Improvement of the Anode Properties of Lithium-Ion Batteries for SiO x with a Third Element

Tomoki Hirono; Hiroyuki Usui; Yasuhiro Domi; Wataru Irie; Toshiyuki Sawada; Hiroki Sakaguchi

doi:10.1021/acsomega.1c05689

Improvement of the Anode Properties of Lithium-Ion Batteries for SiO _x with a Third Element

ACS Omega. 2021 Dec 21;7(1):1223-1231. doi: 10.1021/acsomega.1c05689. eCollection 2022 Jan 11.

Authors

Tomoki Hirono^{1

2

3}, Hiroyuki Usui^{1

2}, Yasuhiro Domi^{1

2}, Wataru Irie^{4

2}, Toshiyuki Sawada³, Hiroki Sakaguchi^{1

2}

Affiliations

¹ Department of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University, 4-101 Minami, Koyama-cho, Tottori 680-8552, Japan.
² Center for Research on Green Sustainable Chemistry, Tottori University, 4-101 Minami, Koyama-cho, Tottori 680-8552, Japan.
³ Sanyo Special Steel Co., Ltd., 3007, Nakashima, Shikama-ku, Himeji, Hyogo 672-8677, Japan.
⁴ Course of Chemistry and Biotechnology, Department of Engineering, Graduate School of Sustainability Science, Tottori University, 4-101 Minami, Koyama-cho, Tottori 680-8552, Japan.

Abstract

Silicon oxide (SiO _x ) has been placed into practical use as an anode active material for next-generation Li-ion batteries because it has a higher theoretical capacity than graphite anodes. However, the synthesis method is typically vapor deposition, which is expensive, and the poor electron conductivity of SiO _x restricts high performance. In this study, we prepared M/SiO _x active materials consisting of SiO _x and a third element (M = Al, B, Sn) using a low-cost mechanical milling (MM) method and investigated their electrode properties as Li-ion battery anodes. Also, the authors added a third element to improve the conductivity of the SiO₂ matrix. Al, B, and Sn were selected as elements that do not form a compound with Si, exist as a simple substance, and can be dispersed in SiO₂. As a result, we confirmed that SiO _x has a nanostructure of nanocrystalline Si dispersed in an amorphous-like SiO₂ matrix and that the third element M exists not in the nanocrystalline Si but in the SiO₂ matrix. The electron conductivity of SiO _x was improved by the addition of B and Sn. However, it was not improved by the addition of Al. This is because Al₂O₃ was formed in the insulator due to the oxidization of Al. The charge-discharge cycle tests revealed that the cycle life was improved from 170 cycles to 330 or 360 cycles with the addition of B or Sn, respectively. The improvement in electron conductivity is assumed to make it possible for SiO₂ to react with Li ions more uniformly and form a structure that can avoid the concentration of stress due to the volume changes of Si, thereby suppressing the electrode disintegration.