Crystalline and amorphous MnO₂ cathodes with open framework enable high-performance aqueous zinc-ion batteries

Abstract

Currently, δ-MnO₂ is one of the popularly studied cathode materials for aqueous zinc-ion batteries (ZIBs) but impeded by the sluggish kinetics of Zn²⁺ and the Mn cathode dissolution. Here, we report our discovery in the study of crystalline/amorphous MnO₂ (disordered MnO₂), prepared by a simple redox reaction in the order/disorder engineering. This disordered MnO₂ cathode material, having open framework with more active sites and more stable structure, shows improved electrochemical performance in 2 mol·L⁻¹ ZnSO₄/0.1 mol·L⁻¹ MnSO₄ aqueous electrolyte. It delivers an ultrahigh discharge specific capacity of 636 mA·h·g⁻¹ at 0.1 A·g⁻¹ and remains a large discharge capacity of 216 mA·h·g⁻¹ even at a high current density of 1 A·g⁻¹ after 400 cycles. Hence disordered MnO₂ could be a promising cathode material for aqueous ZIBs. The storage mechanism of the disordered MnO₂ electrode is also systematically investigated by structural and morphological examinations of ex situ, ultimately proving that the mechanism is the same as that of the δ-MnO₂ electrode. This work may pave the way for the possibility of using the order/disorder engineering to introduce novel properties in electrode materials for high-performance aqueous ZIBs.

Graphical abstract

Keywords

aqueous zinc-ion battery / open framework / cathode / δ-MnO₂

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Acknowledgements

We gratefully acknowledge the Guangxi Natural Science Foundation (No. 2018GXNSFAA138199), Guangxi Engineering and Technology Center for Utilization of Industrial Waste Residue in Building Materials, Guangxi Key Laboratory of New Energy and Building Energy Saving (19-J-21-17), and Guangxi Key Laboratory of Optoelectronic Materials and Devices (20KF-2).

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