batteries: now and future - mit energy initiative now and future yi cui department of materials...
TRANSCRIPT
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Batteries: Now and Future
Yi Cui Department of Materials Science and Engineering
Stanford University Stanford Institute for Materials and Energy Sciences
SLAC National Accelerator Laboratory
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Battery in iphone 6 plusMobile Phone Evolution
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Stationary Storage
Drone Electrical Vehicles
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~10 Wh 1 billion pieces/yr
~70Wh
~85,000Wh
CA, ~60 GWh World ~10 TWh
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How far can battery technology go?- Energy density (Wh/kg, Wh/L) - Cost ($/kWh) - Safety - Cycle life - Charge rate
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Lithium Ion Battery Cells: Now and Future Goals
Cost 150-200 (70) 300-500 (150) ($/kWh)
Energy ~200 (600) ~100 (300) (Wh/kg)
Safety
Cell level (goal) System level (goal)
Cycle life 3000 (10,000 for grid)
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High energy density (weight/volume) -Range increase -Lower cost
Revolution in Transportation, Grid, Renewable
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e− +M +← →⎯ M
How do We Store Electrons?
e− +M + +Host← →⎯ MHostM atomic weight
Li+ (7)
H+ (1)
Na+ (23)
Mg2+ (25)
Al3+ (27)
Zn2+ (65)
Pb2+/4+ (207)
M maximum voltage
Li+ (<4.5V)
H+ (<~1.5V)
Na+ (<4.2V)
Mg2+ (<~3.8V)
Al3+ (<~3.1V)
Zn2+ (<~2.2V)
Pb2+/4+ (<2.1V)
M cost ($/kg)
Li (40)*
H (nearly free)
Na (1)
Mg (2)
Al (2)
Zn (2)
Pb (2)
*The cost of Li in Li ion batteries is only ~3%.
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Battery Operation: Li Ion Batteries
9
(Courtesy of Venkat Srinivasan)
- Ionic diffusion in liquid and solid- Electron transport in solid
- Structure/volume change: strain
- Solid electrolyte intephase (SEI)
Materials issues of batteries
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High Energy Lithium Batteries
Graphite (2D): 370 mAh/g
Negative electrodes
Silicon: 4200 mAh/g
10X
Positive electrodes
LiMn2O4 (3D): 150 mAh/g
LiCoO2(2D) 150mAh/g
LiFePO4 (1D) 170mAh/g
10X
Sulfur ~1670 mAh/g
Li (3860 mAh/g) P (2600 mAh/g)
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0
1500
3000
4500
6000
C anode Si anode Li anode
LiCoO2Layer oxideLi2S or SAir
Cathode
Theo
retic
al S
peci
fic e
nerg
y (w
h/kg
)
3X
Theoretical Specific Energy
6X
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Quinone-based flow batteries
(M. Aziz, R. Gordon, A. Aspuru-Guzik Nature 505, 195 2014)
Li-polysulfide semiflow batteries
Y. Yang, G. Zheng, Y. Cui Energy Environ. Sci 2013,6, 1552-1558.
Liquid metal batteries D. Sadoway, JACS 134, 1895 (2012)
Semi-solid flow batteries Y.M Chiang, C. Carter Adv. Eng. Mater. 2011, 1, 511
Grid-Scale Storage Technology
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High Energy Batteries: Paradigm Shift
Stable Host: past 20 yearsUnstable Host: Now 3-10x specific charge capacity
No bond breaking Significant bonding breaking
Host atoms do not move Host atoms move
Volume change <10% Volume change ~100%
Little structure change Complete structure change
New challenges: - Atomic bonding level: reversibility - Individual material particle level: breaking, SEI, phases - The whole electrode level: expansion, breaking
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Outline
High Energy: - Si, P, Li metal anodes - S cathodes
Nature Nanotechnology 3, 31 (2008). Nature Nanotechnology 7, 310 (2012). Nature Communication 4: 1331 (2013). Nature Communication 4:1943 (2013). Nature Chemistry 5, 1042 (2013). Nature Nanotechnology 9, 187 (2014). Nature Nanotechnology 9, 618 (2014).
Battery SafetyNature Communications 5: 5193 (2014).
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Silicon Anodes With 11X Specific Capacity
For Si: volume expansion to 4 times
Break
Individual particle:
4200 mAh/g
370 mAh/g
Problems: 1) How to avoid breaking? 2) How to build stable solid-electrolyte-interphase (SEI)?
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In-situ Transmission Electron Microscopy (TEM)
(M. McDowell, C. Wang, Yi Cui, Nano Energy 1, 401, 2012)Nanofactory TEM-STM holder
2mm
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Fracture of Surface Cu Coatings
17 5x actual speed
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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))
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Gen 1: NanowireNature Nanotechnology 3, 31 (2008).
Gen 4: Double-walled hollowNature Nanotechnology 7, 310 (2012).
Gen 5: Yolk-shellNano Letters 12, 3315 (2012).
Gen 2: Core-Shell NanowireNano Letters 9, 491 (2009).
Gen 3: HollowNano Letters 11, 2949 (2011).
11 Generations of Si Anode Design from Cui Group
Gen 6: Si-hydrogelNature Communication 4:1943 (2013) with Zhenan Bao
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11 Generations of Si Anode Design from Cui Group
Gen 8: Pomegranate-LikeNature Nanotechnology 9, 187 (2014).
