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Outline
Introduction to Ceramatec
Current Applications Advanced materials and high temperature
batteries
Solid Electrolyte electrochemical
systems: Fuel Cells
Summary
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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
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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
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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.
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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
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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
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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
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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
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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
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Goals of Ceramatec
Li/SOCl2
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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
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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
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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.
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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+
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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
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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
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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
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Superactive Products (>100 mA/cm2)
! Strategic Partner Product
!McDermott Tech. SOFC
!APCI Oxygen
Separation
!Various Sodium NaSICON, Nafion
Separation
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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
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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
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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
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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
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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
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Supported LSGM Electrolyte
Process modification to control reactivity
LSGM thickness ~ 30 microns
Cathode
Electrolyte
Anode
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Thin LSGM Performance
Operation 700C possible with thin supported
LSGM: ~ 0.5 ohm.cm2
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Power Density
500 mW/cm2 at 700C
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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