In:
Advanced Energy Materials, Wiley, Vol. 10, No. 40 ( 2020-10)
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.
Type of Medium:
Online Resource
ISSN:
1614-6832
,
1614-6840
DOI:
10.1002/aenm.202001595
Language:
English
Publisher:
Wiley
Publication Date:
2020
detail.hit.zdb_id:
2594556-7
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