Intergrating Hollow Multishelled Structure and High Entropy Engineering toward Enhanced Mechano‐Electrochemical Properties in Lithium Battery

Abstract Hollow multishelled structures (HoMSs) are attracting great interest in lithium‐ion batteries as the conversion anodes, owing to their superior buffering effect and mechanical stability. Given the synthetic challenges, especially elemental diffusion barrier in the multimetal combinations, this complex structure design has been realized in low‐ and medium‐entropy compounds so far. It means that poor reaction reversibility and low intrinsic conductivity remain largely unresolved. Here, a hollow multishelled (LiFeZnNiCoMn)₃O₄ high entropy oxide (HEO) is developed through integrating molecule and microstructure engineering. As expected, the HoMS design exhibits significant targeting functionality, yielding satisfactory structure and cycling stability. Meanwhile, the abundant oxygen defects and optimized electronic structure of HEO accelerate the lithiation kinetics, while the retention of the parent lattice matrix enables reversible lithium storage, which is validated by rigorous in situ tests and theoretical simulations. Benefiting from these combined properties, such hollow multishelled HEO anode can deliver a specific capacity of 967 mAh g⁻¹ (89% capacity retention) after 500 cycles at 0.5 A g⁻¹. The synergistic lattice and volume stability showcased in this work holds great promise in guiding the material innovations for the next‐generation energy storage devices.