ashok hightemp batt fc

7/31/2019 Ashok HighTemp Batt FC

1/29


2/29

Outline

Introduction to Ceramatec

Current Applications Advanced materials and high temperature

batteries

Solid Electrolyte electrochemical

systems: Fuel Cells

Summary


3/29

Introduction Salt Lake City, Utah Based Small Business

Over 25 years of operation 110 Employees

80,000 sq. ft. R&D space

Key Elements of Ceramatec Mission

Solid State Ionic Devices

Advanced Materials Research Electrochemical Technology Development

Device Commercialization

Strategic Partnerships


4/29

Key Business Alliances

Air Products and Chemicals Oxygen generation and purification

Partial oxidation and chemical synthesis

McDermott Int. (SOFCo) Small SOFCs for POU applications

Large SOFCs for low cost power generation

Microlin Controlled, micro release technologies

Batteries


5/29

Battery Research at Ceramatec

1976-1993: Ceramatec was primarily formed todevelop high temperature Na-S batteries using

-Alumina funded by Ford Motor Company

1987-1992: Worked with SAFT to developelectrolyte for Li batteries

2001 Onwards: Research on ceramic

electrolytes for Li batteries.


6/29

Current Applications

Sensors and

Analyzers

Fluid Delivery

Devices

Passive

< 100 A/cm2

Active

>10 mA/cm

2Superactive

>100 mA/cm

2

Solid Electrolyte Devices

DeOxo

Systems

Batteries Fluid Delivery

Oxygen

Separation

System Fuel Cells

Sodium

Separation

DevicesElectrodes


7/29

Types of Solid Electrolytes

Ion ConductingIon Conducting

MembranesMembranes

Li

ONa, Li Zirconia

Perovskites

LaGa

llate

BismuthO

xide

Ceria

LiCl,KC

l,MgO

Beta-Alu

mina

LiI-A

lumina

Beta-Alumina

NaSI

CON

LiSICO

N

Nafio

n

H

Protonated

Nafion, NaSICONPRONAS


8/29

Capability of Solid State Batteries

Using LiI & LiBr based Electrolytes

Operating temperature of LiI based- solid electrolyte: RT to 450o C

100 A/cm2 to 0.5 amps/cm2

Operating temperature of LiBr based- solid electrolyte:

RT to 550o C

1 A/cm2 to 0.5 amps/cm2


9/29

High Temperature Battery Research

Compositions of anode and cathode are adjusted based on

Rechargabality vs Temperature of Operation

Current Density

Energy Density

Co-pressed (100 KPSI) Anode or Cathode supported

Tape laminated structures- repeat unit arrays

LiI+Al2O3LiI+Al2O3

FeS or FeS2+Electrolyte

LiAl + Electrolyte

Screen

Cathode

Electrolyte

Anode

Screen

5 mil thick


10/29

1/T (x10-3 K)

Conductivity

(S/cm)

10-3

10-4

10-5

10-2

10-1

1.8 2.0 2.2 2.4 2.6 2.81.6

200oC250oC300oC 100oC

LiI-Al2O3

Pure LiI LiBr-Al2O3

LiI-Al2O3+MgO

Conductivity of Specific Compositions


11/29

Goals of Ceramatec

Li/SOCl2


12/29

What is NaSICON ?

Na = Sodium

SI = Super IonicCON = Conductors

Family of Sodium Zirconium Phosphate Ceramics

Originally developed for Na-S battery applications Selectively transport Na+, Li+, H+ in three dimensions

in solid state and aqueous complex salts.

Tolerates radioactivity at higher than 10 9 rads

High mechanical strength and thermal shock resistanceThermally stable in corrosive environments

60: 5 x10-2 S/cm; 300 : 10-1 S/cm


13/29


14/29

Lattice Site M1 M2 A2VI

B3IV

O12

NZP Composition

Substitution Type

Na Zr2VI

P3IV

O12

Isovalent Substitutions at M1(Na) Site

Li, Na, K,Rb, Cs

Isovalent Substitutions at A2VI

(Zr) SiteTi, Hf,Ge, Sn

Heterovalent Substitutions withinM1 and M2 Sites

Ca, Sr,Ba

Balanced Substitutions at A2VI

(Zr) and B3IV

(P) SitesRE, Ta

Balanced Substitutions at M1(Na) and A2

VI(Sr) Sites

RE, Ta

Balanced Substitutions at M1(Na) and B3

IV(P) Sites

Na, K Si

Lattice formula: M1M2A2B3O12


15/29

Lithium Analogs of NaSICON as

Room-Temperature Ionic Conductors

Technical Features

Solid electrolytes based on LithiumTitanium Phosphate (LiZr2(PO4)3(LiZP), for use in high-energy batteries.

Nano structured LiSICON, andLiSICON/Polymer compositeelectrolytes for use in rechargeableLithium batteries is being developed

Key Benefits

(1) Excellent moderate temperature Li ionconductor ( 3x10-3 S/cm at 60 C).

(2) Dense, Solid State membrane providessuperior stability and offers highertemperature operation (RT-800 C).

(3) Operation with Li metal and FeSelectrodes.

