材料科学
电化学
阴极
氧化钒
溶解
电解质
拉曼光谱
同步加速器
钒
水溶液
分析化学(期刊)
化学工程
冶金
物理化学
电极
化学
色谱法
光学
物理
工程类
核物理学
作者
Jae Hyeon Jo,Yauhen Aniskevich,Jongsoon Kim,Ji Ung Choi,Hee Jae Kim,Young Hwa Jung,Docheon Ahn,Tae‐Yeol Jeon,Kug‐Seung Lee,Seok Hyun Song,Hyungsub Kim,Genady Ragoisha,A.V. Mazanik,Е.А. Streltsov,Seung‐Taek Myung
标识
DOI:10.1002/aenm.202001595
摘要
Abstract Herein, the promising properties of open‐structured NaV 3 O 8 as a cathode material for Zn‐ion batteries (ZIBs) are investigated. First‐principles calculations predict the insertion of Zn 2+ (0.74 Å) in NaV 3 O 8 with an interlayer distance of ≈7 Å, enabling delivery of a high discharge capacity of 353 mAh g −1 at 70 mA g −1 (0.2 C) for 300 cycles in the operating window of 0.3−1.5 V in 1 m Zn(CF 3 SO 3 ) 2 aqueous solution. Operando synchrotron X‐ray diffraction, X‐ray absorption near edge structure spectroscopy, and first‐principles calculations validate the insertion of Zn 2+ into the NaV 3 O 8 structure within the operation range. Moreover, operando synchrotron X‐ray diffraction and operando Raman spectroscopy reveal the formation of layered zinc hydroxytriflate (Zn 5 (OH) 8 (CF 3 SO 3 ) 2 ∙ x H 2 O) as a side reaction below 0.8 V on discharge (reduction) and its dissolution into the electrolyte above 0.8 V on charge (oxidation). The formation of the Zn hydroxytriflate interfacial layer increases the charge‐transfer activation energy from 15.5 to 48 kJ mol −1 , leading to kinetics fade below 0.8 V. The findings reveal the charge‐storage mechanism for NaV 3 O 8 , which may also be applicable to other vanadate cathodes, providing new insights for the investigation and design of ZIBs.
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