High Specific Lithium Cells for Security, Military and Aerospace Applications High Energy / Extreme Environments Florence Fusalba, Battery Program Manager Rechargeable Xtrem condition s Product integration Multiform multifunctional systems PAGE 1
Presentation of CEA & LITEN French Atomic and Renewable Energy Commission CEA : 10 R&D Centers in France 4 main research priorities Defense & Global Security Energy Health and Information Technology Fundamental Research R&D «Laboratory for Innovation in New Energy Technologies and Nanomaterials» Solar energy & smart building Transport technologies Energy sources for portable electronics Nanomaterials Biomass & Hydrogen Technologies Key figures (2011-12) Staff : 15 982 Budget : 4,2 b 613 priority patents applications field Staff : 1200 Budget : 186 M (150M turnover) 840 patents >250 p on batteries http://www.cea.fr/ http://www-liten.cea.fr PAGE 2
Embedded Energy : Specific Batteries Customized battery development to stand drastic conditions CEA Tech Competences Applications CEA LITEN has an integrated approach from materials to system dedicated to battery developments : Prototyping (TRL 3-6) have been realized in several application fields : Materials Electrodes Cells Module Battery Pack Safety tests CEA LITEN develops customized Li-ion technologies and designs depending on technical specifications, for example : - Safe & Stable energy or Power batteries integrating LiFePO 4 - High Energy Li-ion cells integrating high capacity electrodes - Costs care Military application Si-C Technology 3.4V - 1.25Ah 260Wh/kg cells Reduced cyclability For 70Wh 13.6V Si Battery pack Higher autonomy at 20 C (+60%) & - 20 C (+180%) versus commercial For Security, Beacons 2D Autonomous sensor with Energy Harvesting NMC/G Technology 3.7V - 5mAh, <1mm thick. >1000 cycles (at C/5-D/10 and 80%DOD) Using Printing Technology Spatial Sensor NCA/G Technology 3.6V - 450mAh Cell mechanical design to sustain extreme environment (vibration, acceleration, vacuum ) Aerospace Battery characteristics aimed : - Long life time: at least 10 years - Resistant to hard environmental conditions - Operational between -50 C to 100 C - Large pressure range : 50 to 1100mbars or for vacuum Satellite application HE-LMO/Si-C Technology 3.2V - 2.5Ah Down scale demonstration (1/6) 278Wh/kg 81% of capacity recovered at -10 C Aeronautic Large Capacity/High Energy Li-ion cells Si-C Technology 3.4V 40Ah 300Wh/kg (C/10 @45 C) Aeronautic Sensor LiFePO 4 Technology 3.2V -180mAh Thin Cell (1.5mm thick) for extreme conditions (Pressure, vibration, T ) Designed electrolytes, components 3 Contact : florence.fusalba@cea.fr
A PILOT PLATFORM Semi Industrial Line: Dry room ca. 1000m² (Dew points: -20 C & -40 C); Facilities (>1000m²) Line capability up to ca. 150kWh/month (cells); ca. 20 to 40 battery packs (EVs sizes)/month Mixing Cell Winding Coating Slitting Electrolyte filling Calendaring All materials & components electronically tracked during the process thanks to bar codes Laser Welding Electrical test benches: High power ~300 channels Low power (Includes formation) 480 channels Battery Modules & pack assembly with e- management Semi automatic assembly with full components tracking PAGE 4
OUTLINE Autonomous Sensors in Severe Conditions Autonomous Sensors Batteries For Aerospace Conditions Titanium cased battery for autonomous μsystem in WireLess transmission for Spatial environment PAGE 5
