R&D of novel power sources: a very good basic science is mandatory for success.

At Bar Ilan University:

Prof. Mikhael Levi

Prof. Gregory Salitra

Prof. Boris Markovsky

Prof. Elena Markevich

Dr. Vali Burgel,

Dr. Ran Elazari

Dr. Ella Zinigrad

At BASF, Germany:

Drs. G. Semrau and M. Schmidt

J. Lampert, A. Garsuch & teams

At GM, USA:

Drs. Bob Powell, Yan Ho, Meng Jiang,

Ion Halalay & teams.

At ETV, Israel

Dr. Arieh Meitav

At Pellion USA

Dr. Robert Doe, Prof. Gerd Ceder & team.

Doron Aurbach

Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel

Support: BSF, BIRD, I-SAEF, 3 Israel-US bi-national science

foundation

GM, BASF, The chief scientist - Israel M. Industry

2 2

2014ד "תשע

To be one of the world’s

leading research and

teaching universities in

Israel and the world,

inspiring academic and

scientific excellence

To be a unique Jewish and

Zionist institution, inspiring

appreciation of cultural,

social and historical

values and commitment to

advancing the State of

Israel

The Primary Challenges

3 3

BlU – Academic Framework

Human

Sciences

4

Strategic shift from Human Sciences to Natural sciences

from 80:20 to 60:40 by 2020

The Faculty of Jewish Studies

The Faculty of Social Sciences

The Faculty of Humanities

The Faculty of

Exact Sciences The Faculty of Engineering

The Faculty of Life Sciences

The Faculty of Law

The Faculty of Medicine in the Galilee

• Largest Faculty in world • 12 Departments • 1,800 Courses • Yiddish/Ladino Center •Basic Jewish Studies Center

• 11 Departments • Interdisciplinary Humanities Program, with emphasis on South/ East Asia

• First place in passing Bar Exam (3 times in 5

• International Programs

• Non-legal Graduate Degrees for Professionals

Natural

Sciences

• 4 Departments • Biophysics Programs

• Established in 2001 • Became Faculty in 2011 • Electrical engineering • computer engineering

• Established on Oct. 2011 Four-year clinical program

• Three year program plan for B.A Graduates

• 13 Departments

• Schools of

Education, Social

Work,

Communication

• 4 Departments

• Bioinformatics

• Optometry

5

Bar-Ilan University – Our Campus

numbers • Geographically situated in central Israel (20 minutes from Tel Aviv and 40 minutes from Jerusalem)

• Two contiguous campuses: historic South Campus and new North Campus (540,000 sq.m)

• Awarded “the Most Beautiful Campus Award”

• 80 Buildings

• Over 300 Laboratories

• 24 Libraries holding more than 1,000,000 titles

6

Bar-Ilan University – Facts & Figures

8 Faculties

52 Departments

69 Research Centers and Institutes

77 Endowed Chairs

6 Regional Colleges

660 Senior faculty

1,101 Junior faculty

1,000 Administrative and technical personnel

10,452 B.A. students

7,599 M.A. Students

1,920 P.HD. Students

111 Post Doctoral Students

123 Medical Students

BINA 2007-2013

“The Leslie and Susan Gonda (Goldschmied) Nanotechnology Triplex”.

The Unique Interdisciplinary Nano Triplex

Center for Scientific Instrumentation The “Aharon & Rachel Dahan Nanotechnology Invariant Zone” contains 1,100 m2 equipment laboratory, designed for vibrational and acoustic isolation

Nano-Fabrication Facility

• FIB - Focused Ion Beam, Helios 600, FEI

• Electron Beam Lithography, CABL-9500C, Crestec

• Evaporation-Sputtering system, Bestec

• ALD - Atomic Layer Deposition, Cambridge

• PLD - Pulse Laser Deposition, Neocera.

