PEM layers also improving interfacial compatibility

Kim and Pivovar US Patent Application LANL 2006

DOE Kick-off Meeting Washington DC ndash September 28 2010 2222

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

Long-Term Stability of MEAs with Different Membranes

Homogenous Thin Membrane Multilayer Membrane

Cur

reent

den

sity

(Ac

m2 )

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

Cur

r eent

den

sity

(Ac

m2 )

025

020020

015015

010010

025

020200

010155

010100010010 010100

005005 000055

6FCN-35 coated BPSH-35

02

01

00 HFFR

(Ohm

cm

2 )

0 250 500 750 1000 1250 1500 1750 2000 0 250 500 750 1000 1250 1500 1750 2000

Time (hour) Time (hour)

Nafionreg 1135 Control PEM Restart test Restart test

025 bull DMFC test conditions 05 V 80degC (a)020 05 M MeOH ambient pressure 015

unrecoverable lossloss No indication of PEM or interface degradationbullbull No indication of PEM or interface degradation010 recoverable loss

Cur

rent

dens

ity (A

cm

2 )

005

02

01

00 0 100 200 300 400 500 600 700

Time (hour)

HFRR

(Ohm

cm2 ) bull Both membrane systems showing superior

performance to the Nafionreg reference system

Kim et al J Electrochem Soc 157 B1602-B1607 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 2323

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

2424

Basic Concepts of Membrane Post-Fluorination

bull No modification Possible poor compatibility with Nafionreg in electrodes No modification Possible poor compatibility with Nafion in electrodes SO3H

OO

OS OOS O 64 O OO O

H3OS

bull Fluorination Phase separation and improved interface with Nafionreg in electrodes

F2 F2

F2

F2

SO3H F F F F O O

OS OOS O 64 O

H OS FF FF FF FF FF FF FF O

H3OS

DOE Kick-off Meeting Washington DC ndash September 28 2010

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

2525

Post-Fluorination of BPSH-40 Membrane

50 nm 50 nm

(a) (b) Tapping mode AFM

(a) SPAES (BPSH 40 control)(a) SPAES (BPSH-40 control) (b) FSPAES ndash 10 minutes (c) FSPAES ndash 30 minutes (d) FSPAES ndash 60 minutes

Relative humidity ~ 35

(c)

50 nm

(d)

50 nm

bull Fluorination developing morphological order on ththe surfface of BPSH-40f BPSH 40 membrane

bull Preliminary data indicating improved DMFC MEA improved DMFC MEA performance at higher current densities

DOE Kick-off Meeting Washington DC ndash September 28 2010

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

Fuel Cell Testing amp Multi-Cell Device

bull Single-cell testing of materials including life-testing for up to 2000 hours (LANL JMFC)

bull Integration of selected materials into 50 cm2

MEA f th fi ll t k (JMFC)MEAs for the five-cell stack (JMFC) bull Integration of MEAs into the stack and stack

testing (SFC Energy) bull Deliverablesbull Deliverables forfor thethe DepartmentDepartment ofof EnergyEnergy

completed by Q16

000777000 141414

707070degC 03degC 03degC 03 MMM CHCHCH 333OHOHOH

erererA

vA

vA

vaaaggg

eee C

elC

elC

ellll V

olVo

lVo

ltttagagag

e (

e (

e (VVV

))) 000666555 121212121212

101010 000666000 26x26x26x

000555555

23x23x23x 20x20x20x 175175175xxx 666

888

000555000 444

000444555 222

000444000 000 000000000 000050505 000111000 000151515 000202020 000222555

CurrenCurrenCurrenttt DenDenDen sssititity (Ay (Ay (A cmcmcm-2-2-2)))

StStStacacac

kkkkkk P PP

ooowwweeerrr

P PPrrro

dododuc

tion

uctio

nuc

tion

(((WWW))))))

Short-stack DMFC stack hardware developed at LANL for militilitary power applilicatitions

