Mechano-thermochemical preparation of nanostructured 1 (FeCoNiCr/Mn)3O4 high and medium entropy oxides: structural, microstructural, magnetic and Li-ion storage characterization

<p dir="ltr">Mechano-thermochemical synthesis of (FeCoNiCrMn)₃O₄ high-entropy oxide (HEO) and (FeCoNiCr)₃O₄ medium-entropy oxide (MEO), and their structural, microstructural, magnetic, surface and electrochemical characteristics are investigated. Ball milling substantially reduces crystalline sizes of oxide precursors, causing their partial solid-state dissolution, driving the rapid formation of HEO and MEO during the subsequent thermal treatment. Nanostructured HEO prepared at 900 °C (HEO-900) comprises single-phase octahedral crystals mostly within the range 60–80 nm, while MEO-900 crystals (80–120 nm) exhibit a greater degree of agglomeration. The contribution of oxygen vacancies to total surface oxygen in MEO-900 (20.6 %) is lower than that of HEO-900 (27.6 %). HEO-900 exhibits a superior reversible Li-ion storage capacity of 1050.6 mAh/g after 300 cycles at 100 mA/g, outperforming MEO-900. However, at the higher current density of 500 mA/g, MEO-900 shows superior performance, with a reversible capacity of 432.2 mAh/g (70.3 % retention) after 750 cycles. The charge transfer resistance of fresh HEO-900 (359.0 Ω) is greater than that of MEO-900 (241.4 Ω), and the average Li-ion diffusion coefficient in HEO-900 (10^-13.3 cm² s⁻¹) is lower than that on MEO-900 at (10^-13.1 cm² s⁻¹) due to the greater structural complexity of the former. Full cells incorporating HEO-900 and MEO-900 anodes with LiFePO₄ cathode demonstrate an energy density of 296.4 and 274.6 Wh kg⁻¹, respectively. The saturation magnetization of HEO-900 and MEO-900 is significantly high at 33.98 and 33.80 emu/g, respectively, enabling the easy magnetic recovery of electrodes made from these compounds in spent LIBs.