High-Performance MnOOH/α-MnO₂ Composite Cathode With Enhanced Capacity and Cycling Stability for Aqueous Zinc-Ion Batteries

Abstract

Manganese-based cathode materials hold great promise for aqueous zinc-ion batteries (AZIBs) due to their high operating voltage and low cost. Among these, manganese dioxide (MnO₂) cathodes exhibit particularly promising electrochemical characteristics but face critical challenges including insufficient electrical conductivity and rapid capacity fading. To address these issues, manganese oxyhydroxide (MnOOH) and α-MnO₂ have been studied. MnOOH offers excellent cycling stability but suffers from a relatively low specific capacity, whereas α-MnO₂ delivers high specific capacity but exhibits poor cycling stability. A rationally designed MnOOH/α-MnO₂ composite was synthesized via a crystal phase transformation method, using δ-MnO₂ as the precursor. The composite features a unique nanowire and nanorod morphology and is employed as a cathode material for AZIBs. It outperforms its individual components, achieving a high specific capacity of 233.4 mAh g⁻¹ after 750 cycles at 1 A g⁻¹. At an elevated current density of 2 A g⁻¹, it maintains a stable specific capacity of 85.0 mAh g⁻¹ after 17,000 cycles. Comprehensive mechanistic investigations reveal that the zinc storage process involves the co-intercalation/extraction of Zn²⁺ and H⁺ ions, coupled with reversible MnO₂ dissolution and redeposition. These findings highlight the potential of MnOOH/α-MnO₂ composites as high-performance cathode materials for AZIBs, effectively addressing the challenges of capacity limitation and cycling stability.

Keywords

aqueous zinc-ion batteries / composite material / crystal phase transformation / manganese-based cathode / MnOOH / α-MnO₂

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