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Vol. 19 (2027)

Atomic High-Spin Cobalt Unlocks Reversible Multi-Electron Transfer Chemistry for Superb Aqueous Zn-Mn Batteries

https://doi.org/10.1007/s40820-026-02328-z
Yajun Zhao
State Key Laboratory of Chemical Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China
Qi Li
State Key Laboratory of Chemical Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China
Yanan Lv
State Key Laboratory of Chemical Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China
Shuoxiao Zhang
Department of Physics, City University of Hong Kong, Hong Kong 999077, People’s Republic of China
Kai Jiang
Beijing Frontier Research Center On Clean Energy, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Meng Xu
State Key Laboratory of Chemical Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China
Mudasir Muhammad
State Key Laboratory of Chemical Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China
Yueyang Wang
State Key Laboratory of Chemical Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China
Yang Ren
Department of Physics, City University of Hong Kong, Hong Kong 999077, People’s Republic of China
Yi Zhao
State Key Laboratory of Chemical Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China
Xiaoming Sun
State Key Laboratory of Chemical Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China

Corresponding Author: Xiaoming Sun

sunxm@mail.buct.edu.cn

Nano-Micro Letters, Vol. 19 (2027), Article Number: 25

Abstract

To settle inherent irreversible phase transition and motivate re-dissolution of deposited “dead” MnO2 without acid and redox mediator addition, we introduced atomic-dispersed Co atoms with high-spin state into layered MnO2, denoted as Co–MnO2, via an in situ topological phase transformation strategy, thereby unlocking reversible multi-electron transfer chemistry for superb Zn–Mn batteries. Specifically, atomic-distributed Co atoms within Co–MnO2 effectively modulate [MnO6] octahedral symmetry and reduce Co–O bond covalency along with enhanced lattice oxygen activity. Based on this, high-spin Co (t2g4eg2) greatly mitigates the Jahn–Teller distortion as well as promotes electrolytic MnO2 deposited onto the cathode surface completely converted from adsorbed Mn2+ for inhibited “Mn dendrites”, achieving reversible MnO2/Mn3+ and electrolytic MnO2/Mn2+ reactions with highly thermodynamical favorability. Benefiting from the “two-step, three-electron” mechanism triggered by high-spin Co, Zn//Co–MnO2 battery delivers an outstanding capacity of 658 mAh g–1 and ultra-long lifespan over 15,000 cycles. This work reveals the critical role of transition-metal spin state modulation for energy-dense and durable Zn-MnO2 batteries with reversible multi-electron storage mechanisms.


Highlights:
1 Atomically dispersed high-spin Co atoms embedded in layered MnO2 are realized via in-situ topological phase transformation from CoMn-LDH.
2 High-spin Co unlocks fast electrode kinetics in Co-MnO2 by regulating the symmetry of [MnO6] and providing available excessive electrons to lattice oxygen.
3 The Co-MnO2 exhibits dual-energy storage mechanisms of MnO2/Mn3+ in bulk and electrolytic MnO2/Mn2+ at interface in Mn2+ containing electrolyte.

Keywords

Aqueous Zn battery Atomic high-spin Co Reversible MnO2 deposition/dissolution Multi-electron transfer chemistry High performance
Zhao, Yajun, Qi Li, Yanan Lv, Shuoxiao Zhang, Kai Jiang, Meng Xu, Mudasir Muhammad, Yueyang Wang, Yang Ren, Yi Zhao, and Xiaoming Sun. 2026. “Atomic High-Spin Cobalt Unlocks Reversible Multi-Electron Transfer Chemistry for Superb Aqueous Zn-Mn Batteries”. Nano-Micro Letters 19 (August):25. https://doi.org/10.1007/s40820-026-02328-z.
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