ionics (category 1) program: status and perspectives
TRANSCRIPT
Grigorii Soloveichik, Program Director
Halle Cheeseman, Program Director
Max Tuttman, T2M Advisor
Sean Vail, Tech SETA
Neal Golovin, Tech SETA
Mark Pouy, Tech SETA
Jared Incorvati, Tech SETA
Daniel Adams, Program SETA
Esther Sperling, Program SETA
Isik Kizilyalli, Associate Director for Technology
Nancy Hicks, Meeting Coordinator
IONICS ARPA-E team
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Drivers for next generation batteries
‣ Higher energy density- The target of 500 Wh/kg impossible without Li metal anode and conversion cathode
‣ Safety, safety, safety…- Larger LiB battery packs are more prone to safety issues – runaway propagation and heat dissipation challenges
‣ Reduction of pack overhead - Mechanical protection- Thermal management system
‣ Cell cost reduction
2Battery safety is inversely proportional to energy density and abuse
E. Cabrera-Castillo et al., J. Power Sources, 324 (2016) 509
ARPA-E programs in batteries
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BEEST (Batteries for Electrical Energy Storage in Transportation, 2010)- Increase battery energy density via material and component development
RANGE (Robust Affordable Next Generation Energy storage systems, 2013)- Improve battery safety thus reducing protective components via intrinsically safe (aqueous and solid-state batteries) or cell design
IONICS (Integration and Optimization of Novel Ion-Conducting Solids, 2016)- Enable lithium metal batteries via solid ion conductor development
IONICS: Integration and Optimization of Novel Ion-Conducting Solids
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IONICS program mission
Create solid separators for electrochemical cells using solid ion conductors to enable transformational performance and cost improvements in electrochemical cells.
Li metal
Block dendrites
Category 1: Li+ conductors to enable the cycling of Li metal
IONICS program goal: overcome property tradeoffs to create transformational components
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Current status: tradeoffs among properties of ion conductors prevent electrochemical cell improvements
LiPON LGPS
IONICS program: from the beginningseek to overcome fundamental property tradeoffs
(Electro)chemical stability
Electronic ASR, conductivity
Thermal properties
Mechanical properties
Processing,cost
Poor
Marginal
Selectivity
Excellent
Device integration
Ionic ASR, conductivity
IONICS Category 1 metrics
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ID Metric Value Rationale
1 Dendrite-free cycling at 25°CModulus, surface, and microstructural
properties that prevent Li metal shorting
Pre-requisite for use of lithium metal
2 Thermal properties −20 to 70°C Ambient operation
3 Component area ≥30 cm2 First market in portable electronics
4 Cost ≤$10/m2 Needed for cell to hit 100 $/kWh
5 Ionic ASR at 25°C ≤5 Ohm-cm2 For 1C rate
6Capacity of Li metal moved per
cycle≥3 mAh/cm2 Enable high-energy cell; reflects
current commercial
7 Current density ≥3 mA/cm2 For 1C rate
8 Number of cycles ≥500 For portable electronics, automotive
9 Electrochemical stability That needed for energy, cycling targets Stability is essential
10 Thickness ≤20 μm Needed to achieve energy targets
11 Fraction of Li cycled ≥80% Avoid excess weight/volume
12 Electronic ASR at 25°C ≥1E5 Ohm-cm2 For high current efficiency
13 Mechanical propertiesSuitable for handling and operating with
large areas (see 1.3)Crucial for manufacturing and cell design
14 Device IntegrationEnable 400 Wh/kg and 1000 Wh/L for
cell repeat unitCaptures other aspects of making
a practical cell
Cost targets for a lithium metal cell
‣ For a 100 $/kWh cell cost target:– 10 to 12 $/m2 cost target for all cell layers– 7 $/m2 for cathode and both current
collectors– ≤5 $/m2 for separator plus any Li metal
‣ Cost of Li foil depends on its thickness- price of 30 m foil 8-10 times of
the Li ingot price- cell assembly in discharged state preferable
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Li metal
2.5 g/cm3
5 g/cm3
0.5 g/cm3
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Polysilicon
Approximate goal for separator and any Li metal
IONICS is focused on the separator component
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Device metrics:W/kg, Wh/kg, $/kW, $/kWh, durability, mA/cm2 at a given V, etc.
Typical ARPA-E program
Component metrics in the device context:Selectivity, stability, separator and interfacial ASR, dendrite resistance, $/m2.
IONICS program
Device metrics revisited:W/kg, Wh/kg, $/kW, $/kWh, durability, mA/cm2 at a given V, etc.
