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Materials Development for
Sodium Metal Halide
Batteries
2009 ASM/TMS Annual Symposium
May 11 & 12, 2009
GE Global Research, Niskayuna, NY
Mohamed Rahmane
Chuck Iacovangelo
Job Rijssenbeek
Mike Vallance
Reza Sarrafi-Nour
GE Global Research
Thanks to the GE Battery team !
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05 11 2009
2009 ASM/TMS Annual symposium
Materials Development for Sodium Metal
Halide Batteries
Outline
Application overview
Comparison with other batteries
Cell chemistry
Cell materials
Modeling
Battery pack materials
Summary
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05 11 2009
2009 ASM/TMS Annual symposium
GE Hybrid Locomotive
Diesel Engine
Grid
Resistors Power
Alternator Electronics
Rectifier 10% Traction 10’s of batteries
Motor
Energy Braking
Storage
90%
Wheels & Rail
Motoring
Benefits
100’s of cells
• 10% fuel savings (32,000 gal/loco/yr)
• 10% emissions reduction
• 1750 HP boost
• 20-year life
• ecomagination
Na-NiCl2 cell
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2009 ASM/TMS Annual symposium
Battery Basics –
Power (W/kg)
Power & Energy Metrics
Energy (Wh/kg)
W/kg
Flow Capability (Power) W/L
Wh/kg $/kW
Wh/L Capacity Capability (Energy)
$/kWh
Li-Ion
Sodium NiMH UltraCap
Lead acid
Power - needed to drive at high speeds…to accelerate and climb grades
Energy - needed to provide range - distance
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2009 ASM/TMS Annual symposium
Batteries by Vehicle Application
Economy Performance PHEV-20 PHEV-40 Performance Economy
HEV’s Plug-in HEV’s EV’s Hybrid Loco
Increase in size of battery (kWh), reducing Power to Energy (P/E) ratio
Peak Power
[kW] 30 50 60 100 90 30 1000
Energy Storage
[kWh] 1.3 2.1 5 14 35 19 750
Pow/Eng
[1/hours] 23 23 12 7 2.6 1.6 1.3
Applicable
Battery Power Dual Energy
Technology
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2009 ASM/TMS Annual symposium
Na-based batteries (Sulfur and metal halide)
Sodium-Sulfur technology Sodium-Metal Halide technology
• Open-circuit voltage: 2.08 V • Open-circuit voltage: 2.58 V
• Temperature range: 310C-350C • Temperature range: 270C-350C
• High vapor pressure of reactants • Lower vap. pressure (< 1 atm up to 800C)
• Severe hardware corrosion by sulfur • Less metal corrosion by halide
• Handling Na in cell assembly • Cell assembly in fully discharged mode
• Violent reaction Na-S in case of solid • Safer reaction Na-NaAlCl4 in case of solid
electrolyte failure electrolyte failure
J.L. Sudworth, A. R. Tilley, Sodium Sulfur Batteries
6
* C.H. Dustmann, J. Power Sources, 127 (2004) p85 05 11 2009
2009 ASM/TMS Annual symposium
Technology areas & challenges for Na-
Metal Halide Batteries
Chemistry Materials Battery pack System Integration
• Cathode chemistry • Beta’’-alumina • Thermal management • Control
• Microstructure • Sealing materials • Vibration hardening • System
• Degradation rate • Joining processes • Packaging materials optimization
• Modeling/diagnostics • Corrosion • FE modeling
Key drivers/tradeoffs: Performance – Reliability - Cost
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2009 ASM/TMS Annual symposium
Na-NiCl2 cell basic chemistry
Cell operating conditions
Current collector (Ni) • Temperature ~ 270C-350C
• Voltage ~ 1.8-3.4V (OCV: 2.58V)
Anode (liquid Na)
• Current ~ 20-100A
Cathode (Ni+NaCl+Additives) • Cell power ~ 100-200W
Liquid electrolyte (NaAlCl4) • Resistance (initial) ~ 7-10mΩ
Beta’’ Alumina Solid Electrolyte (BASE) • Pressure 1-2 bar
Case (mild steel)
charge
e- discharge e-
Charge
Ni + 2NaCl NiCl2 + 2Na+ + 2e- 2Na+ + 2e- + 2Na
Discharge
Ni + 2NaCl NiCl2 + 2Na+ + 2e- 2Na+ + 2e- + 2Na
Cathode Cathode + liquid electrolyte Beta’’ Alumina Solid Anode Anode 8
current electrolyte (BASE) current
05 11 2009
collector collector
2009 ASM/TMS Annual symposium
Na-NiCl2 cell basic structure
Ni-Rings Beta’’-
Seal glass Welds Cell case alumina
Interconnect tube Current
Shims for collector
Na wicking
Cathode
Alumina
collar granules
(metallized)
Beta’’
~ ~
alumina
tube
* After Sudworth et al. 2001
Cell weight distribution
Na CC
anode NaAlCl4
Case electrolyte
Cathode
Current
collector Shims
Seals Cathode
granules
Case
Beta’’ 9
05 11 2009