LI-ION BATTERY DESIGNED FOR SPATIAL ENVIRONMENT Interest of RF Wireless: satellite monitoring (during thermal and vibration tests) satellite/launcher/shuttle monitoring during launch and in flight For temperature, pressure, radiation transmission data Battery Requirements: High energy density, Rechargeable, Lifetime at least 5 years, Temperature range (tests on ground and storage) : -40 C / +60 C, Working in vacuum (P = -10-10 torr) with very specific design (compactness and resistant to vibrations) Electronic part Wedge Battery PAGE 6
Tension (V) Capacity % ASTRAL: SPATIAL CEA LI-ION BATTERY SPECIFIC DESIGN - Rigid and highly hermetic packaging, laser welded - Hermeticity of the casing : < 10-8 mbar.l.s -1 -Connections thanks to straight pins and use of wedge - ~ 60 batteries delivered ASTRAL-V1-PR16 Technology Nominal Capacity (mah) Nominal voltage (V) Nominal Energy (Wh) Cut-off Voltages (V) Internal Resistance (mω) Overall dimensions without pins (mm) Volume (cm 3 ) Mass (g) Volumetric Energy Density (Wh/L) Gravimetric Energy Density (Wh/kg) NCA / Graphite (CEA electrodes) 450 3.6 1.62 3.0-4.0 175 30 x 30 x 8.4 7.6 15.5 213 105 4,2 4 3,8 3,6 3,4 3,2 3 2,8 0 10 20 30 40 50 60 Temps (jours) 100 80 60 40 20 0 0 25 50 75 100 charge discharge Good cyclability : over 80 cycles in profile of use conditions Self-discharge equivalent to Cycle_Index conventional Li-ion technology : about -1%/month PAGE 7
Discharge_Capacity(mAh) ASTRAL: SPATIAL CEA LI-ION BATTERY PERFORMANCES 450mAh - 3.6V Battery for Spatial environment 2 ASTRAL Batteries connected Battery validation in relevant environment TRL 4-6 Batteries under vacuum cycling Full capacity restored after 15 months cooled storage (~-6 C) 400 C/10 C/5 C/10 9 days 300 C/2 C Qualified to the vibration tests: according to the space protocol 200 100 ASTRAL battery reference ASTRAL battery after PR28 thermal PR28-TH cycling ASTRAL PR28-Sous battery vide under vacuum Vacuum: 2.10-5 mbars AT = 27 C (not regulated) 0 0 10 20 30 40 50 60 Cycle_Index Qualified to thermal cycling [0-40 C] and under vacuum: Tests performed at CNES ASTRAL Battery resistant to vibrations, vacuum & thermal conditions Thanks to Benjamin Calvet, Frederic Courtade, Stephane Fredon, Daniel Gervaud, Jeremie Dhennin (CNES) Patrice Pelissou (ASTRIUM) & Hélène Rouault, Hélène Duchemin, Djamel Mourzagh (CEA/Liten) PAGE 8
OUTLINE Autonomous Sensors in Severe Conditions Autonomous Sensors Batteries For Aeronautics Conditions Thin hard cased battery (1.5mm) with high hermiticity (for low pressure environment) & high vibration resistance for Aeronautics sensors To have electric power for sensors on helicopters lead lag dampers or aircrafts wings to monitor vibrations, bending or on missile /launcher PAGE 9
BATTERY FOR AERONAUTIC (HELICOPTER & AIR PLANE) EADS, Dassault, Eurocopter, Goodrich Actuation Systems, CENARO, etc Small Battery in Hard Casing, thin (<1.5mm) & hermetic (low pressure environment), vibration resistant Battery characteristics to be aimed: Development of a high energy density battery Thickness less than 1.5 mm, Surface 55*57 mm (2/3 of the smart tag area) Flexible or conformable (adapted to the plane or helicopter geometry) Electronic part Very long lifetime 10 years, Resistant to very hard environmental conditions: Large range of temperature -50 C to 95 C Corrosive environment, Mechanical strain (vibrations, acceleration ), Operational on a large range of pressure Metallic disk 50 to 1100 mbars welded on the Compatibility with the other components bottom (hole electrolyte filling) of the SMART TAG, Bottom Compatibility with the final integration process 57mm Top 57mm Communication block antenna TRIADE battery Glass to Metal Seals (connections, laser welded on the cover) 1.5mm 55mm 55mm Ring Pt wire Pearl of glass Glass to Metal Seal
