A Highly-Lithiophilic Mn3O4/ZnO-Modified Carbon Nanotube Film for Dendrite-Free Lithium Metal Anodes

Yuting Zhu; Yunfei Yang; Huimin Zhang; Shuxuan Liu; Zhuorun Wu; Chengkai Wu; Xuehui Gao; Enlai Hu; Zhongwei Chen

doi:10.1016/j.jcis.2023.05.101

A Highly-Lithiophilic Mn₃O₄/ZnO-Modified Carbon Nanotube Film for Dendrite-Free Lithium Metal Anodes

J Colloid Interface Sci. 2023 Oct 15:648:299-307. doi: 10.1016/j.jcis.2023.05.101. Epub 2023 May 20.

Authors

Yuting Zhu¹, Yunfei Yang¹, Huimin Zhang¹, Shuxuan Liu¹, Zhuorun Wu¹, Chengkai Wu¹, Xuehui Gao², Enlai Hu³, Zhongwei Chen⁴

Affiliations

¹ Department of Chemistry, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua 321004, China.
² Department of Chemistry, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua 321004, China. Electronic address: gxh0357@zjnu.edu.cn.
³ Department of Chemistry, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua 321004, China. Electronic address: huenlai@zjnu.edu.cn.
⁴ Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L 3G1, Canada. Electronic address: zhwchen@uwaterloo.ca.

PMID: 37301154
DOI: 10.1016/j.jcis.2023.05.101

Abstract

Lithium metal anode is deemed as a potential candidate for high energy density batteries, which has attracted increasing attention. Unfortunately, Li metal anode suffers from issues such as dendrite grown and volume expansion during cycling, which hinders its commercialization. Herein, we designed a porous and flexible self-supporting film comprising of single-walled carbon nanotube (SWCNT) modified with a highly-lithiophilic heterostructure (Mn₃O₄/ZnO@SWCNT) as the host material for Li metal anodes. The p-n-type heterojunction constructed by Mn₃O₄ and ZnO generates a built-in electric field that facilitates electron transfer and Li⁺ migration. Additionally, the lithiophilic Mn₃O₄/ZnO particles serve as the pre-implanted nucleation sites, dramatically reducing the lithium nucleation barrier due to their strong binding energy with lithium atoms. Moreover, the interwoven SWCNT conductive network effectively lowers the local current density and alleviates the tremendous volume expansion during cycling. Thanks to the aforementioned synergy, the symmetric cell composed of Mn₃O₄/ZnO@SWCNT-Li can stably maintain a low potential for more than 2500 h at 1 mA cm^-2 and 1 mAh cm^-2. Furthermore, the Li-S full battery composed of Mn₃O₄/ZnO@SWCNT-Li also shows excellent cycle stability. These results demonstrate that Mn₃O₄/ZnO@SWCNT has great potential as a dendrite-free Li metal host material.