Synergetic Effect of Alkali‐Site Substitution and Oxygen Vacancy Boosting Vanadate Cathode for Super‐Stable Potassium and Zinc Storage. (26th May 2022)

• Record Type: Journal Article
• Authors: Zhao, Yunxiang; Liang, Shuquan; Shi, Xiaodong; Yang, Yongqiang; Tang, Yan; Lu, Bingan; Zhou, Jiang
• Is Part Of: Advanced functional materials. Volume 32:Number 32(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-05-26
• Subjects: alkali‐site substitutions -- oxygen vacancies -- phase transitions -- potassium‐ion batteries -- zinc‐ion batteries; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adfm.202203819
• Languages: English
• ISSNs: 1616-301X

Abstract

Abstract: Layer‐structured metal vanadates have attracted extensive attention as cathode materials due to multi‐electron redox reactions and versatile cations storage capability. Nevertheless, their actual promotion is still hindered by the sluggish reaction kinetics and inferior phase transition upon repeated cations (de)intercalation. Here, large‐sized NH4 + is introduced into the K‐site of K0.43 (NH4 )0.12 V2 O5– δ to enable more kinetically favorable oxygen vacancies. The reinforced structure ensures complete solid‐solution phase transition and buffers the dramatic structural change upon potassium storage. The stable presence of NH4 + as pillars during cycling is also confirmed. Meanwhile, the oxygen vacancies induced by alkali‐site substitution can facilitate ion diffusion and enhance the electronic conductivity, as further demonstrated by theoretical calculations. Therefore, it exhibits a high capacity of 117.8 mA g −1 at 20 mA g −1 with smooth profiles and superior capacity retention of 92.5% after 800 cycles at 1000 mA g −1 . Such an effective synergetic strategy also promotes its zinc storage capability, which performs negligible self‐discharge behavior and retains a reversible capacity of 216.8 mAh g −1 after 3000 cycles at 10 A g −1 . This synergetic strategy may provide novel perspectives to develop layer‐structured cathode and facilitate its practical application in energy storage devices. Abstract : A synergetic strategy of alkali‐site substitution and oxygen vacancy engineering is proposed to address the issues of inferior phase transition and sluggish reaction kinetics in vanadate cathode. The reinforced structure brought by NH4 + in K‐site serving as pillars and the accompanying oxygen vacancies endow K0.43 (NH4 )0.12 V2 O5– δ cathode with ideal cyclic stability and rate capability for both potassium and zinc storage.