Potassium Ammonium Vanadate with Rich Oxygen Vacancies for Fast and Highly Stable Zn-Ion Storage
Quan Zong, Qianqian Wang, Chaofeng Liu, Daiwen Tao, Jiangying Wang, Jingji Zhang, Huiwei Du, Junfu Chen, Qilong Zhang, Guozhong Cao
Abstract
Vanadium-based materials have been extensively studied as promising cathode materials for zinc-ion batteries because of their multiple valences and adjustable ion-diffusion channels. However, the sluggish kinetics of Zn-ion intercalation and less stable layered structure remain bottlenecks that limit their further development. The present work introduces potassium ions to partially substitute ammonium ions in ammonium vanadate, leading to a subtle shrinkage of lattice distance and the increased oxygen vacancies. The resulting potassium ammonium vanadate exhibits a high discharge capacity (464 mAh g–1 at 0.1 A g–1) and excellent cycling stability (90% retention over 3000 cycles at 5 A g–1). The excellent electrochemical properties and battery performances are attributed to the rich oxygen vacancies. The introduction of K+ to partially replace NH4+ appears to alleviate the irreversible deammoniation to prevent structural collapse during ion insertion/extraction. Density functional theory calculations show that potassium ammonium vanadate has a modulated electron structure and a better zinc-ion diffusion path with a lower migration barrier.