崔屹：锂电池Si负极11代纳米技术！

纳米人

2018-05-29

对于锂离子电池而言，Si负极比传统石墨负极比容量大10倍，在这个能源短缺的时代，Si负极锂离子电池技术前景诱人。但是体相Si颗粒至少存在以下两大问题，影响电学传导，并造成容量降低，最终导致电池失效，大大缩短了电池的使用寿命：

1）充放电过程中体积膨胀高达420%，容易导致颗粒和电机的破裂。

2）充放电过程中发生副反应，形成不稳定、不导电的固体电解质界面SEI膜。

崔屹团队多年来致力于应用纳米技术改善锂离子电池的硅负极性能，根据崔屹教授的讲座，本文简要整理了他们开发的11代硅负极电池纳米技术。

1. Nanowire

    解决了体积变化的问题

参考文献：C. K. Chan, H. Peng, G. Liu, K. McIlwrath, X. F. Zhang, R. A. Huggins, Y. Cui "High Performance Lithium Battery Anodes Using Silicon Nanowires" Nature Nanotech. 2008, 3, 31-35.

2. core-shell nanowire

提高循环寿命

参考文献：L.-F. Cui, R. Ruffo, C. K. Chan, H. Peng, Y. Cui "Crystalline-Amorphous Core-Shell Silicon Nanowires for High Capacity and High Current Battery Electrodes" Nano Lett. 9, 2009, 491-495.

3. Hollow

进一步解决体积变化问题，提高循环性能

参考文献：Y. Yao, M. T. McDowell, I. Ryu, H. Wu, N. Liu, L. Hu, W. D. Nix, and Y. Cui, "Interconnected Silicon Hollow Nanospheres for Lithium-Ion BatteryAnodes with Long Cycle Life ", Nano Letters ,2011.

4. Double Walled Hollow

稳定的SEI膜

参考文献：H. Wu, G. Chan, J. W. Choi, I. Ryu, Y. Yao, M. T. McDowell, S. W. Lee, A. Jackson, Y. Yang, L. Hu and Y. Cui, "Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control,"  Nature Nanotechnology , 2012.

5. Yolk-Shell

高容量(∼2800 mAh/g，C/10), 高循环性 (1000 cycles，74% 容量保持率), 以及高库伦效率(99.84%)的统一。

参考文献：N. Liu, H. Wu, M. T. McDowell, Y. Yao, C. Wang, and Y. Cui. "A Yolk-Shell Design for Stabilized and Scalable Li-Ion Battery Alloy Anodes,"  Nano Letters , 2012.

6. Si hydrogel

提高导电性，可规模化制备，

参考文献：H. Wu, G. Yu, L. Pan, N. Liu, M. T. McDowell, Z. Bao, and Y. Cui, "Stable Li-ion battery anodes by in-situ polymerization of conducting hydrogel to conformally coat silicon nanoparticles," Nature Communications, 2013.

7. Self-healing

微米Si颗粒，提高循环寿命

参考文献：C. Wang, H. Wu, Z. Chen, M. T. McDowell, Y. Cui, and Z. Bao, "Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries," Nature Chemistry, 2013, 5, 1042-1048 .

8. Pomegranate-Like

提高堆密度

参考文献：N. Liu, Z. Lu, J. Zhao, M. T. McDowell, H. W. Lee, W. Zhao, and Y. Cui, "A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes", Nature Nanotechnology, 2014, 9, 187-192.

9. Porous Si

微米Si颗粒，稳定的SEI膜

参考文献：Z. Lu, N. Liu, H.-W. Lee, J. Zhao, W. Li, Y. Li, and Y. Cui, "Nonfilling Carbon Coating of Porous Silicon Micrometer-Sized Particles for High-Performance Lithium Battery Anodes", ACS Nano， 2015.

10. Prelithiation of Si Anodes

解决了第一次循环导致的容量损失问题

参考文献：J. Zhao, Z. Lu, N. Liu, H.-W. Lee, M. T. McDowell, and Y. Cui, "Dry-air-stable lithium silicide-lithium oxide core-shell nanoparticles as high-capacity prelithiation reagents", Nature Communications, 2014.

11. Micro Si-Graphene Cage

微米Si纳米颗粒，优异的导电性、机械稳定性和化学稳定性，稳定的SEI膜，长期的循环寿命得到统一

参考文献：Y. Li, K.Yan, H.-W. Lee, Z. Lu, N. Liu, and Y. Cui, "Growth of conformal graphene cages on micrometre-sized particles as stable battery anodes", Nature Energy, 2016, 1, 15029.

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