TRIADE: BATTERY FOR AERONAUTIC (HELICOPTER & AIR PLANE) Battery Specifications: LiFePO 4 /Graphite Technology: Stable & Safe Nominal voltage 3.2V ; [2,6-3,7V] Capacity : 180mAh Stacked inner electrochemical core: Mechanical conception: 57mm x 55mm x 1,5mm Stainless steel casing Laser welding High hermiticity Glass-metal connections Direct pins connections to the electronic PCB to withstand mechanical vibrations, acceleration Specific electrolyte to operate at both low & high temperatures Technology LiFePO4 / Graphite Nominal Capacity (mah) 180 Nominal voltage (V) 3.2 Nominal Energy (Wh) 0.544 Cut-off Voltage (v) 2.6 3.7 Internal resistance (mω) 400 Overall dimensions without pins (mm) 57 x 55 x 1.5 Volume (cm3) 4.7 Masse (g) 17.2 Volumetric Energy density (Wh/L) 115 Gravimetric Energy Density (Wh/kg) 31.6 10 batteries prototypes delivered to industrial partners TRL 4-6 Battery validation in laboratory environment PAGE 11
OUTLINE Introducing High Energy >250Wh/kg Towards Low temperature range mission Objective : New Chemistries At least 250Wh/Kg at the cell level >25% more energy compared to current commercial Li ion cells PAGE 12
Cell Energy CEA Li-ion Cell Technologies for High Energy Technology Gravimetric Energy Density / Wh.kg -1 Status LFP/Graphite 120 to 155 Pilot Line 18Ah 130Wh/kg NCA-NMC/Graph. 180 to 220 State of the art 5V Spinel/Graphite 200 to 240 HE-LMO/Graphite 220 to 280 Ready but R&D on electrolyte Under development LFP/Si-C 155 to 180 Not a target 35Ah 150Wh/kg NCA-NMC/Si-C 250 to 300 Niche markets HE-LMO/Si-C 280 to 350 Under development 40Ah 300Wh/kg State of the art in commercial 18650 ca. 3Ah (3,6V) Li-ion cells: ~230-240Wh.kg -1 PAGE 13
Potential / V vs. Li + /Li Wh/L Discharge Potential / V vs. Li + /Li The technology selected for Energy >250Wh/kg NMC (180mAh/g) or NCA (200mAh/g) LiNiPO 4 HE-Lamellar Oxide (250mAh/g): Li-rich Mn-based layered oxides xli 2 MnO 3 (1-x)LiMO 2 with M=Mn,Co,Ni, 3.5V vs Li 4.5 3.5 Li 2 CoPO 4 F Instability LiCoPO 4 of the LiMn 1.5 Ni 0.5 O 4 electrolyte above 4.3V Li 2 CoSiO 4? (graphite negative electrode) vs. Li LiMnPO LiMn 4 2 O 4 LiCoO 2 NCA, NMC Market Li 3 V 2 (PO 4 ) 3 Li(Li,Ni,Co,Mn, )O 2 LiFePO 4 Energy Density above 250 Wh.kg -1 With Si-C composite 2.5 2 1.5 1 0.5 0 Materials for High Power, Safety and Long Life applications TiO 2 -B Li 4 Ti 5 O 12 Power Market Energy 550 500 450 400 700Wh/L ; 300Wh/kg + vs. Si/C composites + vs. Carbon + vs. Titanium oxides 350 300 250 300Wh/L ; 100-120Wh/kg 500Wh/L ; 200Wh/kg 200 150 50 100 150 200 250 Wh/kg Materials for High Energy applications Carbon-Silicon composites Carbon Li-metal 100 200 300 400 3400 3600 Specific Capacity / mah.g -1 Source: Saft Li LiMnO 2 2 FeSiO 4 2.5 0 50 100 150 200 250 300 Specific Capacity / mah.g -1 In soft packaging NCA or NMC / Si-C 250-300Wh/Kg A HE-LMO /Si-C 350-400Wh/Kg B PAGE 14
Cell Capacity (%) 250WH/KG CELLS FOR SECURITY/BEACONS NCA / Si-C lab prototypes (~1Ah) Graphite Prototype: 850mAh 5 x 34 x 37 mm 3 200Wh/kg 450Wh/L NCA / Si-C 1.25Ah Wound Cell 5 x 34 x 37 mm 3 260Wh/kg (+30%) 600Wh/L 1000+ cells manufactured and assembled in dry room 100 Niche markets which require high energy density but low cycle count Charge Capacity Discharge Capacity 80 60-0,17% per cycle 40 70Wh 13.6V Si Battery Pack 20 0 C/3 [4.2-3V] (80% DOD) 0 10 20 30 40 50 60 Cycle number 260Wh/kg reached on 1.25 Ah lab prototypes Cycle life @ 80% of DOD (< 80 cycles) PAGE 15
