Reconstructing interfacial manganese deposition for durable aqueous zinc-manganese batteries

Yida Hu; Zhexuan Liu; Lanyan Li; Shan Guo; Xuefang Xie; Zhigao Luo; Guozhao Fang; Shuquan Liang

doi:10.1093/nsr/nwad220

Reconstructing interfacial manganese deposition for durable aqueous zinc-manganese batteries

Natl Sci Rev. 2023 Aug 16;10(10):nwad220. doi: 10.1093/nsr/nwad220. eCollection 2023 Oct.

Authors

Yida Hu¹, Zhexuan Liu¹, Lanyan Li², Shan Guo¹, Xuefang Xie³, Zhigao Luo⁴, Guozhao Fang¹, Shuquan Liang¹

Affiliations

¹ School of Materials Science and Engineering, Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan Province, Central South University, Changsha 410083, China.
² School of Science, Hunan University of Technology and Business, Changsha 410205, China.
³ College of Physical Science and Technology, Xinjiang University, Urumqi 830046, China.
⁴ College of Chemistry, Xiangtan University, Xiangtan 411105, China.

Abstract

Low-cost, high-safety, and broad-prospect aqueous zinc-manganese batteries (ZMBs) are limited by complex interfacial reactions. The solid-liquid interfacial state of the cathode dominates the Mn dissolution/deposition process of aqueous ZMBs, especially the important influence on the mass and charge transfer behavior of Zn²⁺ and Mn²⁺. We proposed a quasi-eutectic electrolyte (QEE) that would stabilize the reversible behavior of interfacial deposition and favorable interfacial reaction kinetic of manganese-based cathodes in a long cycle process by optimizing mass and charge transfer. We emphasize that the initial interfacial reaction energy barrier is not the main factor affecting cycling performance, and the good reaction kinetics induced by interfacial deposition during the cycling process is more conducive to the stable cycling of the battery, which has been confirmed by theoretical analysis, quartz crystal microbalance with dissipation monitoring, depth etching X-ray photon-electron spectroscopy, etc. As a result, the QEE electrolyte maintained a stable specific capacity of 250 mAh g^-1 at 0.5 A g^-1 after 350 cycles in zinc-manganese batteries. The energy density retention rate of the ZMB with QEE increased by 174% compared to that of conventional aqueous electrolyte. Furthermore, the multi-stacked soft-pack battery with a cathodic mass load of 54.4 mg maintained a stable specific capacity of 200 mAh g^-1 for 100 cycles, demonstrating its commercial potential. This work proves the feasibility of adapting lean-water QEE to the stable aqueous ZMBs.

Keywords: quasi-eutectic electrolyte; aqueous zinc−manganese batteries; charge transfer; mass transfer; solid−liquid interfacial state.