DOE Kick-off Meeting Washington DC ndash September 28 2010 2626

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

t t

-

Tasks amp Schedule

bull Task 1 DMFC Anode Research minus 11 Catalysts with Improved Activity and Reduced Cost minus 1 2 A C D bilit12 Anodde Catallyst Durability

bull Task 2 Alternative fuels for portable fuel cells minus 21 Ethanol Oxidation Electrocatalysis minus 22 Dimethyl Ether Research

bullbull Task 3 1Task 31 Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes)Innovative Electrode Structures for Better Activity and Durability (Metal Nanotubes) bull Task 4 Hydrocarbon Membranes for Lower MEA Cost and Enhanced Fuel Cell Performance

minus Block Copolymer Synthesis minus Copolymers with Cross-linkable End-groups

bullbull Task 5Task 5 Characterization performance and durability testing multi-cell deviceCharacterization performance and durability testing multi cell device minus Fuel Cell Testing Performance amp Durability minus Multi-cell Device(Five-Cell Stack)

Task Schedule by Quarters with Milestones (M) and Decision Points (G)

TASK QUARTER

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 11 MM MG MM MG M MG MMM

12 MMG M M

21 MM MMG M M M G M MMG MMM MMG M M M G M MMG M

22 M MG MG

31 MMG MG MMG MG MG MG M

41-42 MMG M MMG M MMG MMG

51 MMMM

52 MM M

Periods after a high-risk gono-go decisions are shown in a lighter shade

DOE Kick-off Meeting Washington DC ndash September 28 2010 2727

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

- - -

Approach FY11 Milestones

Date Milestone

Mar 11 Complete evaluation of at least three PtRu catalysts of different compposition for DME oxidation

Apr 11 Conclude synthesis of trisulfonated hydrophilic (SQS) 6F copolymers

Apr 11 Demonstrate a nanotube catalyst with MeOH oxidation activity within 0 05 V of the state-of-the-art PtRu catalysts005 V of the state of the art PtRu catalysts

June 11 Complete equipment set-up for stack evaluation adapt stack hardware to testing hydrocarbon membranes of different thickness

S 11Sep 11 D t t M OH id ti t l t th t i ifi tl dDemonstrate a new MeOH oxidation catalyst that significantly exceeds half-cell mass activity of 200 mAmgPt at 035 V at 80degC (iR-corrected)

Sep 11 Improve the ternary PtRhSnO2 electrocatalyst to oxidize EtOH to CO2 with an efficiency of 50 at the anode potential of 04 V and 80degC

DOE Kick-off Meeting Washington DC ndash September 28 2010 2828

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

Summary

bull This is a multi-partner and multi-task project targeting substantial improvements to the performance of portable fuel cells with a liquid fuel feed to the anodethe performance of portable fuel cells with a liquid fuel feed to the anode

bull The key technical objective for the direct methanol fuel cell (DMFC) is to assure sustained operation at a cell voltage of 06-07 V (depending on specific application and cost requirements)

bull The focus of the DMFC research is on (i) enhancement of the anode catalyst activity through novel catalyst composition and structure (ii) increase in the membrane selectivity (iii) improvement to the MEA stability including that of the membrane-electrode interface and the catalyst itself and (iv) reduction in the cathode loss caused by migration of unstable anode components (eg Ru crossover)

bull Electrocatalysis of dimethyl ether oxidation is studied in the context of a system with ldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFCldquopassiverdquo fuel supply DME anode performance will be referenced to that of a DMFC anode operating under similar conditions

bull Ethanol research concentrates on the development of mostly ternary oxidation catalysts capable of breaking the C-C bond in the C2H5OH molecule and assuringcatalysts capable of breaking the C C bond in the C2H5OH molecule and assuring high CO2 yields

bull Potentially viable materials developed in the project will be tested for long-term stabilityy in a singgle fuel cell and if jjudgged ppractical incor pporated into a short fuel cell stack