alumina
* J. L. Sudworth, J. Power Sources, 100, 149 (2001) 2009 ASM/TMS Annual symposium
Na-NiCl2 cell basic operation Cell cycle example
Cell voltage (V) 60 4
T = 300C 3.5
40
3
Ni + 2NaAlCl4 ↔ 2Na + 2AlCl3 + NiCl 2
3.05 20
2.5
Overcharge 2Na + NiCl 2 ↔ 2NaCl + Ni
(Amp)
(Volt)
2.58 0
Current (A)
2
Normal Voltage (V)
1.5
operation -20
3Na + NaAlCl4 ↔ 4 NaCl + Al
1.58 1
-40
0.5
Overdischarge -60 0
0 20 40 60 80 100 120
time (min)
100 0
SOD (%)
Main contributions to cell resistance Cell total resistance
60 60
50 50
40
40 Charge Discharge
30
R (m )
mΩ
30 20
Total
20 Cathode 10
0
10 Beta’’ alumina -10
0 20 40 60 80 100 120
0
time (min)
0 20 40 60 80 100 120 10
05 11 2009
SOC (%) 2009 ASM/TMS Annual symposium
Liquid electrolyte – NaAlCl4
NaAlCl4 ionic conductivity
Requirements 0.9
Conductivity (Ohm.cm)-1
- High conductivity of Na+ 0.8
0.7
- No interaction with Beta’’-alumina 0.6
- Low solubility of cathode materials (NiCl2) 0.5
0.4
0.3
0.2 After Howie et al. 1971**
0.1
0
150 200 250 300 350
T (C)
Solubility of NiCl2 in NaCl-saturated NaAlCl4 melt
After Pelton et al. 2004*
After Prakash et al. 2000***
* C. Robelin et al. J. Chem. Therm. 36, 683 (2004) 11
** Howie et al J. Inorg. Nucl. Chem., 33, 3686 (1971) 05 11 2009
*** J.Prakash et al., J. Electrochem. Soc., 147502 (2000) 2009 ASM/TMS Annual symposium
Cathode chemistry challenges
Discharging Solubility of NiCl2 in NaCl-saturated NaAlCl4
e- melt with additives (J. Prakash et al., 2000*)
NaAlCl Additives
NaAlCl4 + 4, ZnS,
Carbon wick
Current Collector
β”-alumina
Stainless steel casing
NaI, NaF, Al
NiCl2
e- Ni
Cl-
NaCl Na+ Na
Cathode structure - Post cycling (low amount of additives) Cathode structure - Post cycling (additives)
Additives
Lower NiCl2 solubility
High NiCl2 solubility
Smaller NiCl2
Large NiCl2 crystals crystals
Loss of capacity Slower loss of
NaCl capacity
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05 11 2009
* J. Prakash et al., J. Electrochem. Soc., 147 (2000) p502 2009 ASM/TMS Annual symposium
Beta’’ alumina solid electrolyte - composition
Beta’’ phase composition: “Traditional” process
Na2O.(5~7)Al2O3 ~ Na2Al12O19
AlO(OH)
Pre-calcine ( 800C)
“Al2O3” Na2CO3 + LiOH
(86-90%) (9-10%) (0.75%)
Mix & calcine at 1200C
β”-alumina powder
Mill; Press tubes,
Beta’’-alumina sinter at 1600C
β”-alumina dense
(NaAlO2 in grains)
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05 11 2009
R. C. DeVries and W. L. Roth, J. Amer. Ceram. Soc., 52 367 (1969) 2009 ASM/TMS Annual symposium
Beta’’ alumina solid electrolyte - structure
Crystal structure of Na β”- alumina
Key microstructure factors for Na+ conductivity
- Grain size
- Grain orientation
- Density J.L. Sudworth, A. R. Tilley, Sodium Sulfur Batteries
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05 11 2009
2009 ASM/TMS Annual symposium
Beta’’ alumina solid electrolyte - properties
Na+ conductivity of Beta''-alumina vs temperature
Properties T (C)
394 352 315 282 253 227
- Strength: ~ 200-240 MPa 9.6
ln(σ*T) (Ω-1cm-1K)
- Na+ resistivity at 300C ~ 5-6 Ωcm 9.4
- Density ~ 3.2 g/cm3 9.2
9.0
- CTE ~ 7x10-6 K-1
8.8
- Young modulus: 210GPa 8.6
- Poisson ratio: 0.25 8.4
1.5 1.6 1.7 1.8 1.9 2.0
1000/T (1/K)
Key factors affecting performance Strength of Beta''-alumina vs temperature
- Composition
- Microstructure
- Impurities (CaO, SiO2, …)
- Storage/handling environment (moisture)
- Wetting/Surface finish
- Acidic melt (cathode) After T. Makino et al. 2004*
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* T. Makino et al., J. Ceram. Soc., Japan 112 287 (2004) 05 11 2009
2009 ASM/TMS Annual symposium
Beta’’ alumina solid electrolyte – Design
After J. Sudworth (2001)
Design considerations
Performance, reliability and cost
Performance (power)
- Na+ conductivity (increase Na+ flux)
- Shape (Increase surface area while
maintaining minimum required tube
strength) Increased surface area Increased power density
Reliability
Beta’’-
- Strength (Material & shape) alumina
- Cell assembly (Residual stress from tube
sealing process)
- Pressure cycling during cell operation
- Current density
Stress distribution under pressure 16
05 11 2009
J. Sudworth, J. Power Sources,, 100 (2001) p 149 2009 ASM/TMS Annual symposium
Sealing materials & processes