HIGH ENERGY Li-ION BATTERY FOR ENERGY EFFICIENT MILITARY/SOLDIER 4S5P Battery Pack assembly 70Wh 13.6V Si Battery Pack Acknowledgements to Table legends: Italic= Calculated value Bold = Corrected value due to additional interface resistance at electrical test bench (Pressure connection for the commercial battery not for HE battery) *only between 80-50% SoC Battery HE (4S) Competitor (3S) Capacity @C/5 20 C (Ah) 5 4.2 +20% Weight (g) 371 370 +0.3% Nominal voltage @C/5 20 C (V) 13.6 10.8 +25% Energy @C/5 20 C (Wh) 68 45 +50% Gravimetric energy @C/5 20 C (Wh/kg) 183 120 +50% Volumetric energy @C/5 20 C (Wh/L) 285 225 +25% Internal resistance (mω) 220 330-33% Specific Autonomy 20 C (h) ( cycles 4,5A (6s) 0,1A (54s)) 8h30 7h20 +15% Specific Autonomy 20 C (h) ( cycles of 45W (6s) 1W (54s)) Specific Autonomy -20 C (h) ( cycles 4,5A (6s) 0,1A (54s)) Specific Autonomy -20 C (h) ( cycles of 45W (6s) 1W (54s)) Specific Energy density 20 C (Wh/kg) Specific Energy density -20 C (Wh/kg) 12 8 +50% 7h15 3h50* +85% 10 3h30* +185% 163 103 +60% 136 48* +180% Test protocol: Repeated 1min - cycles, made of 4.5A- 6s pulses corresponding to radio emission followed by CC 100mA-54s for reception or stand-by -Higher autonomy at 20 C (+60%*) & -20 C (+180%) compared to commercial battery (3S5P) -Specific pack design developed by AGLO-DEV for this «breathing» technology with high reproducibility in term of weight (<0.5%) and resistance (<0.5%)
LOW TEMPERATURE APPLICATION FOR SI TECHNOLOGY NMC / Si-C lab prototypes (~1Ah) 53734 ELEMENTS OF 270WH/KG AT 20 C AND C/5 RATE - Self discharge test Research of electrolyte for low temperature applications (-20 C) in power mode Development of batteries which can be stored at full charge 1500+ cells manufactured* in dry room Impact test At -20 C, high performances up to 2C rate +70% of the capacity recovered at -20 C Low self discharge (<2%/month) UL1642 standard compatibility under progress 50% SOC, 20 C, 9kg, 61cm h, 3000images/s *to evaluate silicon materials, electrode formulations, electrolyte compositions, separators PAGE 17
OUTLINE Introducing High Energy >250Wh/kg For AeroSpace Perspectives High Specific Energy Lithium Batteries For AeroSpace High Energy Battery for Electric aircrafts, AUV (Drones ) >250Wh/kg 100 cycles High Specific Energy Li-ion Cells Aluminum cylindrical hard casing C ~ 35Ah, E > 250Wh/kg BOL PAGE 18
2012: Silicon-based 40Ah Li-ion Prototypes for Electric Aircraft Development of 35-40Ah cells, NMC & HELMO/Si-C for E > 250Wh/kg NMC electrode High energy density Separator Si-C electrode High energy density Specifications aimed: -For Aeronautic: Soft pouch C ~ 40Ah, E ~ 300Wh/kg BOL at cell level Loss ~ 0.7%/cycle (100%DOD) Acknowledgement to Winding Assembly 40Ah Prismatic shape 10 x 140 x 140 mm NMC/Si-C technology ca. 300Wh/kg (C/10@45 C) -1%/cycle @100% DoD TRL 4-6 PAGE 19
Voltage (V) 2013 HIGH ENERGY BATTERY STATUS & FORESEEN High Energy Battery Prismatic Soft Pouch 10 x 140 x 140mm 310Wh/kg (@C/8) 44Ah NMC/Si-C technology 3.4V Electrical testing for capacity check @ different T (@C/4 & C; 25, 45 & 55 C) under progress 10.140.140 cell Nominal capacity: U nom : 3,4V Mass: 490g Energy density: Internal resistance (cell) (1kHz) 43 Ah @ C/8 initial 300 Wh/kg @C/8 initial 4mOhm 4.5 4 3.5 3 2.5 2 Electrical specifications Temperature Range: Max charging voltage Min discharge voltage: 2.5V Imax charge (TBC) 8A Imax discharge (TBC) Cycle C/8 @ 40 C [4.3-2.5V] 10x140x140mm 0 100 200 300 Energy density (Wh/kg) -20/ +45 C 4.3-4.4V Foreseen: AUV/UAV applications Specifications: i.e. 700Wh-1.5kWh [30-60V] Energy versus Power Optimized Energy Density: 250 to 270Wh/Kg or 530Wh/L to 615Wh/L; Ri : ~2mΩ Continuous C-rate max: 4C 11A PAGE 20
SPACELION: Spatial CEA Li-ion Chemistry High specific energy is the most important criteria for GEO and LEO satellites 2006-2011 Program TRL 3
