Na-MCl 2 CELL MULTIPHYSICS MODELING: STATUS AND CHALLENGES

Transcription

1 Rémy Christin*, Mikael Cugnet**, Nicola Zanon***, Giorgio Crugnola***, Pascal Mailley**** Na-MCl 2 CELL MULTIPHYSICS MODELING: STATUS AND CHALLENGES *R&D Batteries- Sodium-Nickel and new tech, FIAMM (Aubergenville, France) **Laboratory for Electrochemical Storage, CEA (Le Bourget-Du-Lac, France) ***R&D Batteries- Sodium-Nickel and new tech, FIAMM (Montecchio, Italy) ****Laboratory of Chemistry for Materials and Interfaces, CEA (Grenoble, France)

2 Na-MCl 2 TECHNOLOGY (300 C) Design and active materials Clover-shaped beta alumina beta alumina felt 3.5 cm x 3.5 cm steel casing Ni current collector Mixed Ni/Fe cell 23.5 cm NaCl solid (100% of SOC) Ni solid (80% of SOC + 70% excess) Fe solid (20% of SOC) Additives Secondary liquid electrolyte NaAlCl 4 Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 2

3 Na-MCl 2 TECHNOLOGY (300 C) Design and active materials Clover-shaped beta alumina Discharge scheme negative: 2Na 2Na + + 2e - beta alumina felt 3.5 cm x 3.5 cm steel casing Ni current collector Mixed Ni/Fe cell 23.5 cm NaCl solid (100% of SOC) Ni solid (80% of SOC + 70% excess) Fe solid (20% of SOC) Additives Secondary liquid electrolyte NaAlCl 4 positive: MCl 2 + 2Na + + 2e - M + 2NaCl MCl 2(s) + 2Na (l) M (s) + 2NaCl (s) M = Ni then Fe Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 3

4 FIAMM MIXED 40 Ah CELL Experimenal 40 Ah discharges from 270 C for validation Oven settings: temperature changes emanate only from the cell (increases during discharge) «Ni» plateau (Ni 1-x Fe x Cl 2 ) * Fe plateau *a fluorinated additive contributes for 2 Ah between Ni and Fe plateaus Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 4

5 FIAMM MIXED 40 Ah CELL Experimenal 40 Ah discharges from 270 C for validation Oven settings: temperature changes emanate only from the cell (increases during discharge) «Ni» plateau (Ni 1-x Fe x Cl 2 ) * Fe plateau *a fluorinated additive contributes for 2 Ah between Ni and Fe plateaus Simultaneous contribution of Ni & Fe Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 5

6 2D MODEL IMPLEMENTATION Geometry, Meshing and Governing Equations (from seminal paper) Casing domain Ohm s law in metal (Φ 1 ) Origin of potential (Φ 1 = 0V) Anodic domain Ohm s law in metal (Φ 1 ) Linearized Butler-Volmer on beta alumina external surface (i N ) Solid electrolyte domain Ohm s law in electrolyte (Φ 2 ) Current collector Ohm s law in metal (Φ 1 ) Applied current (I exp ) on collector surface Cathodic region and felt Ohm s law in NaAlCl 4 (Φ 2 ) Ohm s law in metal backbone and carbon (Φ 1 ) Electrochemical reactions (j i ) Porosity, volume fractions, exchange current densities ϵ = 1 ϵ M ϵ MCl2 ϵ NaCl ϵ M/MCl2 Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 6 t j M and ϵ NaCl t j = j Ni + j Fe j

7 THERMAL IMPLEMENTATION From Li-ion cells studies 1,2, distributed heat sources flux can be expressed as: Q irrev = j i η i + σ( φ 1 ) 2 + κ( φ 2 ) 2 i = Ni or Fe Q rev = j i T OCV cell,i T overpotentials in positive electrode electronic ohmic losses in all cell ionic ohmic losses in BASE and positive electrode entropic term from experimental Measurements Q = f(variables of the electrochemical model), Variables of the electrochemical model = f(t) fully coupled model 1 Srinivasan V, Wang CY, J Electrochem Soc 150, Somasundaram K, Birgersson E, Mujumdar AS, J Power Sources 203, 2012 Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 7

8 BASELINE SIMULATION 40 Ah discharge at C/5, T initial = 270 C Cell Voltage Surface temperature The model is validated for this cell voltage and cell surface temperature simulation (relative error < 2 % Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 8

9 BASELINE SIMULATION 40 Ah discharge at C/5, T initial = 270 C Volume fractions of active materials with time At beta alumina interface Fe contributes only if U cell < OCV Fe (T) NaCl produced Results at end of discharge are very closed to expected values from initial weights a diffuse reaction front moves from the beta alumina towards the central collector Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 9

10 INFLUENCE OF THE THICKNESS OF THE SOLID ELECTROLYTE 40 Ah discharge at C/5, T initial = 270 C Cell Voltage Only the thickness of the beta alumina has been changed between simulations 1.0 mm 1.5 mm As expected, the model predicts less overall polarization with a thinner solid electrolyte Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 10

11 THANK YOU FOR YOUR ATTENTION Alternative Energies and Atomic Energy Commission INES RDI Savoie Technolac BP avenue du Lac Léman F Le Bourget-du-Lac - FRANCE T. +33 (0) rémy.cristin@cea.fr Technological Research Division Solar Technologies Department Laboratory LSE Public establishment with commercial and industrial character RCS Paris B

12 INFLUENCE OF THE RATE 40 Ah discharge at C/2 and C/10 from 270 C Cell Voltage Only the I exp parameter has been changed from the reference simulation C /2 C/10 The model is validated from C/10 to C/2 (error < 2%) Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 12

