Secondary-Phase-Induced Charge–Discharge Performance Enhancement of Co-Free High Entropy Spinel Oxide Electrodes for Li-Ion Batteries

High entropy oxide (HEO) has emerged as a new class of anode material for Li-ion batteries (LIBs) by offering infinite possibilities to tailor the charge–discharge properties. While the advantages of single-phase HEO anodes are realized, the effects of a secondary phase are overlooked. In this study, two kinds of Co-free HEOs are prepared, containing Cr, Mn, Fe, Ni, and Zn, for use as LIB anodes. One is a plain cubic-structure high entropy spinel oxide HESO (C) prepared using a solvothermal method. The other HESO (C+T) contains an extra secondary phase of tetragonal spinel oxide and is prepared using a hydrothermal method. It is demonstrated that the secondary tetragonal spinel phase introduces phase boundaries and defects/oxygen vacancies within HESO (C+T), which improve the redox kinetics and reversibility during electrode lithiation/delithiation. Density functional theory calculation is performed to assess the phase stability of cubic spinel, tetragonal spinel, and rock-salt structures, and validate the cycling stability of the electrodes upon charging–discharging. The secondary-phase-induced rate capability and cyclability enhancement of HEO electrodes are for the first time demonstrated. A HESO (C+T)||LiNi_0.8Co_0.1Mn_0.1O₂ full cell is assembled and evaluated, showing a promising gravimetric energy density of ≈610 Wh kg⁻¹ based on electrode-active materials.