Phase-Modified Strongly Coupled /-MnO₂ Homojunction Cathode for Kinetics-Enhanced Zinc-Ion Batteries

Rechargeable Zn-MnO2 batteries using mild water electrolytes have garnered significant interest owing to their impressive theoretical energy density and eco-friendly characteristics. However, MnO2 suffers from huge structural changes during the cycles, resulting in very poor stability at high charge-discharge depths. Briefly, the above problems are caused by slow kinetic processes and the dissolution of Mn atoms in the cycles. In this paper, a 2D homojunction electrode material (delta/epsilon-MnO2) based on delta-MnO2 and epsilon-MnO2 has been prepared by a two-step electrochemical deposition method. According to the DFT calculations, the charge transfer and bonding between interfaces result in the generation of electronic states near the Fermi surface, giving delta/epsilon-MnO2 a more continuous distribution of electron states and better conductivity, which is conducive to the rapid insertion/extraction of Zn2+ and H+. Moreover, the strongly coupled Mn-O-Mn interfacial bond can effectively impede dissolution of Mn atoms and thus maintain the structural integrity of delta/epsilon-MnO2 during the cycles. Accordingly, the delta/epsilon-MnO2 cathode exhibits high capacity (383 mAh g(-1) at 0.1 A g(-1)), superior rate performance (150 mAh g(-1) at 5 A g(-1)), and excellent cycling stability over 2000 cycles (91.3% at 3 A g(-1)). Profoundly, this unique homojunction provides a novel paradigm for reasonable selection of different components.