Voltage / V 2006-2011 Program SPACELION: Spatial CEA Li-ion Chemistry Voltage (V) Voltage (V) 5 5 4.5 4-10 C 25 C -19% +16% 50 C 6 5 4 T4-PR13 25 C C/10 24h OCV 4 3.5 3 3 3 2 2 1 C/10 25 C 2.5 2 charge @ C/10 0 20 40 60 80 100 120 Capacity (% capacity @ 25 C) 1 0-3.5% 0 0.5 1 1.5 Capacity (Ah) 0 50 100 150 200 250 300 Gravimetric energy density / Wh.kg -1 81% of capacity at -10 C with a conventional electrolyte PR12 PR13 PR14 PR15 PR16 PR17 PR18 PR19 PR20 PR22 PR23 PR24 116% of capacity at +50 C thanks to the increase of capacity of the layered-layered oxide with temperature -High energy density (~250Wh/kg) Li-ion cells developed -EADS-Astrium tested -Partial satisfaction of the main requirements for space application obtained: -Low self-discharge <5% per day of capacity loss -Cell operation at a large temperature range; i.e. -10 C to +50 C -BUT Cyclability requirements not reached (>-2%/cycle) PAGE 22
2011-2013 CEA PROGRESS BEYOND SPACELION TRP ESA capacité en mah/g Work to stabilize Si/C negative upon cycling: Coin cell results CEA Patent: Coulombic efficiency stabilized at 100% & capacity at 1200mAh/g upon cycling (150 cycles demonstrated, cycling still under progress) Li-ion cell prototype (ca.1ah/soft pouch) 1600 1200 800 400 0 0 50 100 150 200 nombre de cycles 1 µ m Li-ion pouch cell proof of concept: => 90% capacity restored after 60 cycles (-0,17% capacity loss per cycle) =>100% coulombic efficiency and greatly improved cycle life of Silicon-Carbon composite negative electrodes =>0.17% capacity loss per cycle in 2012 (@C/10 100% SoC/100%DOD or @C/3 100%SoC/80%DOD) PAGE 23
Energy density / Wh.kg -1 PERSPECTIVES FOR HIGHER Li-ion ENERGY At the Positive, switch NMC for High Energy-Layered-Lamellar Oxides -HELMO or xli 2 MnO 3 (1-x)LiMO 2 thanks to our upscale synthesis capability In soft packaging NMC / Si-C 270-300 Wh/Kg A HE-LMO /Si-C 350-400Wh/Kg B In rigid casing HE-LMO/Si-C > 250 Wh/Kg B Capacity / mah.g -1 300 250 200 150 100 50 1000 800 600 400 200 2.5-4.8V 25 C C/10 0 0 10 20 30 40 50 60 Cycle # 0 0 10 20 30 40 50 60 Cycle # at Cell-level Capacity to be sized depending on mission profile Pilot co-precipitation reactor: ~1kg batches Today (2013), HELMO upscale synthesis is stabilized at 245mAh/g with high synthesis reproducibility. Pilot batch performances = Lab reference performances PAGE 24
HIGH SPECIFIC ENERGY BATTERIES FOR SATELLITES Cycle Life Specifications aimed: -Today: Soft pouch Capacity Loss ~ 0.2%/cycle (100%DOD) OK 40Ah Prismatic shape for electric aircraft NMC/Si-C technology ca. 300Wh/kg (C/10 @45 C) 10 x 140 x 140 mm Perspectives OK -To Spatial 1 st Stage: 2014 Hard casing E > 250Wh/kg BOL at cell level Loss < 0.07% per cycle* (80%DOD) Under Progress *300 cycles with C/10 charge rate and C/2 discharge rate at 80%DoD (-10, 20 C & 50 C) 20 cells (18650) 3 Ah 240Wh/kg (NMC/Si-C) First step prototyping for space Space Rechargeable Li-ion Battery Li-rich/Si-C Technology >250Wh/kg BoL at CEA 50125 or D size like -cell level PAGE 25
Thank you for your attention Special thanks to involved team members, To Séverine Jouanneau, Sébastien Patoux, Lise Daniel, Marlène Rey, Willy Porcher, Gilles Moreau Contact: florence.fusalba@cea.fr Thank you! PAGE 26 Commissariat à l énergie atomique et aux énergies alternatives Centre de Grenoble 38054 GRENOBLE Cedex 09 T. +33 (0)4 38 78 29 20 F. +33 (0)4 38 78 51 98 Direction de la Recherche Technologique Liten Authors thank ESA for SPACELION granted projects (2006-2011) Etablissement public à caractère industriel et commercial RCS Paris B 775 685 019 PAGE 26