IONICS Plus program
Success in the separator development allowed for building full batteries
IONICS portfolio16 Project Teams • 3 Technology Areas
Category 1: Li+ conductors to enable the cycling of Li metal
RANGE, OPEN Battery related projects
Four key metrics to evaluate lithium cycling
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1-2: Goals3-6: LiPON7-9: PEO10-12: Inorganic13-14: Nanostructures15-26: Liquids
2: Fast-charge goal
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3
46
7
8
9
1220
14
25
24
16
19 11
1721
22
15
18
13
23
26
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Per-cycle arealcapacity (mAh/cm2)
1: ARPA-E IONICS goal
Plating current density, mA cm-2
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P. Albertus, S. Babinec, S. Litzelman & A. Newman Nature Energy, 3 (2018) 16–21
Current program status
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• Stable Li cycling at high current densities• Large area ceramics manufacturing• Flexible SSE• Novel high capacity cathode materials• High energy density cells
Main lithium cycling issues in solid state batteries
Dendrite formation/battery shorts• Loss of Li
- Li segregation- non-uniform plating- mossy lithium plating- plating on other conducting surface
• Li wettability towards SSE• Anode volume change• Membrane thickness/high ASR• Soft shorts/defects• Interfacial resistance growth/chemical reactions• High cost of thin Li foil
Main lithium metal battery issues
All Li metal anode issues plus…• Growth of interfacial resistance
- reaction of SSE with cathode components• Low conductivity of solid catholyte• Cathode volume change• High cost of separators• Handling of fragile membranes• High manufacturing cost• Safety of batteries with liquid electrolytes
Strategies to address high interfacial resistance
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Xia et al., Chem. 5 (2018) 1–33
‣ NaMg(Mn)F3@C core@shell microstructures as the matrix for Li metal- CE 98% at 2 mA/cm2 (H. Yuan et al., Sci. Adv. (2020) 6, eaaz3112)
‣ Cell with a Ag–C nanocomposite anode (no Li excess) and argyrodite SSE demonstrated >900 Wh/L and 1000 cycles- CE 99.8% at 6.8 mA/cm2 (Y.G. Lee et al., Nature Energy, 2020, 5, 299)
‣ For sulfide separator, the pressure positively correlated with critical current densities for Li striping and negatively for Li deposition (Y. Wang et al., ACS Appl. Mater. Interfaces 2020, 12, 31, 34771)
‣ A hybrid lithium-ion/lithium metal cell with capacity of 890 Wh/L with Li metal plated on graphite (C.Martin et al., Joule, 2020, 4, 1296)
Li metal battery news: anode
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‣ Fluorinated 1,4-dimethoxylbutane/LiTFSI electrolyte demonstrated CE of 99.5% and achieved 325 Wh/kg and 80% capacity retention after 100 cycles in anode-free pouch cells (Zhiao Yu et al. Nature Energy. 2020, 5, 526)
‣ Anode-free lithium-metal pouch cells with a dual-salt lithium difluoro(oxalate)borate /LiBF4 liquid electrolyte showed 80% capacity retention after 90 cycles (R. Weber et al., Nature Energy, 2019, 4, 683)
‣ K4BiI7 additive to the electrolyte increases CE to 99.57% and enables 400 cycles of 5.0 mAh/cm2 at 1C rate (Y. Cui et al., Front Chem. 2020, 7, 952)
‣ Tellurium-stabilized lithium deposition improves cycloability 7x (S. Nanda et al. Joule, 2020, 4, 1121)
Li metal battery news: electrolytes
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‣ Solid electrolyte interface (SEI) improvement - Use of fluorinated solvents (e.g. FEC, fluoro-1,4-dimethoxylbutane) and/or Li salts (e.g. LiF, bisisoxalatodifluorophosphate, difluoro(oxalate)borate)- Use of additives (Te, Bi, octaphenyl polyoxyethylene, etc.) to liquid electrolyte
‣ Li plating/stripping improvement- Use of a 3D matrix for Li plating (carbon, ceramic)- Li alloying (Sn, Sr)- Li-free anode
Li metal anode research directions
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‣ Solid Power delivered 250 first-generation 10-layer, 2 Ah pouch cells with Li anode and sulfide separator made by R2R process https://chargedevs.com/newswire/solid-power-introduces-all-solid-state-lithium-metal-batteries/
‣ XNRGI’s PowerChip opens a 240 MWh factory in India to produce battery that uses metallic lithium by depositing it into a silicon 3D substrate coated with thin films and etched with millions of tiny cells. It is claimed to achieve energy density of 1600 Wh/L (405 Wh/kg). https://xnrgi.com/products-2/
‣ SES (SolidEnergy Systems) sells 5.8 Ah HermesTM Trio cells (357 Wh/kg, 645 Wh/L cell level). Larger cells for VTOL under development.https://www.ses.ai/product
Li metal battery manufacturing
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Conclusions
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• Prevention of dendrite formation at high critical current density demonstrated in symmetrical cells
• Compatibility of cathode formulation with solid electrolyte remains an issue (capacity fade)
• Manufactureability of large format solid state cells is a major roadblock to implementation
• Safety of large capacity solid state battery packs to be demonstrated
• Three major focus research areas:- design of lithium metal free anode cells- high capacity cathode development- cell/stack design for automated manufacturability
Annual meeting objectives
• Report out at the end of IONICS Cat1 Year 3
• Hear about the technical & commercialization progress of IONICS and associated projects
• Discuss common challenges, lessons learned, and solutions to common problems
• Get understanding of the state of the art and future directions from industry, government and policy leaders
• Provide engagement with stakeholders
• Continue to build an R&D and commercialization ecosystem around energy storage programs
• Gain a feedback from performers