• ICP/RIE – Reactive Ion etcher, Plasma-Therm,

VERSALINE

• Wafer Bonder, SUSS

• Thermal Evaporation System, Vinci

• Clean room & Packaging Facilities

BINA 2007-2013 Equipment Infrastructure

Surface Analysis Facility

• AFM – Atomic Force Microscope, Bruker AXS,Veeco, Multi Mode

• AFM – Atomic Force Microscope, Bruker AXS, ICON

• AFM – Atomic Force Microscope, Dimension Fast Scan Bio AFM (High speed imaging), Bruker

• RBS – Rutherford Backscattering Spectrometry, NEC

• XRD – X-Ray Diffraction, Rigaku

BINA 2007-2013 Equipment Infrastructure

Center management: Doron Aurbach, Arie Zaban, (BIU), Emanuel Peled, Dina Golodnitsky (TAU),Yair Ein-Eli (Technion)

BIU Prof. Doron Aurbach Prof. Arie Zaban Dr. Dan Major Dr. David Zitoun Dr. Daniel Nessim Dr. Adi Solomon (new recruit) Dr. Lior Elbaz (new recruit)

Research groups

TAU Prof. Emanuel Peled Prof. Dina Golodnitsky Prof. Yosi Shacham Dr. Amir Natan (new recruit)

TECHNION Prof. Yair Ein-Eli Prof. Yoed Tsur AUC Dr. Alex Schechter

Research Topics • Developing the most advanced research methodologies and analytical techniques. • Advanced cathode materials for high energy density Li ion batteries,. • Li-oxygen and Li-sulfur systems, revisiting Li metal anodes. • Wide potentials liquid and solid electrolyte systems for advanced batteries.. • Graphene and CNT based electrodes for batteries & super-capacitors.. • High capacity Li- Silicon anodes. • Pt free catalysts for fuel cells and metal air batteries. • Combinatorial preparation of catalysts for fuel cells.

INREP כ"מלא

INREP Collaborations

Lead-Acid batteries with 2 types of electrolytes, and addition of CNT to the active materials

Li-O2 Cells with High Surface Carbon

Pristine ASF+ MnO2 catalyst

Discharged in oxygen atmosphere

Charged with fully reversibility

*V. Etacheri, D. Sharon, A. Garsuch, M. Afri, A. Frimer and D. Aurbach, Journal of Materials Chemistry A 2013, 1, 5021-5031

*R. Shapira, G-D. Nessim, T. Zimrin, D. Aurbach, ENERGY & ENVIRONMENTAL SCIENCE 2013, 2, 587-594.

Superb monolithic electrodes for super-capacitors based on nano-MoO3/CNT/activated-carbon matrices: high capacity, high rates and very prolonged cycle life.

Li&Mn rich high capacity Li[MnNiCo]O2 cathodes for EV Li ion batteries

*S. Okashy, M. Noked, T. Zimrin, and D. Aurbach, J. Electrochem. Soc. 2013 volume 160, issue 9,A1489-A1496

*F. Amalraj, M. Talianker, B. Markovsky, D. Sharon, L. Burlaka, E. Zinigrad, O. Haik, D. Aurbach,

J. Lampert, M. Schulz Dobrick, J. Electrochem Soc., 160, A324 (2013).

Rechargeable lithiated silicon-sulfur (SLS) battery prototypes

* R Elazari, G Salitra, G Gershinsky, A. Garsuch, A.Panchenko, D. Aurbach,. Electrochem. Commun. 2012, 14, 21–24.

Sampling the activity of the Electrochemistry/Energy group led by Prof. Doron Aurbach, Chemistry Dpt. ,BIU on Energy storage devices and nano-materials (2013)

Thin film V2O5 and MoO3 cathodes for rechargeable Mg batteries

Aurbach et al. Energy & Environ. Sci. 6, 2265-2297 (2013).

Scope of topics

1. Basic aspects of electrochemistry

a. Solutions thermodynamics.

b. Half cells.

c. Nernst equations.

d. Full galvanic cells.

2. Non-aqueous electrochemistry

a. Ragone plots

b. Types of cells.

c. Solutions characterization.

d. Surface aspects.

e. Interesting electrodes and their response.

g. Analytical aspects, spectroscopy.

h. Technical aspects, transfer methods.

i. Important responses.

Basic thermodynamics:

Chemical potential of charged species:

Breaking the electro-neutrality in the interface

of electrochemical systems, requires additional

potential dependent term in the definition of the

chemical potential of ionic species in solutions.

Now we have electrochemical potential.

eLF

FzeLz iiiii

*

Ionic solutions

essdimensionl -

lnlnln

lnln

1/

ln

1ln

m

RTmRTmRT

aRTaRT

mmma

aRT

m

mRT

iiiii

i

i

Ions activities: no ideal solutions anymore! We

have to define activity via molality times activity

coefficient.

