Regulating the kinetics of zinc-ion migration in spinel ZnMn2O4 through iron doping boosted aqueous zinc-ion storage performance

Feiran Chen; Yan Zhang; Shuai Chen; Hu Zang; Changjiang Liu; Hongxia Sun; Baoyou Geng

doi:10.1016/j.jcis.2023.06.152

Regulating the kinetics of zinc-ion migration in spinel ZnMn₂O₄ through iron doping boosted aqueous zinc-ion storage performance

J Colloid Interface Sci. 2023 Nov:649:703-712. doi: 10.1016/j.jcis.2023.06.152. Epub 2023 Jun 24.

Authors

Feiran Chen¹, Yan Zhang¹, Shuai Chen¹, Hu Zang¹, Changjiang Liu¹, Hongxia Sun¹, Baoyou Geng²

Affiliations

¹ College of Chemistry and Materials Science, The Key Laboratory of Functional Molecular Solids, Ministry of Education, The Key Laboratory of Electrochemical Clean Energy of Anhui Higher Education Institutes, Anhui Provincial Engineering Laboratory for New-Energy Vehicle Battery Energy-Storage Materials, Anhui Normal University, Wuhu 241002, China.
² College of Chemistry and Materials Science, The Key Laboratory of Functional Molecular Solids, Ministry of Education, The Key Laboratory of Electrochemical Clean Energy of Anhui Higher Education Institutes, Anhui Provincial Engineering Laboratory for New-Energy Vehicle Battery Energy-Storage Materials, Anhui Normal University, Wuhu 241002, China; Institute of Energy, Hefei Comprehensive National Science Center, Anhui, Hefei 230031, China. Electronic address: bygeng@mail.ahnu.edu.cn.

PMID: 37385035
DOI: 10.1016/j.jcis.2023.06.152

Abstract

Spinel ZnMn₂O₄ with a three-dimensional channel structure is one of the important cathode materials for aqueous zinc ions batteries (AZIBs). However, like other manganese-based materials, spinel ZnMn₂O₄ also has problems such as poor conductivity, slow reaction kinetics and structural instability under long cycles. Herein, ZnMn₂O₄ mesoporous hollow microspheres with metal ion doping were prepared by a simple spray pyrolysis method and applied to the cathode of aqueous zinc ion battery. Cation doping not only introduces defects, changes the electronic structure of the material, improves its conductivity, structural stability, and reaction kinetics, but also weakens the dissolution of Mn²⁺. The optimized 0.1 % Fe-doped ZnMn₂O₄ (0.1% Fe-ZnMn₂O₄) has a capacity of 186.8 mAh g^-1 after 250 charge-discharge cycles at 0.5 A g^-1 and the discharge specific capacity reaches 121.5 mAh g^-1 after 1200 long cycles at 1.0 A g^-1. The theoretical calculation results show that doping causes the change of electronic state structure, accelerates the electron transfer rate, and improves the electrochemical performance and stability of the material.

Keywords: Aqueous zinc ion battery; Fe doping; Hollow mesoporous microspheres; ZnMn(2)O(4).