High Temperature Batteries and Fuel Cells

Ceramatec Technology Division

Ashok Joshi Shekar Balagopal Sai Bavaraju

May 2003 NASA/JPL Workshop for Extreme Environment Technologies

Outline Introduction to Ceramatec Current Applications Advanced materials and high temperature batteries Solid Electrolyte electrochemical systems: Fuel Cells Summary

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

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

Battery Research at Ceramatec

1976-1993: Ceramatec was primarily formed to develop high temperature Na-S batteries using -Alumina funded by Ford Motor Company 1987-1992: Worked with SAFT to develop electrolyte for Li batteries 2001 Onwards: Research on ceramic electrolytes for Li batteries.

Current Applications
Solid Electrolyte Devices Passive < 100 A/cm2
Sensors and Analyzers Fluid Delivery Devices

Active >10 mA/cm2

DeOxo Systems Batteries Fluid Delivery
Electrodes

Superactive >100 mA/cm2

Oxygen Separation System Fuel Cells Sodium Separation Devices

Types of Solid Electrolytes

Be ta -A lu Li m Cl in ,K a Cl ,M gO

Na, Li

Na fio n

Beta-Alumina

Ion Conducting Membranes

H
Protonated Nafion, NaSICON PRONAS

Pe La rov G skit all e at s e

m lu I-A Li a in

Li

N CO SI ON Na SIC Li

Zirconia

ria th Ce smu Bi

O d xi e

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

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
Screen Anode Electrolyte Cathode Screen

LiAl + Electrolyte LiI+Al2O3 FeS or FeS2+Electrolyte

5 mil thick LiI+Al2O3

Conductivity of Specific Compositions

10-1

Conductivity (S/cm)

10-2

LiI-Al2O3

10-3

LiI-Al2O3+MgO
10-4

Pure LiI

LiBr-Al2O3

10-5
300oC 250oC 200oC 100oC

1.6

1.8

2.0

2.2

2.4

2.6

2.8

1/T (x10-3 K)

Goals of Ceramatec

Li/SOCl2

What is NaSICON ?
Na = Sodium SI = Super Ionic CON = 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 resistance Thermally stable in corrosive environments 60: 5 x10-2 S/cm; 300 : 10-1 S/cm

Lattice formula: M1M2A2B3O12

Lattice Site NZP Composition

M1

M2

A2VI
VI

B3IV
IV

O12

Na Substitution Type Isovalent Substitutions at M1 (Na) Site Isovalent Substitutions at A2 (Zr) Site
VI

Zr2

P3

O12

Li, Na, K, Rb, Cs Ti, Hf, Ge, Sn Ca, Sr, Ba RE, Ta RE, Ta Na, K Si

Heterovalent Substitutions within M1 and M2 Sites Balanced Substitutions at A2 IV (Zr) and B3 (P) Sites
VI

Balanced Substitutions at M1 VI (Na) and A2 (Sr) Sites Balanced Substitutions at M1 IV (Na) and B3 (P) Sites

Lithium Analogs of NaSICON as Room-Temperature Ionic Conductors

Technical Features 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 to achieve chemical stability and Li-ion conductivity.

Solid electrolytes based on Lithium Titanium Phosphate (LiZr2(PO4)3 (LiZP), for use in high-energy batteries. Nano structured LiSICON, and LiSICON/Polymer composite electrolytes for use in rechargeable Lithium batteries is being developed

Key Benefits (1) Excellent moderate temperature Li ion conductor ( 3x10-3 S/cm at 60 C). (2) Dense, Solid State membrane provides superior stability and offers higher temperature operation (RT-800 C). (3) Operation with Li metal and FeS electrodes. (4) Addition of nano dispersed LiSICON in PEO type polymer, suppresses formation of crystalline phases and also increases the ionic conductivity (5) Membranes at 20 microns thickness fabricated

