车用动力锂离子电池纳米硅/碳负极材料的制备技术与发展

doi:10.11896/cldb.19020040

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Abstract With the increasing environmental and energy problems, traditional cars are gradually moving toward new energy. Lithium-ion batteries are considered to be one of the most promising new energy vehicle powers due to their high discharge voltage platform, low self-discharge rate and friendly environment. However, with the increasing demand for the driving distance of new energy vehicles, improving the energy density of batteries has become a hot topic. Therefore, improving the energy density of batteries for pure electric vehicles and developing high energy density positive and negative materials are one of the research directions of batteries. At present, the cathode materials of commercial pure electric vehicles are mainly LiFePO₄ and Li(Ni_xCo_yMn_1-x-y)O. The anode material is graphite. This type of battery has an energy density of only 200—300 Wh·kg^-1. Silicon has a high theoretical specific capacity of 4 200 mAh·g^-1, which is one of the most promising anode materials for high energy density lithium ion batteries.
However, the dramatic volume change of silicon in the charge and discharge reaction hinders the commercial application of silicon materials. The alloying reaction of silicon can store lithium ions. The alloying reaction provides a high specific capacity accompanied by a 300% volume expansion. A drastic volume change causes the active material to fall off, and the SEI film continues to form, which causes a rapid decay of the battery capacity in actual use. In addition, pure silicon is a semiconductor with low intrinsic carrier concentration, so it can not meet the requirements for conductivity.
The most common methods for the above problems are listed below: (ⅰ) Synthesis of nano-sized silicon. The diffusion of lithium ions in solids is difficult. Although with the help of the electric field, the diffusion rate of lithium ions in silicon is still very slow. Silicon nanocrystallization can shorten the diffusion distance of lithium ions from the silicon surface to the center, which effectively shortens the battery charging time. (ⅱ) Pre-paration of silicon/carbon composite. Carbon materials have good cycle stability and electrical conductivity. If silicon is combined with carbon, carbon can buffer the volumetric change of silicon in the alloying reaction and increase the electronic conductivity of the negative electrode. The outer carbon shell can prevent direct contact between silicon and electrolyte to form a stable SEI film. (ⅲ) Design the microstructure of the material. Special structures such as hollow core-shell structure and 3D porous structure can alleviate the volume expansion effect of silicon, which will effectively inhibit the falling off of the electrode material. The above three methods are often used in combination to prepare high-performance nano-sized silicon/carbon anode materials, such as 3D porous nano-silicon/carbon materials, hollow core-shell nano-silicon/carbon materials.
This paper first explains the electrochemical reaction mechanism and the reasons for capacity decay of silicon-lithium alloys. Next, the preparation method of nano-sized silicon is given. Then, the common modification methods of silicon/carbon composites are reviewed from surface coa-ting, structure preparation, doping and MOF modification. Furthermore, the advantages of hollow core-shell structure and porous structure in improving electrochemical performance are analyzed. Finally, this paper summarizes the advantages and disadvantages of nano-silicon/carbon as a negative electrode material and analyzes the performance differences and causes of different covering materials, different coating methods and different ion doping. The key point in nano-silicon/carbon industrialization is proposed and the fascinating application prospect of nano-silicon/carbon is envisioned in pure electric vehicles.

Key words： silicon carbon anode electrode Li-ion battery high energy density coating and doping silicon based material

Published: 10 April 2020

CLC number:

TM912. 6

Fund:This work was financially supported by National Basic Research (973 Program) Project (2015CB931901), Shanghai High-tech Field Project (18511110000) and Shanghai Major Projects (18JC1410604).

About author:: Limin Zhaoreceived his B.S. degree in Harbin Institute of Technology in 2017. He is pursuing his M.S. degree at Shanghai Jiao Tong University. His research focused on silicon-carbon materials for lithium-ion batteries, and the supervisors were Prof. Dannong He and Fang Zhang.
Fang Zhangreceived her Ph.D. degree in Shanghai Jiao Tong University. She has been doing researches on the industrialization of cathode and anode materials, separators and electrolytes for lithium-ion batteries for a long time.
Dannong Heis a professor and doctoral supervisor in Shanghai Jiao Tong University. His main research direction is the design and application of nano-scale devices.

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Cite this article:

ZHAO Limin,WANG Huiya,XIE Qifei, et al. Preparation and Development of Nano-sized Si/C Anode Material for Li-ion Battery Used in Vehicle[J]. Materials Reports, 2020, 34(7): 7026-7035.

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http://www.mater-rep.com/EN/10.11896/cldb.19020040 OR http://www.mater-rep.com/EN/Y2020/V34/I7/7026

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