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Understanding the Li diffusion mechanism and positive effect of current collector volume expansion in anode free batteries

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Chinese Physics B 2020年第6期29卷 17-24页

作者： Yan Zhuang Zheyi Zou Bo Lu Yajie Li Da Wang Maxim Avdeev Siqi Shi State Key Laboratory of Advanced Special Steel Shanghai Key Laboratory of Advanced FerrometallurgySchool of Materials Science and EngineeringShanghai UniversityShanghai 200444China Materials Genome Institute Shanghai UniversityShanghai 200444China Shanghai Institute of Applied Mathematics and Mechanics School of Mechanics and Engineering ScienceShanghai UniversityShanghai 200444China Shanghai Key Laboratory of Mechanics in Energy Engineering Shanghai UniversityShanghai 200444China Australian Nuclear Science and Technology Organisation Locked Bag 2001Kirrawee DC NSW 2232Australia School of Chemistry The University of SydneySydney 2006Australia

In anode free batteries(AFBs), the current collector acts as anode simultaneously and has large volume expansion which is generally considered as a negative effect decreasing the structural stability of a battery. Moreover, despite many studies on the fast lithium diffusion in the current collector materials of AFB such as copper and aluminum, the involved Li diffusion mechanism in these materials remains poorly understood. Through first-principles calculation and stress-assisted diffusion equations, here we study the Li diffusion mechanism in several current collectors and related alloys and clarify the effect of volume expansion on Li diffusion respectively. It is suggested that due to the lower Li migration barriers in aluminum and tin, they should be more suitable to be used as AFB anodes, compared to copper, silver, and lead. The Li diffusion facilitation in copper with a certain number of vacancies is proposed to explain why the use of copper with a thickness≤100 nm as the protective coating on the anode improves the lifetime of the batteries. We show that the volume expansion has a positive effect on Li diffusion via mechanical–electrochemical coupling. Namely, the volume expansion caused by Li diffusion will further induce stress which in turn affects the diffusion. These findings not only provide in-depth insight into the operating principle of AFBs, but also open a new route toward design of improved anode through utilizing the positive effect of mechanical–electrochemical coupling.

关键词： anode free battery current collector Li diffusion mechanism mechanical-electrochemical coupling stress-assisted diffusion

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