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Wiring Up Silicon Nanostructures for High Energy
Lithium Ion Battery Anodes
Yi Cui Stanford University
May 15, 2013 Project ID #ES148
This presentation does not contain any proprietary, confidential, or otherwise restricted information
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• Start: Jan 1, 2011 • End: Dec. 31, 2014 • Percent complete: 60%
Barriers of batteries - Low energy density - High cost - Cycle and calendar life Targets: high energy electrode
materials and cells
• Total project funding $1,200k from DOE • Funding received in FY12 $300k • Funding for FY13 $300k
Timeline
Budget
Barriers
• Collaboration - BATT program PI’s - PNNL: In-situ TEM - SLAC: In-situ X-ray - UT Austin: Prof. Korgel,materials - Stanford: Prof. Nix, mechanics;
Prof. Bao, materials. - Amprius Inc.
Partners
Overview
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Project Objective and Relevance
Objective - To develop Si anodes with 10x specific charge capacity to replace the existing C anodes for high energy Li ion batteries for transportation, relevant to VT Program. - To Understand and design nanostructure Si can address the challenging issues caused by the large volumetric expansion and provide a good cycle life. - To Develop scalable low-cost methods for nanostructured Si anodes.
Si: 4200 mAh/g, 10X of carbon
Si Li4.4Si
For Si: volume expansion by 4 times
Break
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Milestones for FY12 and 13 Month/year Milestones
9/2011 Find out the relationship of critical breaking size versus capacity for deep lithiation . Identify a method to produce hollow silicon structure. (completed)
3/2012 Obtain detailed information on the volume expansion and contraction of Si. Fabricate hollow anodes with high reversible capacity and high Coulombic efficiency (Completed)
6/2012 Determine effect of hollow structure on volume expansion, compared to non-hollow nanostructures (completed)
10/2012 Optimize nanostructured Si for long cycle life (>1000 cycles). (completed)
12/2012 Go-no go
Start to develop scalable and low-cost nano-Si with the identified materials design rules. (completed)
3/2013
Develop low cost and scalable Si yolk-shell nanostructures with stable cycle life (completed)
5/2013 Develop low-cost synthesis of Si nanoparticles from renewable sources (on-schedule)
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Approach/Strategy Advanced nanostructured Si materials design and synthesis
Structure and property characterization - Ex-situ transmission electron microscopy - In-situ transmission electron microscopy - Ex-situ scanning electron microscopy
Electrochemical testing - Coin cells and pouch cells. - A set of electrochemical techniques.
5 µm 500nm 400 nm
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Previous Results on Silicon Nanowire Anodes
Cui group, Nature Nanotechnology 3, 31 (2008).
Cui group Nano Letters 9, 491 (2009).
Crystal-amorphous Si core-shell nanowires
Cui group Nano Letters 9, 3370 (2009).
Carbon-silicon core-shell nanowires
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(Cui group, Nano Letters 11, 3034 (2011))
Accomplishment
200nm
500 nm
Discovering anisotropic expansion of crystalline Si upon lithiation
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500 nm
Accomplishment
- Identified critical breaking size: 240 ~ 360 nm
- Discovered fast charging enhances fracture
Cui group, Proc. Natl. Acad. Sci. U.S.A., 109, 4080 (2012).
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Accomplishment Discovering anisotropic fracture of crystalline Si
Cui group, Proc. Natl. Acad. Sci. U.S.A., 109, 4080 (2012).
500 nm
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8% decay per 100 cycles
0 cycle 40 cycle 700 cycles
Accomplishment Developed hollow Si nanophere anodes
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Designing double walled hollow Si structures to address - Mechanical breaking - Solid Electrolyte Interphase (SEI)
Accomplishment
(Hui Wu, Yi Cui Nature Nanotech 7, 310 (2012))
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Synthesis and Characterization of Double-Walled Si Nanotubes
Accomplishment
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- Outer diameter has no change. - Inner diameter changes.
Characterization of Double-Walled Si Nanotubes by ex-situ transmission electron microscopy
Accomplishment
(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
Accomplishment: Comparison Study
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Accomplishment
12C rate
High performance double-walled Si nanotubes
(Hui Wu, Yi Cui Nature Nanotech 7, 310 (2012))
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Successfully designed and synthesized Si yolk-shell structure with long cycle life for low-cost and scalable anodes.
N. Liu, M. McDowell, Yi Cui, Nano Letters 12, 3315 (2012).
Accomplishment
C/10 for 1st cycle, C/3 for 10 cycles, 1C for the rest)
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N. Liu, M. McDowell, Yi Cui, Nano Letters 12, 3315 (2012).
Video of In-situ TEM
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Collaboration and Coordination
- PNNL: In-situ TEM, Dr. C. Wang - SLAC: In-situ X-ray, Dr. M. Toney - UT Austin: Prof. Korgel, a-Si materials - Stanford: Prof. Nix, mechanics; Prof. Bao,
polymer materials - Companies: Amprius Inc.
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Proposed Future Work
- Further understand the nanoscale design to optimize Si anodes, for example, the ratio of Si material dimension vs porosity/hollow space . - Further develop scalable and low-cost method for synthesizing nano-Si with desired performance. - Test the Si electrodes with high areal mass loading up to 2-3mg/cm2. - Develop surface modification to increase the first cycle coulombic efficiency >90% and improve the later cycle coulombic efficiency.
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• Objective and Relevance: The goal of this project is to develop high capacity Si anodes with nanomaterials design to enable high energy batteries, highly relevant to the VT Program goal.
• Approach/Strategy: This project combines advanced nanosynthesis, characterization and battery testing, which has been demonstrated to be highly effective.
• Technical Accomplishments and Progress: The project has produced many significant results, meeting milestones. They include identifying the fundamental materials design principles, synthesizing and testing, and developing low-cost and scalable methods. The results have been published in top scientific journal. The PI has received numerous invitations to speak in national and international conferences.
• Collaborations and Coordination: The PI has established a number of highly effective collaboration.
• Proposed Future Work: Rational and exciting future has been planned.
Summary