Progress and challenges Generation 4

Transcription

1 Progress and challenges Generation 4 Battery Workshop, Bruxelles 11 th of January 2018 C. Barchasz, V. Tarnopolskyi, L. Picard, D. Bloch, S. Patoux, S. Perraud

2 CONVENTIONAL LITHIUM-ION SYSTEMS Volumetric energy density (Wh/L) Practical limits of Li-ion to keep cycleability & safety Packs for BEV Cylindrical Prismatic Laminate Practical limits of Li-ion to keep cycleability & safety Gravimetric energy density cell level

3 CONVENTIONAL LITHIUM-ION SYSTEMS LIQUID/GEL ELECTROLYTES High conductivity electrolytes Low interfacial resistances Fast kinetics Restricted choice of active materials Limited energy POWER ENERGY DENSITY State of the art Li-ion Low flash point Gas generation Thermal runaway Possible leakage SAFETY MARKET Costs High cobalt content Limited cyclability

4 CONVENTIONAL LITHIUM-ION SYSTEMS LIQUID/GEL ELECTROLYTES High conductivity electrolytes Low interfacial resistances Fast kinetics Restricted choice of active materials Limited energy POWER ENERGY DENSITY State of the art Li-ion Low flash point Gas generation Thermal runaway Possible leakage SAFETY MARKET Costs High cobalt content Limited cyclability

5 MOTIVATION FOR SOLID STATE BATTERIES (GEN 4) Improved safety Improved performances Lower costs (at pack level) 3 types of solid electrolytes : Inorganic Crystalline Materials (Perovskites, Garnets, Nasicon) Inorganic Amorphous Materials (LiPON, glass sulfides ) Solid polymers (Polyethylene oxide, PILs, single-ion) Y. Janek et al., Nature Energy, 2016, 1

6 MOTIVATION FOR SOLID STATE BATTERIES (GEN 4) Improved safety Improved performances Lower costs (at pack level) 3 types of solid electrolytes : Inorganic Crystalline Materials (Perovskites, Garnets, Nasicon) Inorganic Amorphous Materials (LiPON, glass sulfides ) Solid polymers (Polyethylene oxide, PILs, single-ion) Source: ORBIT

7 MOTIVATION FOR SOLID STATE BATTERIES 2017: Toyota's 2022 EV to pack fast-charging, solid-state batteries Commercialize all-solid-state batteries by : VW To Decide On QuantumScape Solid-State Battery Potential for 1,000 Wh/l 435-Mile Range 2017: SolidEnergy Systems has raised $30m including carmaker General Motors 1/solidenergy-recharges-with-30m-series-c?tag_id= : Honda Motor developing all solidstate batteries for electric vehicles (EVs) : BMW taps Solid Power for battery program Solid-Power-battery.html 2017: Continental eyes investment in solid-state batteries Next generation solid-state batteries into production in 2025

8 MOTIVATION FOR SOLID STATE BATTERIES 2017: Toyota's 2022 EV to pack fast-charging, solid-state batteries Commercialize all-solid-state batteries by : Saft developed a solid-state battery with a sulfur cathode and LiBH 4 electrolyte 2015: VW To Decide On QuantumScape Solid-State Battery Potential for 1,000 Wh/l 435-Mile Range doi: /j.jpowsour : SolidEnergy Systems has raised $30m including carmaker General Motors 1/solidenergy-recharges-with-30m-series-c?tag_id= : Honda Motor developing all solidstate batteries for electric vehicles (EVs) 2017: Continental eyes investment in solid-state batteries Next generation solid-state batteries into production in solid-state battery pioneer Sakti3 2015: Dyson acquired 100% of 19/dyson-sakti3-battery-acquisition/ / h/sol212/sol glanz.html 2017: Hitachi Zosen ready to commercialise solid state lithium battery Solid-Power-battery.html : BMW taps Solid Power for battery program

9 GLASS FAMILY : SULFIDES NO COMMERCIAL PRODUCTS YET Inorganic Amorphous Materials (Glass sulfides) 2010: Toyota announced 4-layers Graphite/LCO All-solid-state Battery S_EN/ /187553/ Y. Ishiguro, Batteries 2014 conference 2017: i Ride, an EV concept car is presented 2014: Toyota announced 20- layers All-solid-state battery for ultra-compact car : Solid Power, a spin-off from the University of Colorado, Boulder, claims its lithium-sulfide solid electrolyte can be produced at about the same cost as a liquid electrolyte High capacity cathode Lithium metal anode Sulfide-based solid electrolyte 100% inorganic battery materials 2-3X greater higher energy than conventional lithium ion

