Energy Storage Yi Cui

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1 Energy Storage Yi Cui Department of Materials Science and Engineering Stanford University Stanford Institute for Materials and Energy Sciences SLAC National Accelerator Laboratory

2 CA, ~60 GWh World ~10 TWh ~70Wh ~85,000Wh ~1million soon ~10 Wh 1 billion pieces/yr

3 Lithium Ion Battery Cells: Now and Future Goals Cell level (goal) System level (goal) Energy ~200 (600) ~100 (300) (Wh/kg) Cost (70) (150) ($/kwh) Cycle life 3000 (10,000 for grid) Safety

4 Grand Challenges of Batteries - High energy density: 3x - Low cost: 3x lower - Safe Revolution in Transportation, Grid, Renewable

5 Cui Group Energy Storage Program High capacity chemistries: - Si, Li metal anodes - S cathodes - P anodes Pre-storage of Li-ions Advanced tools: - In operando TEM - In operando X-ray Semiflow batteries for grid Solid-state electrolyte Architecture design and safety

6 Current negative electrodes High Energy Lithium Batteries Graphite (2D): 370 mah/g Future negative electrodes (10 time higher capacity) Silicon: 4200 mah/g Li metal: 3860 mah/g

7 High Energy Lithium Batteries Current positive electrodes LiCoO 2 (2D) 150mAh/g LiMn 2 O 4 (3D): 150 mah/g LiFePO 4 (1D) 170mAh/g Future positive electrodes (10 time higher capacity) Sulfur (S 8 ) ~1670 mah/g Li 2 S

8 Theoretical Specific Energy Theoretical Specific energy (wh/kg) Cathode 6X 3X

9 Silicon Anodes With 11X Specific Capacity 4200 mah/g 370 mah/g Individual particle: Break For Si: volume expansion to 4 times Problems: 1) How to avoid breaking? 2) How to build stable solid-electrolyte-interphase (SEI)?

10 1 st GCEP Project Funding on Battery (Jan, 2007): Nanowire Battery PI: Yi Cui, co-pi: Fritz Prinz

11 In-situ Transmission Electron Microscopy (TEM) 2mm Nanofactory TEM-STM holder (M. McDowell, C. Wang, Yi Cui, Nano Energy 1, 401, 2012)

12 Fracture of Surface Cu Coatings 12 5x actual speed

13 Nanoparticle critical breaking size: ~150nm Nanowire critical breaking size: ~300nm (M. McDowell, I. Ryu, S.W. Lee, W. Nix, Y. Cui Adv. Materials 24, 6034 (2012))

14 11 Generations of Si Anode Design from Cui Group Gen 1: Nanowire Nature Nanotechnology 3, 31 (2008). Gen 2: Core-Shell Nanowire Nano Letters 9, 491 (2009). Gen 3: Hollow Nano Letters 11, 2949 (2011). Gen 4: Double-walled hollow Nature Nanotechnology 7, 310 (2012). Gen 6: Si-hydrogel Nature Communication 4:1943 (2013) with Zhenan Bao Gen 5: Yolk-shell Nano Letters 12, 3315 (2012).

15 11 Generations of Si Anode Design from Cui Group Gen 7: Self-Healing Nature Chemistry 5, 1042 (2013). with Zhenan Bao Gen 8: Pomegranate-Like Nature Nanotechnology 9, 187 (2014). Gen 10: Prelithiation of Si anodes Nature Communications 5, 5088, 2014 Gen 9: Non-filling carbon coating or porous Si ACS Nano 9, 2540 (2015). Gen 11: Micro-Si gaphene cage Nature Energy 15029, 2016

16 Gen 8: Pomegranate-Like Si Batteries - Reduce surface area - Increase mass loading - Dense packing N. Liu, Z. Lu, Y. Cui Nature Nanotech 9, 187 (2014).

17 Gen 8: Pomegranate-Like Si Batteries N. Liu, Z. Lu, Y. Cui Nature Nanotech 9, 187 (2014).

18 Gen 7: Self-Healing Batteries C. Wang, H. Wu, Y. Cui, Z. Bao Nature Chemistry 5, 1042(2013)

19 3-8 µm Si particles C. Wang, H. Wu, Y. Cui, Z. Bao Nature Chemistry 5, 1042(2013)

20 Battery Safety - Smart separators for detecting internal shorts - Reversible thermal fuse inside batteries

21 Battery Safety In the News Airplanes Electric cars Consumer electronics Hoverboard

22 External short: accident Internal short: overcharge defects, charge at cold weather Fast release of battery electricity Battery temperature > C Exothermic decomposition of SEI Battery temperature >180 C Exothermic reaction of oxide cathode with electrolyte Thermal Runaway

23 Smart Separators for Battery Safety Hui Wu, Denys Zhuo, Yi Cui Nature Communications 5: 5193 (2014).

24 Battery Safety: Reversible Thermal Fuse Z. Chen, Y. Cui, Z. Bao Nature Energy (2016)

25 Ni Nanospikes coated with graphene Ni nanospikes mixed with polyethylene polymer Z. Chen, Y. Cui, Z. Bao Nature Energy (2016)

26 Reversible Thermal Fuse

27 Reversible Thermal Fuse Z. Chen, Y. Cui, Z. Bao Nature Energy (2016)

28 Impact of GCEP Funding Little US government funding on batteries Jan 2007, $1.6M 1 st GCEP Battery Project 100x external funding 60x 1) KAUST investigator 2) ONR Young Investigator 3) DOE EERE BMR Program - Si anode - S cathode - Li metal - Battery materials and characterization 4) Battery Hub (JCESR) 5) Battery 500 Consortium New efficient catalysts