An experimental test of the Debye-Huckel

limiting law. Although there are marked

deviations for moderate ionic strengths,

the limiting slopes as l 0 are in good

agreement with he theory, so the law can

be used for extrapolating data to very low

molalities.

loglog0 RTmRT

The extended Debye-Huckel law gives

agreement with experiment over a

wider range of molalities (as shown

here for a 1,1-electrolyte), but it fails

at higher molalities.

Electrodes in solutions,

types of electrodes

A+BC+D

B D + e-

e- + A C

When a spontaneous reaction takes place in

a galvanic cell, electrons are deposited in one

electrode (the site of oxidation, the anode)

and collected from another (the site of

reduction, the cathode), and so there is a net

flow of current which can be used to do work.

Note that the + sign of the cathode can be

interpreted as indicating the electrode at

which electrons enter the cell, and the - sign

of the anode is where the electrons leave the

cell.

Galvanic cell

In an electrolytic cell, electrons are

forced through the circuit by an

external source. Although the

cathode is still the site of

reduction, it is now the negative

electrode whereas the anode,

the site of oxidation, is positive.

Electrolytic cell

Definition of electrodes and their characteristic in

galvanic and electrolysis cells.

The state of Potential:

Cathode:

Always

reduction

Anode:

Always

oxidation

High

Electron

acceptance

Low

Electron

transfer

Galvanic cell

Low

Electron

transfer.

High

Electron

acceptance

Electrolytic cell

Types of electrode systems = half cells

All unlimited number of possible systems

converge to only 4 prototype cells.

Typical electrode types: (a)

metal/metal ion; (b) metal/insoluble

salt; (c) gas; (d) redox electrodes.

a. Metal / metal ion electrodes

MMMMessM

MMesM

z

FzzF

z

MzeM

z

z

z

z

z

zz

z

M

M

MMMesM

MMMMesM

MMMesMsM

az

azF

RT

zzF

azF

RTz

zF

zzF

log059.0

ln

1

ln1

1

:log ,1e C,0

25

0

0

b. Gas electrodes

GGsG

G

GgG

ssGMMegG

sGMegG

aRT

barP

fRT

FF

a

GeGb

GeGa

PtGG

ln

1ln

2

1

2

1.

2

1.

2

1.

||

2

22

2

2

2

2

2

:iespossibilit two

G

G

G

G

G

G

sGMegG

a

f

F

RT

a

f

F

RT

a

f

F

RT

F

2

1

2

1

2

1

2

2

2

2

ln

ln

ln2

11

c. Metal/insoluble salt electrodes

xxMMxMeMXsM

sxxMMMMeMX

sxMMMeMX

aF

RTa

F

RT

F

FaRTF

XMeMX

XMMX

MeM

AgAgClCl

HgHgClCl

MMXX

lnln1

ln

||

||

||

(calomel)

:examplean

2

d. Redox electrodes

d

Ox

d

Ox

MesdsOx

MesdsOx

sdMesOx

a

a

F

RT

a

a

F

RT

F

F

deOx

Re

Re

Re

Re

Re

ln

ln1

1

Re

Membrane potential

M

M

MM

MM

a

a

F

RT

FF

ln

:mequilibriu

PtAgAgClHClHPt

MMMM

EEE

mP

aqaq

sMsMsMMPtsMMPtlrcell

|,|||,

|||

2

''

,,,,,,

:examplean

''''

A typical cell for measuring a standard

potential consists of a hydrogen

electrode (on the left) and the

electrode for the couple of interest

(on the right).

Two electrodes

One version of the Daniell cell. The

copper electrode is the cathode and

the zinc electrode is the anode.

Electrons leave the cell from the

zinc and enter it again through the

copper electrode.

MaRT ln

The salt bridge, essentially an inverted

U-tube full of concentrated salt

solution in a jelly, has two opposing

liquid junction potentials which

almost cancel.

The electrochemical series of the metals Least strongly reducing

Gold

Platinum

Silver

Mercury

Copper

(Hydrogen)

Lead

Tin

Nickel

Iron

Zinc

Chromium

Aluminium

Magnesium

Sodium

Calcium

Potassium

Most strongly reducing

The dependence of the e.m.f on the concentrations

equationNernst

:cell complete

:reactions half

ln

ln

ln

||||

A

BLR

ALL

BRR

L

R

a

a

F

RTEEEE

aF

RTEE

aF

RTEE

EAeAL

EBeBR

BABA

BAXBXA

BBAA

PbePbL

OHPbeHPbOR

OHPbSOSOHPbOPb

ZneZnL

CueCuR

CuZnSOCuSOZn

2

224

222

.2

2

1

2

1

2

1

2

1

4

2

2

2

2

24422

4

1.

