4.7 Article

Unraveling the structural mechanism of Li insertion in γ′-V2O5 and its effect on cycling properties

Journal

ACTA MATERIALIA
Volume 165, Issue -, Pages 183-191

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.actamat.2018.11.043

Keywords

gamma '-V2O5; Li-ion battery; Cathode material; Electrochemical properties; Structural mechanism

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We report the first electrochemical and structural study of the gamma'-V2O5 polymorph toward Li insertion, with cycling properties evaluated in the 4 V-2.4 V, 3.6 V-2.4 V and 4 V-2.15 V potential ranges. This cathode material is synthesized through topotactic lithium removal from the ternary gamma-LiV2O5 bronze, using a strong oxidizing agent. It exhibits two pairs of well-defined reversible steps at 3.58/3.47 V and 2.42/2.36 V separated by a sharp potential drop of about 1 V. A high specific capacity of 285 mAh g(-1) is involved in the 4.00 V-2.15 V voltage window corresponding to the insertion of nearly 2 Li/mole of oxide. The gamma'-V2O5 material can deliver stable specific capacities of 120-185 mAh g(-1) over 45 cycles at C/10 when the lower cut-off voltage is limited to 2.4 V. Cycling experiments in the widest 4.00 V-2.15 V potential range induce however a significant capacity decline. A detailed XRD and Raman spectroscopy study delivers a detailed picture of the structural changes occurring in gamma'-V2O5 as a function of Li content. A complete phase diagram of the gamma'-V2O5/Li system is provided during the first discharge-charge cycle in the extended 4.00 V-2.15 V voltage range, i.e. for 0 <= x <= 1.94 in LixV2O5. It is demonstrated the existence of a wide solid solution domain in the 0.4 <= x < 1.4 composition range (3.6 V-2.4 V), leading to a remarkable enhancement of the cycle performance in the corresponding controlled voltage window. The Raman fingerprint of the fully lithiated zeta-Li1.94V2O5 phase is newly identified, indicating that deep structural rearrangements at the atomic scale take place during the gamma-Li1.4V2O5 -> zeta-Li1.94V2O5 transition. The resulting phase diagram accounts for the potential-composition profile and sheds light on the nature of the cycling properties in the different voltage windows. (C) 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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