Charge Storage Mechanism in Electrospun Spinel‐Structured High‐Entropy (Mn _0.2Fe _0.2Co _0.2Ni _0.2Zn _0.2) ₃O ₄ Oxide Nanofibers as Anode Material for Li‐Ion Batteries

Abstract

High‐entropy oxides (HEOs) have emerged as promising anode materials for next‐generation lithium‐ion batteries (LIBs). Among them, spinel HEOs with vacant lattice sites allowing for lithium insertion and diffusion seem particularly attractive. In this work, electrospun oxygen‐deficient (Mn,Fe,Co,Ni,Zn) HEO nanofibers are produced under environmentally friendly calcination conditions and evaluated as anode active material in LIBs. A thorough investigation of the material properties and Li ⁺ storage mechanism is carried out by several analytical techniques, including ex situ synchrotron X‐ray absorption spectroscopy. The lithiation process is elucidated in terms of lithium insertion, cation migration, and metal‐forming conversion reaction. The process is not fully reversible and the reduction of cations to the metallic form is not complete. In particular, iron, cobalt, and nickel, initially present mainly as Fe ³⁺, Co ³⁺/Co ²⁺, and Ni ²⁺, undergo reduction to Fe ⁰, Co ⁰, and Ni ⁰ to different extent (Fe < Co < Ni). Manganese undergoes partial reduction to Mn ³⁺/Mn ²⁺ and, upon re‐oxidation, does not revert to the pristine oxidation state (+4). Zn ²⁺ cations do not electrochemically participate in the conversion reaction, but migrating from tetrahedral to octahedral positions, they facilitate Li‐ion transport within lattice channels opened by their migration. Partially reversible crystal phase transitions are observed.