High-entropy oxides (HEOs), as a new type of single-phase solid solution with a multi-component design, have shown great potential when they are used as anodes in lithium-ion batteries due to four kinds of effects (thermodynamic high-entropy effect, the structural lattice distortion effect, the kinetic slow diffusion effect, and the electrochemical “cocktail effect”), leading to excellent cycling stability. Although the number of articles on the study of HEO materials has increased significantly, the latest research progress in porous HEO materials in the lithium-ion battery field has not been systematically summarized. This review outlines the progress made in recent years in the design, synthesis, and characterization of porous HEOs and focuses on phase transitions during the cycling process, the role of individual elements, and the lithium storage mechanisms disclosed through some advanced characterization techniques. Finally, the future outlook of HEOs in the energy storage field is presented, providing some guidance for researchers to further improve the design of porous HEOs.

Silicon is a well-known anode material for lithium-ion batteries that has attracted a lot of interests because of its high theoretical specific capacity (4200 mAh g⁻¹). However, its severe volume expansion during cycling leads to structural degradation and rapid capacity fading. The design of porous silicon architectures has emerged as a fundamental and effective strategy to mitigate these issues by accommodating mechanical stress and preserving electrode integrity. Concurrently, the development of advanced in situ/operando characterization techniques has shifted the research paradigm, enabling direct observation of dynamic structural and interfacial evolution under operating conditions. This review systematically summarizes recent progress in the rational design of porous Si-based anodes and critically examines how state-of-the-art in situ methods provide direct mechanistic validation of these designs. The work highlights the synergistic interplay between targeted material engineering and in situ/operando characterization, offering a roadmap for the development of high-performance porous silicon anodes.