(4) Addition of nano dispersed LiSICON inPEO type polymer, suppressesformation of crystalline phases and alsoincreases the ionic conductivity

(5) Membranes at 20 microns thicknessfabricated

Proton

CONDUCTIVITY OF HLiSICON & GLiSICON IN 1 M

0.0001

0.001

0.01

0.1

0.0029 0.003 0.0031 0.0032 0.0033 0.0034 0.0035

1/T (K

-1

)

H LiSICON

G LiSICON

H regression

G regression

NASH - LiSICON# 0831Densiity = 3.58 gms/ccSurface Area = 3.29 cm2

Thicknes = 0.10 cmSurface Porosity = 0.7 %

NASG - LiSICON# 0832Densiity = 3.54 gms/ccSurface Area = 3.29 cm2

Thickness = 0.075 cmSurface Porosity = 0.9 %

60 C 50 C 40 C 20 C

Li = Lithium

SI = Super Ionic

CON = Conductors

Family of Sodium Rare Earth Ceramics (NZP)Selectively transports Li+ over other ions They conduct Li-ions in three dimensions Properties can be tailored by ionic substitution toachieve chemical stability and Li-ion conductivity.


16/29

Proprietary InformationCeramatec

LiSICON Compositions

LiSICON Chemical Formula

M3Zr2Si2PO12 (NZP)

( M = Li+, Na+, K+)

Belongs to NaSICON family originally developed for Na-S batteryapplications: Hong et al -1976

Lithium rare-earth silicate has different

structure than NZP

Rare Earth (RE) LiSICON Formula

M5RESi4O12 RE = La, Sm ,Dy, Nd etc.,

M = Li+, Na+, K+


17/29

Conductivity of NASG membrane

determined by Linear Sweep Voltammetry

0.000

0.005

0.010

0.015

0.020

0.025

0.030

0.035

0 100 200 300 400 500 600

Current Density, mA/cm2

C

onductivity,

S/cm

22 oC

31 oC

40 oC

47 oC

57 oC

65 oC


18/29

Chemical Stability of LiSICON

series in LiOH at 80 C

2

2.5

3

3.5

4

4.5

5

5.5

6

0 20 40 60 80 100 120 140 160

Days Tested

Weight(grams)

NASD NASE

NASG


19/29

LiSICON Properties

Ionic substitution flexibility Compositions can be tailored to achieve desired transport

properties

Corner linked Polyhedra provides superior thermal and

corrosion stability Compositions can be tailored to achieve desired transport

properties

Excellent resistance to corrosion and resistance to reactants

at temperatures above 350 C

We currently tape cast structures at 50 microns thickness


20/29

Superactive Products (>100 mA/cm2)

! Strategic Partner Product

!McDermott Tech. SOFC

!APCI Oxygen

Separation

!Various Sodium NaSICON, Nafion

Separation


21/29

Planar Solid Oxide Fuel Cell

Interconnect Plate

Interconnect Plate

ZrO2 Electrolyte

Planar SOFCPlanar SOFC

Electrode

Compact, High Power Density

Fuel Flexibility (Hydrogen, NG,Diesel)

Modular, Scalable to Volume

Production

Stack Development Stage

Direct Conversion ofHydrocarbon Fuels to Electricity


22/29

SOFC Endurance Tests

Cell and Stack Endurance Demonstrated

Materials set allows long-term operation

Stack life > 14,000 hoursSingle cell life > 40,000 hours

0.0

0.2

0.4

0.6

0.8

1.0

CellPot

ential,V

0 10000 20000 30000 40000Time, Hrs

0.0 1.0 2.0 3.0 4.0

Time, yrs

Temp: 1000CFuel: H2 + 3% H2OLoad: 200mA/cm2

0.0

0.2

0.4

0.6

0.8

1.0

Voltage/cell,

V

0 2000 4000 6000 8000 10000 12000 14000

Time, Hrs

H2+3%H2O vs Air

Temp: 850 - 900CLoad: 100 mA/cm2

0.00 0.50 1.00 1.50

Time, Yrs


23/29

Solid Oxide Fuel Cells

Multi-kW class Planar SOFC Pipeline Natural Gas (1993)

1.4 kWe output

POx reformed Diesel (1997) 1.2 kWe output


24/29

SOFC - Current Focus

Cost Reduction through co-fired cell

technology

Stackable 10x10 cm co-fired cells demonstrated Single Cell 1,000 hr. life demonstrated

Co-firing trials with interconnect in progress

US-DOE Sponsored

Strategic Partnership with McDermott Technology, Inc

0.0

0.1

0.2

0.3

0.4

0.5

0.60.7

0.8

C

ellVoltage,

V

0 200 400 600 800 1000 1200

Time, Hours

Temp: 850C

Fuel: H2 + 3% H2O

Load: ~200mA/cm 2

Electrolyte Thickness ~180 microns


25/29

SOFC Intermediate temperature Systems

Lower temperature Operation using Lanthanum Gallate

Electrolyte

High performance cells (500 mW/cm2) with 500 micron electrolyte

Presently developing anode supported thin electrolyte technology

US-DOE Sponsored SBIR Phase II

-

0.2

0.4

0.6

0.8

1.0

1.2

- 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800 0.900 1.000

Current Density, A/cm2

CellVoltage,

V

0.0

0.1

0.2

0.3

0.4

0.5

0.6

PowerDensity,

W/cm2

Temperature 800 C

H2-3%H2O vs. AirElectrolyte Thickness: 500 microns

cell ASR = 0.6 ohm.cm2


26/29

Supported LSGM Electrolyte

Process modification to control reactivity

LSGM thickness ~ 30 microns

Cathode

Electrolyte

Anode


27/29

Thin LSGM Performance

Operation 700C possible with thin supported

LSGM: ~ 0.5 ohm.cm2


28/29

Power Density

500 mW/cm2 at 700C


29/29

Summary

Classification of products based on current density

capabilities

Several products identified in each classification with

market applications

Time to market these products depends on complexity of

technology Passive products have short period while super active

products have very long period

Ceramatec is well positioned to develop & commercialize

several solid electrolyte based products

ashok hightemp batt fc

Documents