Achieving highly reversible zinc metal anode via surface termination chemistry

Yu Liu; Shulin Chen; Hao Yuan; Fangyu Xiong; Qin Liu; Yongkang An; Jianyong Zhang; Lu Wu; Jianguo Sun; Yong-Wei Zhang; Qinyou An; John Wang

doi:10.1016/j.scib.2023.09.034

Achieving highly reversible zinc metal anode via surface termination chemistry

Sci Bull (Beijing). 2023 Dec 15;68(23):2993-3002. doi: 10.1016/j.scib.2023.09.034. Epub 2023 Sep 25.

Authors

Yu Liu¹, Shulin Chen², Hao Yuan³, Fangyu Xiong², Qin Liu², Yongkang An², Jianyong Zhang², Lu Wu², Jianguo Sun⁴, Yong-Wei Zhang³, Qinyou An⁵, John Wang⁶

Affiliations

¹ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China; Department of Materials Science and Engineering, National University of Singapore, Singapore 117574, Singapore.
² State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China.
³ Institute of High Performance Computing, Agency for Science, Technology and Research (A*Star), Singapore 138632, Singapore.
⁴ Department of Materials Science and Engineering, National University of Singapore, Singapore 117574, Singapore. Electronic address: sjg07@nus.edu.sg.
⁵ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China. Electronic address: anqinyou86@whut.edu.cn.
⁶ Department of Materials Science and Engineering, National University of Singapore, Singapore 117574, Singapore; Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research (A*Star), Singapore 138634, Singapore. Electronic address: msewangj@nus.edu.sg.

PMID: 37858408
DOI: 10.1016/j.scib.2023.09.034

Abstract

An oxidation layer on a Zn surface is considered to play a negative role in hindering the practical applications of aqueous zinc ion batteries (AZBs). Herein, we demonstrate the importance of Zn-surface termination on the overall electrochemical behavior of AZBs by revisiting the well-known bottleneck issues. Experimental characterizations in conjugation with theoretical calculations reveal that the formation of a dense Zn₄(OH)₆SO₄·xH₂O (ZSH) layer from the well-designed surface-oxide termination layer improves the interface stability of the Zn anode and reduces the dehydration energy of Zn(H₂O)₆²⁺, thereby accelerating the interface transport kinetics of Zn²⁺. Moreover, instead of directly diffusing over the ZSH layer, a new "edge dehydration-along edge transfer" mechanism of Zn²⁺ is discovered. Owing to the presence of a Zn anode with a ZnO-derived ZSH layer, an ultrahigh stability of over 1200 h with a high cumulative-plated capacity of 6.24mAh cm^-² is achieved with a symmetrical cell. Furthermore, high cycling stability (over 1000 cycles) and Coulombic efficiency (99.07%) are obtained in the entire AZBs with a MnO₂ cathode. An understanding of the oxygen surface termination mechanism is beneficial to Zn-anode protection and is a timely forward step toward the long-pursued practical application of AZBs.

Keywords: Dendrite-free; Solid electrolyte interphase; Zn Anode; Zn ion battery; Zn-O termination.