Journal
JOURNAL OF POWER SOURCES
Volume 556, Issue -, Pages -Publisher
ELSEVIER
DOI: 10.1016/j.jpowsour.2022.232435
Keywords
Li-ion batteries; Phase transition; VO2(B); Operando synchrotron PXRD; Structural distortion; Galvanostatic intermittent titration technique; Cyclic voltammetry
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This study investigates for the first time the effects of intercalating >0.5Li on the structural phase evolution of VO2(B) using operando X-ray diffraction. The experimental results show that deep discharge causes severe structural deformations in VO2(B), leading to capacity fade and irreversible decrease in Li-ion diffusion coefficients.
Bronze vanadium oxide, VO2(B), has gained significant interest as electrode for Li-ion mainly due to the ease of preparation and the experimentally obtainable capacities of >325 mAh g-1 with intercalation of >1Li. In this work, we investigate for the first time the effects of intercalating >0.5Li on the structural phase evolution. Using operando X-ray diffraction, we find that deep discharge (i.e. inserting >0.7Li), has a dramatic effect on the subsequent charge process by introducing significant solid-solution behavior in the two-phase transition between the Li-rich and Li-poor phases. Rietveld refinement shows that the discharge-charge asymmetry is caused by severe structural deformations in the Li-rich state. Furthermore, we find that deep discharge causes capacity fade. This appears to be linked to the structural deformation causing an irreversible decrease in the Li-ion diffusion coefficients, determined herein by galvanostatic intermittent titrations.
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