13 FIAMM ML3X GENERIC 40 Ah CELL C/2 40 Ah discharges from different initial temperatures For experimental data, furnace is supplied by constant power, hence temperature changes emanate from the cell (increase during discharge) polarization if temperature Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 13

14 INFLUENCE OF THE INITIAL TEMPERATURE 40 Ah discharges at different temperatures Cell Voltage Only the T parameter has been changed from the related simulation 300 C C/5 simulated discharges C/5 experimental discharges singular thermal effect during transition between active material plateaus The model is validated in terms of operational temperature. Temperature does not have a significant effect on the voltage curves Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 14

15 PREVIOUS WORKS Eroglu & West* (small modifications, isothermal) Discharge MCl 2 + 2e M + 2Cl Electrochemical process involving a soluble metal complex r = [MX 4 ] 2- involved in two mass transfers j = exp α a F RT η 1 i 0 a m nfc r,e k m a m Bulk: X = Cl or AlCl 4 c [MX4] 2 = c r,e = K sp,mcl2 Rate determining step c r,b c r,e exp α c F RT η exp α c F RT η c r,b k m k s c r,s MCl 2 c r,e NaCl M *D. Eroglu and A. C. West, Journal of Power Sources, vol. 203, pp , Apr Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 15

16 PREVIOUS WORKS Orchard and Weaving implementation results Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 16

17 FIAMM MIXED 40 Ah CELL 40 Ah discharges from 270 C For experimental data, furnace is supplied by constant power, hence temperature changes emanate from the cell (increase during discharge) polarization if temperature Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 17

18 PREVIOUS WORKS Orchard & Weaving* (important model simplifications) Discharge MCl 2(s) + 2e + 2Na + M (s) + 2NaCl (s) Solid state process, eventual solubilities not taken into account (no mass transfer limitations) j = j 0 e α a F RT η e α c F RT η j 0 = j 0,ref 1 DOD p p: exponential term (= 2/3 assuming regular shaped particles, cubical or spherical) constant bulk composition (x A cst) Specific area involved MCl 2 NaCl M *S. W. Orchard and J. S. Weaving, J Appl Electrochem, vol. 23, no. 12, pp , Dec Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 18

19 REFERENCE SIMULATION CONSTANT OPERATIONAL TEMPERATURE 40 Ah discharge C/5, 270 C Simulated ohmic resistance of the cell In accordance with the literature: at the beginning of the iron chloride active material reaction, a new reaction front appears at the interface of the beta alumina where the ohmic loss in the melt is minimum (nickel backbone) Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 19

20 INFLUENCE OF THE THICKNESS OF THE SOLID ELECTROLYTE 40 Ah discharge at 270 C Cell Voltage Only the thickness of the beta alumina has been changed between simulations As expected, the model predicts less overall polarization with a thinner electrolyte Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 20

21 INFLUENCE OF THE THICKNESS OF THE SOLID ELECTROLYTE 40 Ah discharge at 270 C Cell Voltage Only the thickness of the beta alumina has been changed between simulations 1.5 mm 1.0 mm As expected, the model predicts less overall polarization with a thinner solid electrolyte Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 21

22 REFERENCE SIMULATION CONSTANT OPERATIONAL TEMPERATURE 40 Ah discharge C/5, 270 C Cell Voltage Ohmic loss in negative and charge transfer in negative contributions are surimposed on the cell voltage From U cell = E Fe, displaying all the contributions is tricky because we don t know the mixed potential related to C/5, and charge transfer in positive is spatially inhomogeneous Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 22

23 Resistivity [Ohm*cm] FIAMM BETA ALUMINA RESISTIVITY Relation implemented in the model (FIAMM data) Temperature [ C] Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 23

24 2D MODEL IMPLEMENTATION Solid-state mechanism and constant melt composition Current collector Ohm s law in metal (Φ 1 ) Applied current (I exp ) on collector surface Casing domain Ohm s law in metal (Φ 1 ) Origin of potential (Φ 1 = 0V) Anodic domain Ohm s law in metal (Φ 1 ) Linearized Butler-Volmer on beta alumina external surface (i N ) Solid electrolyte domain Ohm s law in electrolyte (Φ 2 ) Cathodic region and felt Ohm s law in NaAlCl 4 (Φ 2 ) Ohm s law in metal backbone and carbon (Φ 1 ) Material balance (x A ) Electrochemical reactions (j i ) Chemical reaction (ε NaCl ) Porosity, volume fractions, exchange current densities ϵ = 1 ϵ M ϵ MCl2 ϵ NaCl ϵ M/MCl2 Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 24 t j = j Ni + j Fe j M and ϵ NaCl t k p j

25 SIMULATION ISOTHERMAL MODE 40 Ah discharge C/5, 270 C Cell Voltage n MCl2,init from cyclic voltammetry measurements (apparent Ah contributions) S collector = 48 cm 2 i 0,ref,Ni = A/cm 2 i 0,ref,Fe = A/cm 2 Active material form: p = 1.3 Simulation does not managed temperature rise and fluorinated additive contribution Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 25

26 Na-MCl 2 TECHNOLOGY General Principles Beta alumina with conductivity similar to common aqueous electrolytes ( o C) secondary electrolyte melt Na + conductor NaAlCl 4 Na β"- Al 2 O 3 MCl 2 Negative active material Solid electrolyte and separator Positive active material 23.5 cm x 3.5 cm Fe based solution Na-FeCl 2 OCV Fe = o C Ni based commercial solution Na-NiCl 2 OCV Ni = o C Multi-physics Modeling of a Na-NiCl 2 Commercial Cell Comsol Conference Grenoble 15 octobre 2015 Rémy Christin 26