DOE Kick-off Meeting Washington DC ndash September 28 2010 2929

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

Title

3030DOE Kick-off Meeting Washington DC September 28 2010

Supplemental Slides

ndash

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

Interfacial Stability Poor wetting-adhesion water uptake of cathode

water uptake of anodeMEA 6060

50

proton conducting chhannell

HFFR

gai

n (m

Ω c

mm2 ) 40

30

20

10

Water transport mismatch MEMEMEAAA MEMEAA

HH22OO HH OOHH22OO

0 Sulfonated poly(arylene ether)

-10

-20

Nafionreg

Recast Nafionreg

0 20 40 60 80 100 120 140 hihighgh dd rraagg polpolyymmeerr llooww dd rraagg popollyymmeerr

Water uptake (vol )Dimensional mismatch

Dry state

Water uptake lower than 40 vol assuring good stability of the membraneelectrode interface

mechanical stress at th l dthe electtrodeshymembrane interface may lead to delaminationHydrated state

Kim and Pivovar J Electrochem Soc 157 B1616-B1623 (2010)

DOE Kick-off Meeting Washington DC ndash September 28 2010 3131

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

t

λ

onc

P l A hit t

Effect of Chemistry on Membrane Properties

FCV=035

SO H C λ Relative Rel MeOH Polymer Chemistry SO3H Conc (mgramequivcm3)

λ (H2OSO3H)

Relative Conductivity

Rel MeOH Permeability

PFSA 18 165 (18) 085 (018) 096 (006)

P tiPartialllly flfluoriinatedd 19 157 (18) 087 (023) 069 (017)

HC-based 23 141 (25) 086 (024) 038 (013)

Functional 2 5 12 4 (3 1) 0 83 (0 33) 0 24 (0 12)25 124 (31) 083 (033) 024 (012)

FCV=025

SO3H Conc λ Relative Rel MeOH Polymer Architecture 3 (mgramequivcm3) (H2OSO3H) Conductivity Permeability

Random copolymer 16 120 (19) 046 (02) 019 (008)

H l 2 2 87 (15) 0 39 (0 1) 018 (005)Homopolymer 22 8 7 (1 5) 039 (01) 0 18 (0 05)

Cross-linked copolymer 31 56 (17) 066 (02) 010 (004)

Standard deviation given in parenthesisStandard deviation given in parenthesis

DOE Kick-off Meeting Washington DC ndash September 28 2010 3232

Acknowledgments

bull DOE-EERE Fuel Cell Technologies Program

bull T hTechnollogy DDevellopmentt MManager DDr NNancy GGarllandd

DOE Kick-off Meeting Washington DC ndash September 28 2010 3333

• Advanced Materials and Concepts for Portable Power Fuel Cells
• • Overview
  • Relevance Objective amp Targets
  • Approach Focus Areas
  • DMFC Anode Research Activity
  • DMFC Anode Research Innovative Nanostructures
  • DMFC Anode Research Durability
  • Alternative Fuels Dimethyl Ether and Ethanol
  • Ethanol Oxidation Scheme amp Catalyst Concept
  • Ethanol Improved Synthesis amp Catalyst Composition Optimization
  • Ethanol Oxidation Performance Ternary Catalyst vs PtC
  • Ethanol Oxidation In situ IRRAS Quantification of Reaction Products
  • Advanced Membranes for Portable Power Fuel Cells
  • Relative Selectivity of Various Sulfonated PEMs
  • Three Approaches to Advanced Membranes
  • PEM Structures for Homogeneous Thin Membranes
  • Polymer Processing for Homogeneous Thin Membranes
  • DMFC Performance of MEAs with Homogeneous Thin Membranes
  • Multi-Layer Membranes
  • Long-Term Stability of MEAs with Different Membranes
  • Basic Concepts of Membrane Post-Fluorination
  • Post-Fluorination of BPSH-40 Membrane
  • Fuel Cell Testing amp Multi-Cell Device
  • Tasks amp Schedule
  • Approach FY11 Milestones
  • Summary
  • Supplemental Slides
  • • Interfacial Stability
    • Effect of Chemistry on Membrane Properties
    • Acknowledgments