:examples

)(

)(

2

)(

)(

1

)(

)(

2)(

)(

1

21

][

4

][

Reln

Reln

Re

lnRe

ln

ln2

: cell half second

: cell halffirst

equationNernst -

:generalin

2

right

left

right

left

right

left

right

left

Pb

H

LR

d

Ox

F

RT

d

Ox

F

RT

d

Ox

F

RT

d

Ox

F

RTEE

a

a

F

RTEEEE

ba

dc

dc

ba

LR

L

R

BA

DC

nF

RTEE

DC

BA

nF

RTEE

CD

AB

nF

RTE

A

C

nF

RT

D

B

nF

RTEEE

EAneC

EDneB

DCBA

ln

ln

lnlnln

:or

:1than different tscoefficien tricstoichiome

Equilibrium constant:

ERT

FK

aa

aaK

DCBA

KF

RTE

CD

AB

F

RTE

E

BA

DC

ln

ln

ln0

0

:isreaction theif

:mequilibriu

Measuring E and activity coefficients from E

ClH

G

G

atm

aaF

RTAgAgClClEE

a

f

F

RT

XF

RT

EHClHPt

AgAgClCl

ln||

1ln

ln

0||

||

2

1

)1(2

2 :potential G|

2G|Pt:cell half

:potential -

X|MX|M :cell half

:electrodecounter

:sy stem

:examplean

mEERT

F

xAgAgClClEy

mF

RTAgAgClClEm

F

RTE

m

F

RTm

F

RTAgAgClClEE

ln2

ln

||

34.2||ln2

059.0log

lnln||

:tcoefficienactivity gcalculatin

:E gcalculatin

:eelectroly t-1:1 afor

: theoryckeluH Deby e toaccordingmolality offunction are tscoefficienactivity the

2

2

1

2

22

Thermodynamics of electrochemical cells

Calculating G

LiLisLiLivsVE

HOHeOH

LieLi

molekcalGHLiOHOHLi

FEG

KRTG

KF

RTE

vs

//

22

0

22

296500

1000*4*50

2

1

/502

1

ln

ln

:electrode lithium water ofreduction theof potential the

:examplean

FEG

CD

AB

F

RTEE

AB

CDRTGG

m

m

ln

ln

Potentiometric titrations

2

3

23

3

4

34 lnln

10

61.1

771.0

//

143342

34

23

:2

Fe ofion concentrat

Fe

Fe

FeFe

Ce

Ce

CeCe a

a

F

RTE

a

a

F

RTEE

KCeFeCeFe

VECeeCe

VEFeeFe

0 1

:1

ln

1ln

:function

23 /

x

x

x

x

F

RTEE

FeFe

34

34

/

/

4

2

2

ln

324

5.0

: titrationof end

CeCe

CeCe

added

EEfc

f

fcRTEE

Cec

Fef

product Ce

initial Fe

addedCe

EEx

end point

0.8

23 ,FeFeE

1.61

f f

pH and pKa

H

a

MA

H

w

a

H

HA

H

MAHAMAHA

OHAMH

OHHw

HA

AHa

m

K

m

m

K

K

m

mm

mmmm

mmmm

mmKOHOHOH

m

mmKAOHOHHA

11

102

00

00

14

32

32

:balance mass

:balance charge

ion? hydronium theofion concentrat theisWhat

pKapHmm

SAAHA

mS

m

mpKapH

mm

AHA

m

HAmpKa-pH

MAHA

MA

MA

HA

AMAM

:point tricstoichiome thehalfway to pH the

:reached) ispoint tricstoichiome thebefore(but base some ofaddition After the 2.

:acid weak a ofsolution a is analy te the, titration theofstart At the 1.

:base strong with acidweak

'

log

0

0log2

1

2

1

Titration

0

0

OH

OH

OH

OH

B

MA

MA

OHHA

mB

mpKwpH

m

Kwm

mpKw-pKbpH

mS

mpKwpKapH

mm

'

log

)log2

1

2

1

2

1

log2

1

2

1

2

1

3

:point tricstoichiome thepassed wellcarriedbeen has titration When the4.