CONDUCTIVITY OF HLiSICON & GLiSICON IN 1 M

0.1

NASG - LiSICON # 0832 Densiity = 3.54 gms/cc G LiSICON Surface Area = 3.29 cm 2 Thickness = 0.075 cm H regression Surface Porosity = 0.9 % H LiSICON G regression

Proton

NASH - LiSICON # 0831 Densiity = 3.58 gms/cc 2 Surface Area = 3.29 cm Thicknes = 0.10 cm Surface Porosity = 0.7 %

0.01
60 C 50 C 40 C 20 C

0.001

0.0001 0.0029

0.003

0.0031

0.0032 1/T (K-1)

0.0033

0.0034

0.0035

LiSICON Compositions
LiSICON Chemical Formula M3Zr2Si2PO12 (NZP) ( M = Li+, Na+, K+) Belongs to NaSICON family originally developed for Na-S battery applications: 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+

Proprietary InformationCeramatec

Conductivity of NASG membrane determined by Linear Sweep Voltammetry

0.035 0.030
65 oC

Conductivity, S/cm

0.025 0.020
47 oC

57 oC

0.015 0.010 0.005 0.000 0 100 200

22 oC 31 oC

40 oC

300

400

500

600

Current Density, mA/cm2

Chemical Stability of LiSICON series in LiOH at 80 C

6
NASD NASE

5.5 5

NASG

Weight (grams)

4.5 4 3.5 3 2.5 2 0 20 40 60 80 Days Tested 100 120 140 160

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

Superactive Products (>100 mA/cm2)

! Strategic Partner Product ! McDermott Tech. SOFC ! APCI ! Various Oxygen Separation Sodium NaSICON, Nafion Separation

Planar Solid Oxide Fuel Cell

Planar SOFC Planar SOFC Compact, High Power Density
Interconnect Plate

Fuel Flexibility (Hydrogen, NG, Diesel)

ZrO2 Electrolyte

Electrode

Modular, Scalable to Volume Production Stack Development Stage

Interconnect Plate

Direct Conversion of Hydrocarbon Fuels to Electricity

SOFC Endurance Tests

Single cell life > 40,000 hours
0.0 1.0 0.8 Cell Potential, V 1.0 Time, yrs 2.0 3.0 4.0

Stack life > 14,000 hours

Time, Yrs 0.00 1.0 0.8 0.50 1.00 1.50

Voltage/cell, V
Temp: 1000C Fuel: H2 + 3% H2O Load: 200mA/cm2 0 10000 20000 Time, Hrs 30000 40000

0.6 0.4 0.2 0.0

0.6 0.4 0.2 0.0 H2+3%H2O vs Air Temp: 850 - 900C Load: 100 mA/cm2 0 2000 4000 6000 8000 Time, Hrs 10000 12000 14000

Cell and Stack Endurance Demonstrated

Materials set allows long-term operation

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

SOFC - Current Focus Cost Reduction through co-fired cell 0.8 technology 0.7
0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 Cell Voltage, V
Temp: 850C Fuel: H2 + 3% H2O Load: ~200mA/cm Electrolyte Thickness ~180 microns 2

200

400 600 800 1000 1200 Time, Hours

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

SOFC Intermediate temperature Systems

Lower temperature Operation using Lanthanum Gallate Electrolyte
1.2 0.6 1.0
2 cell ASR = 0.6 ohm.cm

0.5 Power Density, W/cm2

Cell Voltage, V

0.8

0.4

0.6

0.3

0.4

0.2

0.2

Temperature 800 C 0.1 H2-3%H2O vs. Air Electrolyte Thickness: 500 microns 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800 0.900 0.0 1.000

Current Density, A/cm2

High performance cells (500 mW/cm2) with 500 micron electrolyte Presently developing anode supported thin electrolyte technology

US-DOE Sponsored SBIR Phase II

Supported LSGM Electrolyte

Cathode Electrolyte Anode

Process modification to control reactivity LSGM thickness ~ 30 microns

Thin LSGM Performance

Operation 700C possible with thin supported LSGM: ~ 0.5 ohm.cm2

Power Density

500 mW/cm2 at 700C

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