Metalloid Phosphorus Induces Tunable Defect Engineering in High Entropy Oxide Toward Advanced Lithium‐Ion Batteries

Abstract The inferior electrical conductivity and sluggish lithium storage kinetics of conventional high‐entropy oxide (HEO) are critical issues hindering their commercialization. The high electronegativity of metalloids can ameliorate this predicament by altering the electronic configuration of HEO compared to metals. Herein, metalloid phosphorus doping in spinel‐type HEO (P_xA_1‐x)B₂O₄ (A/B = Cr, Mn, Fe, Co, Ni) (P‐HEO) is achieved through a facile sol–gel process. The metalloid phosphorus doping facilitates the transfer of electrons from transition metal sites to phosphorus‐doped sites, resulting in the formation of electron‐rich and electron‐deficient local regions on the HEO surface and is conducive to an increase in the total number of active lithium sites in the electrochemical reaction process. Density functional theory calculation reveals Li adsorption energy on the synthesized P‐HEO is only −1.102 eV, demonstrating that the phosphorus doping enables a strong electronic coupling between lithium ions and P‐HEO. Furthermore, metalloid phosphorus doping also leads to oxygen vacancies formation and lattice distortion, which significantly enhances charge transfer efficiency and diffusion kinetics and results in the enhanced lithium storage performance with impressive rate capability and long‐term stability. These findings provide valuable insights for the design of lattice‐engineered HEO as versatile electrodes for future energy storage applications.