10 GLASS FAMILY : SULFIDES Inorganic Amorphous Materials and glass-ceramics (LiPON, glass sulfides ) Not stable at High Voltage with Cathode Conductivity up to 17 ms/cm Material synthesis Not Stable with Lithium (LiPON is stable) Implementation in batteries Low GB Resistance Good Electrolyte H 2 S Safety and processability

11 GARNET MATERIAL : LLZO (Li 7 La 3 Zr 2 O 12 ) NO COMMERCIAL PRODUCTS YET Inorganic Crystalline Materials (Garnets) Li/LLZO/Li 4 Ti 5 O 12 Li/LLZO/LiFePO 4 Wet cell assembly: thin layers by casting and drying J. Rupp et al., Adv. Energy Mater. 2016, 6, J. Phys. Chem. C 2017, 121, > 100 cycles >25 cycles 2012: Patented new electrolyte material (Lithium ion Rich Anti-Perovskite or LiRAP ) > 10-3 S/cm Y. Zhao et al., J. Am. Chem. Soc. 2012, 134,

12 GARNET MATERIAL : LLZO Inorganic Crystalline Materials (Perovskites, Garnets, Nasicon) σ = 1.35 x 10-3 S/cm Stability at high/low voltage Material synthesis /!\ germanium containing materials Electrolyte density Implementation in batteries GB Resistance Good Electrolyte Environmentally Benign

13 BOTTLENECK: SOLID CELL IMPLEMENTATION Densification & cell assembly 1. Densification 2. Electrodes stacking 3. Cell design Different methods (cold & hot pressing, sintering, SPS, ) Splitting dies, hot pressing Packaging Pressure control Lithium dendrites propagation Crucial against lithium dendrites

14 ADVANTAGES & CHALLENGES - Improved safety - No leakage - High temperature stability - Packaging downsizing (less cooling and safety devices in the pack) - Possibility to use advanced electrode materials (5V, Li 0 ) - Improved durability - High interfacial resistance and poor interface contacts - Reactivity between solid electrolyte and electrodes during cell assembly & cycling - Thick electrolyte layers / high density materials - NEW ARCHITECTURES, NEW PROCESSES NEEDED Main problem to solve: IMPLEMENTATION in lithium battery AT COMPETITIVE COSTS

15 POLYMER SOLID STATE BATTERIES Solid polymers (Polyethylene oxide, PILs, single-ion) Lithium Metal Polymer (LMP) battery available at Bolloré group Fabrication process based on extrusion Clean process with no solvent, high production yields Already available/demonstrated in the BlueCar Main limitations: Working temperature ~80 C + limited energy density Pack thermal management, efficiency loss Other actors in the field of polymer solid cells 2015: Seeo announced 220Wh/kg and a target of 400 Wh/kg DryLyte electrolyte: block copolymer solid electrolyte m/2015/01/ seeo.html

16 POLYMER SOLID STATE ELECTROLYTES Solid polymers (Polyethylene oxide, PILs, single-ion) PEO-BASED POLYMER ELECTROLYTES Studied since the early 80 s 1,2 Lots of polymeric structures investigated 2,3 Bloc copolymers, hyperbranched, grafted polymers Polysiloxane, polyboron, polyphosphazene, polyphosphates, polyacrylates, polystyrene, polycarbonates, POSS backbone Main limitations Working temperature > 60 C avoid the crystallinity Electrochemical stability <4V vs Li 0 /Li + limit to LFP Slight improvement in the working temperature but not in the ESW 1. M. Armand, Solid State Ionics, 1983, 9 10(2), X. Xie, J. Mater. Chem. A, 2015, 3, Y. Meng, J. Mater. Chem. A, 2016, 4, 10038

17 POLYMER SOLID STATE ELECTROLYTES Solid polymers (Polyethylene oxide, PILs, single-ion) PILS BASED POLYMER ELECTROLYTES Studied since ,5 PILs are often gelified with ILs 4,5 Main advantage Wide variety (infinity) of structures Main limitations Good conductivity but low Li + transference number Working temperature >40 C Price Decrease in the working temperature but still a poor T li+ + SEI issues 4. S. Passerini, Angew. Chem. Int. Ed. 2016, 55, D. Mecerreyes, Electrochimica Acta 175 (2015) 18 34