:acid strong with base(weak

:point tricstoichiome At the 3.

A summary of the regions of the pH

curve of the titration of a weak acid

with a strong base, and the

equations used in different regions.

i = io[exp(()f – exp-(1-f]; f=F/RT

Butler-Volmer equation

io=nFAkoCO(1-)CR

Slow diffusion

Tafel plot

II<< RT/F=25 mV;

i=io [-1+f+1+(1-)f ]=iof

=i/fio

(RT/nfio) =/ i

exp x =1 + x/1! + x2/2! + ….

A scheme of electron transfer

P. Delahay, New Instrumental Methods in Electrochemistry, Interscience Publ., New York, 1954)

• CV using triangular potentials sweeps were developed by Sevcik and Delahay; • Controlled current (measuring voltage) chronopotentiometry and controlled potential (measuring current) chronoamperometry, including short-pulse applications

Bard&Faulkner, Electroanalytical Methods, 2nd ed., p. 435

Sem

i-in

fin

ite

dif

fusi

on

Pb-Acid

Pb-Acid

Spiral Wound

Ni-Cd

Ni-H2

Ni-MH

Li-ion

High Power

Li-Polymer

AgO-Zn

Li-ion

High Energy Fuel

Cell

0 40 20 60 80 100

0 120 140

0 160

0 180

0 200

0 300

0 400

0 500

0 600

0 700

0

1

10

102

103

104

105

Specific Energy, Wh/kg

Sp

ecif

ic P

ow

er,

W/k

g

Ragone Plots of Energy Storage Domains for

Various Electrochemical Energy Conversion Systems

Only Li ion

battery

technology

can do the

work for EV

applications

in the near

future.

A general scheme of a battery

Zinc Deposit at Charged

State Membrane

Mixer Pump runs

at Discharge only

At Charge: Neg. electrode side: Zn2+ +2e Zn0 (Zn plated on neg. electrode)

Pos. electrode side: 2Br Br2 (aq) +2e

(Br2 complexed into a thick oily sludge, is stored in a separate location

inside container)

At Discharge: Neg. electrode side: Zn0 Zn2+ + 2e (Zn ions dissolved in both electrolytes)

Pos. electrode side: Br2 (aq) +2e 2Br (Br ions dissolved in both electrolytes )

Br -

Zn+2,Br -

Ion densities

increase with

Discharge

Zn+2

Br -

Zn+2

Zn+2,Br -

Ion

densities

increase

with

Discharge

Br2 Complex

Decrease

s

with

Discharg

e

A general scheme of flow battery

H2O

H2O

H2 H2

H2

H2

O2

O2

O2

O2

Solid Oxide Fule Cell(SOFC)

Electrical Current

InletHydrogen

InletAir

Outletwaterand

west heatand

ExcessFuel

Anode CathodeElectrolyte

OutletExcess

Air

anode reaction

O2-+H2 H2O+2e-cathode reaction

CO+O2 CO2+2e-

H2O

H2O

H2

H2

H2

H2

O2

O2

O2

O2

Alkaline Fuel Cell(FAC)

Electrical Current

InletHydrogen

InletOxygen

Outletwaterand

west heatAnode Cathode

Electrolyte

cathode reaction

2O2+2H2O+4e- 4OH-anode reaction

2H2+4OH- 4H2O+4e-

H2O

CO2

CO2CO2

H2

H2

H2

H2

O2

O2

O2

O2

Molten Carbonate Fuel Cell(MCFC)

Electrical Current

InletHydrogen

InletAir

Outletwaterand

west heatand

ExcessFuel

Anode CathodeElectrolyte

InletCarbonDioxid

CO2

CO2

CO2

anode reaction

CO32-+H2 H2O+CO2+2e-

cathode reaction

CO2++ O2+2e- 4OH-+CO32-

2

1

H2O

H2O

H2

H2

H2

H2

O2

O2

O2

O2

PEM FUEL CELL(proton exchange membrane)

Electrical Current

InletHydrogen

InletAir

Outletwaterand

west water

Anode CathodeElectrolyte

OutletExcess

Fuel

anode reaction

2H2 4H++4e-cathode reaction

O2+4H++4e- 2H2O

B A

A scheme of dye sensitized solar cell (DSSC)

A general scheme of Li ion battery

EC-DMC/LiPF6 150 Wh/Kg