Cation-Anion Coordination for Covalent Anchoring of Manganese Oxides to Stabilize Mn Ion Valence and Suppress Jahn-Teller Distortion and Dissolution

Abstract

The increasing demand for high-capacity energy storage, spurred by the growth of renewable energy, has accelerated the pursuit of cost-effective and sustainable aqueous zinc-ion batteries as a viable alternative to traditional lithium-ion batteries. In this study, a cation-anion coordination cathode material (Zn-MnO₂F_X) is proposed, which regulates the central valence state of Mn ions by covalently anchoring manganese oxides with Zn ions and F ions to inhibit Jahn-Teller distortion and manganese dissolution. Density Functional Theory calculations elucidate the intercalation of Zn²⁺ extends the MnO₂ layer spacing, reduces ion diffusion barriers, and accelerates ion diffusion, while F^– ions repair defects and enhance the electronic conductivity of MnO₂, which stabilizes the cathodes and prolongs the life span of batteries. The co-insertion of Zn²⁺/H⁺ in MnO₂ and the auxiliary effect of Zn₄SO₄·(OH)₆·xH₂O on dissolution/deposition were elucidated by analyzing the changes in structure, morphology, and impedance during the cycling process. The Zn-MnO₂F_x cathode exhibits a high reversible capacity of 365.5 mA h g^–1 at 0.1 A g^–1, with remarkable capacity retention of 96.7% after 1000 cycles at 1 A g^–1. The initial specific capacity of the flexible yarn battery reaches 112.5 mA h g^–1 at 0.1 A g^–1. This work adeptly addresses the kinetic-stability balance in cathode materials, offering a pioneering strategy for sustainable and efficient large-scale energy storage.

Keywords

cathode / flexible electrode design / heterointerface engineering / Zn/MnO₂ battery / Zn-MnO₂F_x

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2025 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.