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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 !
                                                                                   1
                                                                          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
                                                                                                                                                                                          12
                                                                                                                                                                                  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)
                                                                                                                        13
                                                                                                                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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                                                                           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*


                                                                                                                                            15
                       * 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
                                                                                         18
                                                                                 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
                                                                     05 11 2009
                                              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 !
                                                                                                           20
                                                                                                   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
                                                                                                                                                                 21

                                                                                                                                       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


                                                                                             22
                                                                                     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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