Silicon (Si) is recognized as a promising anode material for next-generation lithium-ion batteries owing to its exceptionally high lithium storage capacity. Recently, micro-sized Si (micro-Si) based anodes have re-emerged as alternatives to nano-sized Si (nano-Si) owing to their higher tap density and reduced interfacial side reactions. Considerable efforts are devoted to addressing the rapid capacity decay caused by severe volume expansion, sluggish kinetics, and continuous accumulation of the solid electrolyte interphase. In this review, the primary failure mechanisms of micro-Si anodes is first analyzed and subsequently summarize recent advances in enhancing their structural and interfacial stability. The design of Si-containing materials (primarily Si/C composites and SiOx structures) that meet the current industrial requirements is discussed. Additionally, binder optimization and electrolyte exploration are analyzed. Finally, the potential application of advanced spectroscopic, electronic, and mechanical characterization techniques is explored, coupled with machine learning, in developing Si-based anodes. This review aims to comprehensively understand the rational design and in-depth analysis of next-generation micro-Si based lithium-ion batteries.

College of Energy Soochow Institute for Energy and Materials Innovation Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province Key Laboratory of Core Technology of High Specific Energy Battery and Key Materials for Petroleum and Chemical Industry Soochow University Suzhou 215006 P R China

Electron Beam Emergent Additive Manufacturing VSB Technical University of Ostrava 17 Listopadu 15 Ostrava 708 33 Czech Republic

Faculty of Chemistry Wrocław University of Science and Technology Wybrzeże Wyspiańskiego 27 Wrocław 50 370 Poland

i Lab CAS Center for Excellence in Nanoscience Suzhou Institute of Nano Tech and Nano Bionics Suzhou 215123 P R China

Jiangsu Key Laboratory of Advanced Negative Carbon Technologies Soochow University Suzhou Jiangsu 215123 P R China

Key Laboratory of Core Technology of High Specific Energy Battery and Key Materials for Petroleum and Chemical Industry Soochow University Suzhou 215006 P R China

School of Electronic and Information Engineering Changshu Institute of Technology Changshu 215500 P R China

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