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Chin. Phys. B, 2020, Vol. 29(6): 068202    DOI: 10.1088/1674-1056/ab943c
Special Issue: SPECIAL TOPIC — Advanced calculation & characterization of energy storage materials & devices at multiple scale
SPECIAL TOPIC—Advanced calculation & characterization of energy storage materials & devices at multiple scale Prev   Next  

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

Yan Zhuang(庄严)1, Zheyi Zou(邹喆乂)1, Bo Lu(吕浡)3,4, Yajie Li(李亚捷)1, Da Wang(王达)1, Maxim Avdeev5,6, Siqi Shi(施思齐)1,2
1 State Key Laboratory of Advanced Special Steel, Shanghai Key Laboratory of Advanced Ferrometallurgy, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China;
2 Materials Genome Institute, Shanghai University, Shanghai 200444, China;
3 Shanghai Institute of Applied Mathematics and Mechanics, School of Mechanics and Engineering Science, Shanghai University, Shanghai 200444, China;
4 Shanghai Key Laboratory of Mechanics in Energy Engineering, Shanghai University, Shanghai 200444, China;
5 Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC NSW 2232, Australia;
6 School of Chemistry, The University of Sydney, Sydney 2006, Australia

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.

Keywords:  anode free battery      current collector      Li diffusion mechanism      mechanical-electrochemical coupling      stress-assisted diffusion  
Received:  09 March 2020      Revised:  16 May 2020      Accepted manuscript online: 
PACS:  82.47.Aa (Lithium-ion batteries)  
  66.30.-h (Diffusion in solids)  
  81.40.Jj (Elasticity and anelasticity, stress-strain relations)  
  47.11.St (Multi-scale methods)  

Project supported by the National Natural Science Foundation of China (Grant Nos. 11874254, 51802187, and 51622207), Shanghai Sailing Program, China (Grant No. 18YF1408700), Shanghai Pujiang Program, China (Grant No. 2019PJD016), Open Project of the State Key Laboratory of Advanced Special Steel, Shanghai University, China (Grant No. SKLASS2018-01), the Project of the State Key Laboratory of Advanced Special Steel, Shanghai University, China (Grant No. SKLASS2019-Z023), and the Science and Technology Commission of Shanghai Municipality, China (Grant No. 19DZ2270200).

Corresponding Authors:  Siqi Shi     E-mail:

Cite this article: 

Yan Zhuang(庄严), Zheyi Zou(邹喆乂), Bo Lu(吕浡), Yajie Li(李亚捷), Da Wang(王达), Maxim Avdeev, Siqi Shi(施思齐) Understanding the Li diffusion mechanism and positive effect of current collector volume expansion in anode free batteries 2020 Chin. Phys. B 29 068202

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