Silicon Anodes for Next‐Generation Li‐Ion Batteries: Design, Metrics, and Practical Routes to 500 Wh kg ⁻¹ and 1000 Cycles

Silicon (Si) anodes are key to enabling 500 Wh kg ⁻¹ lithium‐ion batteries for longer‐range electric vehicles, lightweight aerospace systems, and high‐energy consumer electronics. However, despite their high theoretical capacity (3579 mAh g ⁻¹ ), commercialization remains limited by severe volume expansion, unstable solid electrolyte interphase (SEI), low initial Coulombic efficiency (ICE), and insufficient long‐term Coulombic efficiency (CE). Here, we critically evaluate Si‐dominant anode architectures across three classes: nanoparticles and their secondary microspheres, micro‐silicon (µ‐Si), and structured Si, including nanowires and thin films supported on three‐dimensional scaffolds. Performance is benchmarked using practical capacity, ICE/CE, cycling stability, and volumetric metrics. We show that current Si technologies can realistically deliver ~400 Wh kg ⁻¹ , with defined pathways toward ~500 Wh kg ⁻¹ ; however, achieving ≥1000 cycles remains a major challenge, primarily due to insufficient long‐term CE. Across architectures, high‐surface‐area electrodes, while beneficial for kinetics and strain accommodation, increase irreversible losses and limit cycle life. Strategies that reduce exposed surface area while maintaining transport and mechanical integrity, particularly through dense secondary particle design, offer a practical route toward scalable implementation. Progress toward commercial viability will require coordinated advances in interfacial passivation, contact‐preserving architectures, electrode densification, and manufacturing compatibility.