Cell assembly steps Thermal
Welds compression
α-alumina collar Ni rings bond (TCB)
metallization
Thermal Seal glass
compression bond
Alumina-Ni
BASE
Seal α-alumina- (β’’-alumina)
β’’-alumina
Weld subassembly Cell case
to case
α-alumina Current collector
Assembly to cell fill
and final weld
Bonds strength of all joints and
resistance to cell chemical fill are most critical 17
05 11 2009
2009 ASM/TMS Annual symposium
Seal glass
Requirements
- Chemical resistance to Na and halide melt
- No interaction with Beta’’-alumina (ion
exchange)
- High bond strength Alpha-alumina
- CTE close to β’’ and α-ceramics
- Hermiticity
- Low process temperature (800-1050C) Seal
Beta’’-
Technology areas alumina
Na
- Material composition
- Corrosion mechanism in Na and halide melt Halide
- Characterization (Properties & Bonding)
- Sealing process
Sodium-sulfur batteries (GE) Sodium-Metal Halide batteries
- Aluminoborate glasses (GE 2093) Improved properties for compatibility
- Borosilicate glasses (GE 2112) with cell chemistry
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05 11 2009
2009 ASM/TMS Annual symposium
Thermal compression bond Ceramic
metallization
Requirements
- Chemical resistance to Na and halide
- High bonding strength
- CTE close to α-alumina
- Hermiticity
Thermal
Technology areas Compression
- Metallization material composition Bond
- Sintering and TCB processes
- Characterization (Properties & Bonding)
- Corrosion mechanism in Na and halide
Ni
Metallization layer
Ni
Alpha-alumina
Alpha-alumina 19
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2009 ASM/TMS Annual symposium
Materials interaction with cell chemistry
Pristine seal sample After 1 week at 425 C
Challenge
Ability to predict material life in cell
environment without testing the cell for years
Accelerated life test In Liquid Na In Liquid halide
- Accelerate corrosion by increasing
After 1 week in liq Na at 425c
temperature and/or using liquid phase vs
vapor without introducing “un-real” failure
mechanisms ~ 20 microns
- Establish stress-life curves through test data
- Estimate material life & degradation rate
Thermodynamic modeling
- Proven to be effective in several materials
applications where thermochemical data are
available
- Very limited data for Sodium-Metal Halide
battery materials and chemistry !
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05 11 2009
2009 ASM/TMS Annual symposium
Advanced modeling
Electrochemical Thermal Mechanical
Beginning of cycle End of cycle
b
0.007
Temperature profile for charge cycle
0.006 Na / FeCl₂ Model 360
Cell Resistance (Ω-m)
0.005
Na / NiCl₂ Experiment
350
0.004 340
T (C)
0.003 330
0.002 320
0.001 310
0.000
300
0.0 0.2 0.4 0.6 0.8 1.0 0 10 20 30 40 50
DoD
time (min)
Current density & cell Cell temperature vs time Stress distribution from cell
resistance vs SOD and cycling conditions assembly and operation11 2009
05
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2009 ASM/TMS Annual symposium
Battery materials & packaging
Requirements
- Light weight
- Small size (compact)
- Mechanical robustness
(vibration)
- Thermal control (~300C)
Technology needed
- Thermal management
(cooling & heating)
- High-temperature insulation
materials (electrical & thermal)
- Vibration hardening
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05 11 2009
C.H. Dustmann, J. Power Sources,, 127 (20041) p.85
2009 ASM/TMS Annual symposium
Summary
Na-Metal Halide Batteries are demonstrated to be suitable
for a wide spectrum of energy applications (Transportation,
Power infrastructure, …)
Maturing technology for high energy density….More
research needed to improve power density
Remaining technology challenges
Chemistry: Quantitative understanding of the chemical and
electrochemical behavior of the positive electrode under cycling
(electrochemistry+material science)
Materials
- Electrolyte with increased conductivity, strength & stability
- Seals that are compatible with cell chemistry
- Fundamental data (e.g. thermodynamic) for cathode chemistry and
materials compatibility
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05 11 2009
2009 ASM/TMS Annual symposium
Acknowledgments
Thanks to the GE Battery team !
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