29 Commercialization of Si Anodes from Cui Group 2007 Si nano anode invention in Cui group 2008 April, Amprius founded 2009 Feb, Series A $5M 2011 Mar, Series B $25M 2013 Dec, Series C $30M 2014 Wuxi City Joint Venture, Series D $40M, production 2016 More than a few million batteries sold in market Amprius Product Line: Gen 1: in production (2013), 650 Wh/L, 270 Wh/kg Gen 2: in production (2016), 750Wh/L, 280Wh/kg Gen 3: in pilot (2016), 900Wh/L, 360Wh/kg

30 Amprius, Sunnyvale Nanowire production tool Amprius, Wuxi Amprius, Nanjing

31 Battery500 Consortium Consortium Battery 500

32 Consortium Battery 500 Battery500 Consortium The Battery500 Consortium aims to triple the specific energy (to 500 WH/kg) relative to today's battery technology while achieving 1,000 electric vehicles cycles. The consortium aims to overcome the fundamental scientific barriers to extract the maximum capacity in electrode materials for next generation Li batteries. The consortium leverages advances in electrode materials and battery chemistries supported by DOE.

33 The People Executive Committee J. Virden, D. Schwartz, M. Hartney, G. Tynan, K. Adjemian, A. Harris Operation Deputy, M. Hartney Project Coordinator, N. Henderson Safety Manager, M. Gross IP Manager, P. Christiansen Director, Jun Liu Co-Director, Yi Cui Chief Scientist, A. Manthiram Advisory Board S. Chu(Stanford), JB Straubel(Tesla), W. Wilcke(IBM), auto industry Industry Committee Seedling project V. Subramanian/ X. Yang Keystone Project 1 Materials and Interfaces J. Zhang/S. Whittingham Keystone Project 2 Electrode Architecture E. Dufek/P. Liu Keystone Project 3 Cell Design and Integration V. Vishwanathan/J. Yang 500 Wh/kg 1000 cycles Industry Off-Ramp New Test Bed Spin Off

34 Using ideas from batteries to find better catalysts

35 Important Electrochemical Reactions HER: OER: 0 V 2 H e - H V 4OH - - 4e - 2 H 2 O + O 2 Pt, 0 V IrO 2, RuO 2, 1.5 V Searching for catalysts: - as efficient or better for HER, OER etc. - high abundance, low cost, robust - CO 2 reaction catalysts

36 Edge Terminated MoS 2 and MoSe C for 10 min MoS 2 MoSe 2 D. Kong, H. Wang, Y. Cui, Nano Lett. 13, 1341 (2013)

37 Chemical Potential Tuning of Electrocatalysts 1.23 V 4 OH e - 2 H 2 O + O 2 Chemical Potential MoS 2 Li + + e - 0 V 2 H e - H 2

38 Electrochemical Tuning of Catalysts Pristine 1.8V 1.5V 10 nm 1.2V 1.1V H. Wang, Z. Lu, Y. Cui PNAS 110, (2013)

39 Electrochemical Tuning of HER Catalysts H. Wang, Z. Lu, Y. Cui PNAS 110, (2013)

40 Bifunctional Catalyst for Overall Water Splitting Morphology tuning by Lithium conversion reaction MO x +2xLi M+xLi 2 O Example: CoO H. Wang, Y. Cui, Nature Communications 6, 7261, 2015.

41 Electrochemical Tuning of CoO H. Wang, Y. Cui, Nature Communications 6, 7261, 2015.

42 Same NiFeOx/CFP catalyst for both OER and HER in the same solution OER HER H. Wang, Y. Cui, Nature Communications 6, 7261, 2015.

43 Strain-tuning of catalysts

44 Using Battery Electrode to Tune Catalyst Strain LiCoO 2 tuning: generate 5% compression and 5% tension. H. Wang, F. Prinz, J. Norskov, Y. Cui (Science, in press, 2016)

45 H. Wang, F. Prinz, J. Norskov, Y. Cui (Science, in press, 2016)

46 Tuning the Pt Strain for ORR H. Wang, F. Prinz, J. Norskov, Y. Cui (Science, in press, 2016)

47 H. Wang, F. Prinz, J. Norskov, Y. Cui (Science, in press, 2016)

48 Future of Batteries High Energy Battery Cells 1) Graphite/NMC: ~300Wh/kg 2) Si/NMC: ~400Wh/kg 3) Li metal/nmc: ~500Wh/kg Li metal/sulfur: >500 Wh/kg Grid Scale Battery Cells 1) Aqueous batteries 2) Flow batteries 3) Li ion batteries

49 Acknowledgement Fundings - DOE EERE Vehicle Technology Office, BMR Program - JCESR (Joint Center for Energy Storage Research) - Battery 500 Consortium - GCEP Collaborators: - William Nix - Mike Toney (SLAC) - Zhenan Bao - Robert Huggins - Hongjie Dai - Steven Chu - Jens Norskov

50 Backup slides

51 Global reserve of lithium: 40 million ton Nissan Leaf, 24 kwh, 84 miles 4 kg Lithium 10 Billion Leaf Tesla S model, 85 kwh, 265 miles 14 kg Lithium 3 Billion Tesla There are ~1 billion cars in the world. In 2009, Li production: 92,000 ton, which is 23,000,000 Nissan Leaf. Ocean: 230,000 million ton (0.1778ppm)

52 World Electricity Consumption: ~4 TW Need TeraBattery for 6 hours: ~24 TWh Global reserve of lithium: 40 million ton Battery 240TWh

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54 Our GCEP Programs on Batteries : Nanowire Battery (Yi Cui, Fritz Prinz) : Prussian Blue Materials for Aqueous Batteries for Grid Scale Storage (Yi Cui, Robert Huggins) : Self-Healing Polymer Batteries (Zhenan Bao, Yi Cui)