Enhanced Li-Ion Diffusion and Cycling Stability of Ni-Free High-Entropy Spinel Oxide Anodes with High-Concentration Oxygen Vacancies

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Abstract

High-entropy oxide (HEO) is an emerging type of anode material for lithium-ion batteries with excellent properties, where high-concentration oxygen vacancies can effectively enhance the diffusion coefficient of lithium ions. In this study, Ni-free spinel-type HEOs ((FeCoCrMnZn)₃O₄ and (FeCoCrMnMg)₃O₄) were prepared via ball milling, and the effects of zinc and magnesium on the concentration of oxygen vacancy (O_V), lithium-ion diffusion coefficient (D_Li+), and electrochemical performance of HEOs were investigated. Ab initio calculations show that the addition of zinc narrows down the band gap and thus improves the electrical conductivity. X-ray photoelectron spectroscopy (XPS) results show that (FeCoCrMnZn)₃O₄ (42.7%) and (FeCoCrMnMg)₃O₄ (42.5%) have high O_V concentration. During charge/discharge, the O_V concentration of (FeCoCrMnZn)₃O₄ is higher than that of (FeCoCrMnMg)₃O₄. The galvanostatic intermittent titration technique (GITT) results show that the D_Li+ value of (FeCoCrMnZn)₃O₄ is higher than that of (FeCoCrMnMg)₃O₄ during charge and discharge. All of that can improve its specific discharge capacity and enhance its cycle stability. (FeCoCrMnZn)₃O₄ achieved a discharge capacity of 828.6 mAh g-1 at 2.0 A g-1 after 2000 cycles. This work provides a deep understanding of the structure and performance of HEO.

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