Gen 9: Non-filling carbon coating or porous SiACS Nano 9, 2540 (2015).
Gen 10: Prelithiation of Si anodes
Nature Communications 5, 5088, 2014
Gen 7: Self-HealingNature Chemistry 5, 1042 (2013). with Zhenan Bao
Gen 11: Micro-Si gaphene cage Nature Energy 15029, 2016
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Gen 4: Double Walled Hollow Structure: Stable Solid Electrolyte Interphase (SEI)
(Hui Wu, Yi Cui Nature Nanotech 7, 310 (2012))
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- Outer diameter has no change. - Inner diameter changes.
Double-Walled Si Nanotubes
(Hui Wu, Yi Cui Nature Nanotech 7, 310 (2012))
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0 cycle 200 cycle with SEI 200 cycle without SEI
0 cycle 200 cycle with SEI 200 cycle without SEI
0 cycle 2000 cycle with SEI 2000 cycle without SEI
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Ultralong Cycle Life of Si Nanotubes
12C rate
(Yi Cui Group Nature Nanotech 7, 310 (2012))
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Gen 8: Pomegranate-Like Si Batteries
N. Liu, Z. Lu, Y. Cui Nature Nanotech 9, 187 (2014).
- Reduce surface area - Increase mass loading - Dense packing
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Gen 8: Pomegranate-Like Si Batteries
N. Liu, Z. Lu, Y. Cui Nature Nanotech 9, 187 (2014).
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Gen 8: Pomegranate-Like Si Batteries
99.87%
N. Liu, Z. Lu, Y. Cui Nature Nanotech 9, 187 (2014).
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Micron Si Particles as Anodes
(Y. Li, K. Yan, Y. Cui Nature Energy 15029, 2016)
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(Y. Li, K. Yan, Y. Cui Nature Energy 15029, 2016)
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Amorphous carbon cage
Graphene cage
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(Y. Li, K. Yan, Y. Cui Nature Energy 15029, 2016)
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Lithium IonGraphite LiC6Electron
~10 % Volume change
Lithium IonSilicon Li4.4SiElectron
~300 %
Host: Graphite, Si No Host: Li metal, electroplating
Flat film
Dendrite
Lithium Ion Electron
Infinite
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Nanoscale Interfacial Materials Design
Guangyuan Zheng, Steven Chu, Yi Cui . Nature Nanotechnology 9, 618 (2014).
Stable interfacial design using nanomaterials: chemically and mechanically stable
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Guangyuan Zheng, Steven Chu, Yi Cui . Nature Nanotechnology 9, 618 (2014).
Interconnected Hollow Carbon Sphere Fabrication
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Control experiment
After Li metal electrodeposition
Guangyuan Zheng, Steven Chu, Yi Cui . Nature Nanotechnology 9, 618 (2014).
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Guangyuan Zheng, Steven Chu, Yi Cui . Nature Nanotechnology 9, 618 (2014).
1 M LiTFSI in DOL:DME w/ 2% LiNO3
CE: 99%
CE: 98.5%
CE: 97.5%
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Do we understand how Li metal nucleates on different substrate?
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40 mV overpotential
K Yan, S. Chu, Y. Cui Nature Energy (March, 2016)
1 M LiPF6 in EC:DEC
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Phase Diagrams of Li-Cu and Li-Au
Cu has negligible solubility in Li. Au has some solubility in Li.
K Yan, S. Chu, Y. Cui Nature Energy (March, 2016)
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K Yan, S. Chu, Y. Cui Nature Energy (March, 2016)
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K Yan, S. Chu, Y. Cui Nature Energy (March, 2016)
Seeded Li Metal Deposition fro Spatial Control
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Nanocapsule as a “Host” for Lithium Metal
K Yan, S. Chu, Y. Cui Nature Energy (March, 2016)
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K Yan, S. Chu, Y. Cui Nature Energy (March, 2016)
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In-situ TEM
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Tesla S model, 85 kWh, 265 miles 14 kg Lithium
3 Billion TeslaNissan Leaf, 24 kWh, 84 miles
4 kg Lithium
10 Billion Leaf
Global reserve of lithium: 40 million ton
Ocean: 230,000 million ton (0.1778ppm)
In 2009, Li production: 92,000 ton, which is 23,000,000 Nissan Leaf.
There are ~1 billion cars in the world.
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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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Z. Chen, Y. Cui, Z. Bao Nature Energy (2016)
Battery Safety: Reversible Thermal Fuse
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Ni Nanospikes coated with graphene
Ni nanospikes mixed with polyethylene polymer
Z. Chen, Y. Cui, Z. Bao Nature Energy (2016)
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Reversible Thermal Fuse
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Reversible Thermal Fuse
Z. Chen, Y. Cui, Z. Bao Nature Energy (2016)
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Lithium Ion Battery Cells: Now and Future Goals
Cost 150-200 (70) 300-500 (150) ($/kWh)
Energy ~200 (600) ~100 (300) (Wh/kg)
Safety
Cell level (goal) System level (goal)
Cycle life 3000 (10,000 for grid)
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Acknowledgement
Funding - DOE EERE Vehicle Program, BMR - JCESR (Joint Center for Energy Storage Research) - Global Climate & Energy Projects (Stanford) - Precourt Institute for Energy (Stanford) - ONR Young Investigator
Collaborators: - William Nix - Mike Toney (SLAC) - Zhenan Bao - Robert Huggins - Steven Chu