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Potassium Ammonium Vanadate with Rich Oxygen Vacancies for Fast and Highly Stable Zn-Ion Storage.

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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… Click to show full 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.

Keywords: ammonium vanadate; potassium ammonium; oxygen vacancies; ion

Journal Title: ACS nano
Year Published: 2022

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