18 POLYMER SOLID STATE ELECTROLYTES Solid polymers (Polyethylene oxide, PILs, single-ion) NEW GENERATIONS OF POLYMER ELECTROLYTES Single ion conducting polymer electrolytes 6 Anchoring the anion for improving safety Polyester-based SPE 7,8 Going higher in potential vs Li 0 /Li + /!\ most of the actual SIC-SPE are based on PEO with its limitations (Working temperature, ESW) High transference number, High ESW, low Tg Conductivity to be optimized 6. Z. Zhou, Angew. Chem. Soc. Rev., 2017, 46, D. Brandell, Journal of Power Sources 298 (2015) X. Liu, Nano Research 2017, 10(12):

19 ADVANTAGES & CHALLENGES - Improved safety - No leakage - Process and low cost - Flexibility - Improved interfacial resistance / interface contacts - Accomodation of volume changes - Ionic conductivity - Electrochemical stability - Working temperature - Lithium dendrites Main problem to solve: WORKING TEMPERATURE of lithium battery

20 HYBRID ALL-SOLID-STATE ELECTROLYTES Conductivity Polymers Composite: Polymer solid electrolyte + ceramic nanoparticles Solid electrolytes Implementation Inorganic Performances Hybrid Cost Process Fu et al., PNAS Source: ORBIT Ceramic phase: Higher conductivity Polymer matrix: Lower grain-boundary resistance More flexibility, tolerance to volume changes, more simple process Very thin separator can be envisionned C. Yang et. al., Nano Research, 10 (2017)

21 HYBRID ALL-SOLID-STATE ELECTROLYTES NO COMMERCIAL PRODUCTS YET Hermes High Energy Rechargeable Metal cells for Space High energy density NCM cathode Lithium metal anode, combined with: 1) A solid protective coating consisting of polymer and inorganic materials applied on lithium 2) A solvent-in-salt electrolyte 450Wh/kg and 1200Wh/L in 3Ah cells demonstrated High voltage, Up to 10C at room temperature Target: >500Wh/kg by end of 2017 Current applications: aeronautics, space & drones 90 Wh/kg 12 V > 600 cycles N. Takami et al., J. Electrochem. Society, 164 (2017) A6254-A6259 Main challenges: Polymer stability (high voltage) Transport mechanisms to be solved Role and importance of interfaces in the composite to be understood

22 PERSPECTIVES FOR GENERATION 4 Improved safety Improved performances Lower costs (at pack level) Inorganic Crystalline Materials (Perovskites, Garnets, Nasicon) Inorganic Amorphous Materials (LiPON, glass sulfides ) Solid polymers (Polyethylene oxide, PILs, single-ion)???? Performances? Hybrid Cost Process Discussion during session 2

23 PERSPECTIVES FOR GENERATION 4 GEN 4a All-solid-state Li-ion battery Conventional Li-ion materials e.g. NMC/Si 325 Wh/kg cell > 1000 Wh/L cell GEN 4b All-solid-state lithium metal battery e.g. NMC/Li 2030 > 400 Wh/kg cell Excluding garnet approach > 1200 Wh/L cell 18

24 PERSPECTIVES FOR GENERATION 4 >1000 Wh/L >400 Wh/kg Volumetric energy density (Wh/L) Practical limits of Li-ion to keep cycleability & safety Packs for BEV Cylindrical Prismatic Laminate Practical limits of Li-ion to keep cycleability & safety Gravimetric energy density cell level

25 FOR FURTHER INFORMATION P. Novak et al., J. Electrochem. Soc., 162 (2015) A2468-A2475 Y. Janek et al., Nature Energy, 2016, 1 C.K. Chan et al., Electrochimica Acta 253 (2017) J. Goodenough et al., J. Electrochemical Society, 162 (14) A2387-A2392 (2015) Y. S. Jung et al., Isr. J. Chem. 2015, 55, R. Chen et al., Mater. Horiz., 2016, 3, X. Xie, J. Mater. Chem. A, 2015, 3, Y. Meng, J. Mater. Chem. A, 2016, 4, S. Passerini, Angew. Chem. Int. Ed. 2016, 55, D. Mecerreyes, Electrochimica Acta 175 (2015) Z. Zhou, Angew. Chem. Soc. Rev., 2017, 46, 797 X. Liu, Nano Research 2017, 10(12):

26 Commissariat à l énergie atomique et aux énergies alternatives 17 rue des Martyrs Grenoble Cedex Établissement public à caractère industriel et commercial RCS Paris B