Defect regulation, which enables better charge transfer and capacity retention in manganese-based cathode materials, is the key to the development of rechargeable aqueous zinc-ion batteries. Herein, yolk-shell structured NiCoMnO4-VO with gradient oxygen vacancies are synthesized by spray pyrolysis and ammonia etching. The generation of the yolk-shell structures are regulated by the diffusion rate of ions in the atomized droplets during the nucleation process instead of adding template agent. In addition, the etching effect of ammonia gradually dissolves nickel oxide in the material from the surface to the interior, creating abounding gradient oxygen vacancies and thereby achieving more active sites for zinc storage and faster charge transfer. Therefore, the material exhibits superior electrochemical performances with initial discharge capacities of 277.9 mA h g-1 at 0.2 A g-1, and the long-term capacities retention rate is 89.3% after 2800 cycles at 5 A g-1. Ex-situ XRD demonstrates NiCoMnO4-VO belongs to the embedding-extraction mechanism of H+ and Zn2+. In-situ optical microscopy reveals that the formation of zinc dendrites is suppressed to some extent.
Keywords: Aqueous Zinc ion battery; Gradient oxygen vacancy; NiCoMnO(4); Yolk-shell structure.
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