Si has been considered as a promising alternative anode for next‐generation Li‐ion batteries (LIBs) because of its high theoretical energy density, relatively low working potential, and abundance in nature. However, Si anodes exhibit rapid capacity decay and an increase in the internal resistance, which are caused by the large volume changes upon Li insertion and extraction. This unfortunately limits their practical applications. Therefore, managing the total volume change remains a critical challenge for effectively alleviating the mechanical fractures and instability of solid‐electrolyte‐interphase products. In this regard, we review the recent progress in volume‐change‐accommodating Si electrodes and investigate their ingenious structures with significant improvements in the battery performance, including size‐controlled materials, patterned thin films, porous structures, shape‐preserving shell designs, and graphene composites. These representative approaches potentially overcome the large morphologic changes in the volume of Si anodes by securing the strain relaxation and structural integrity in the entire electrode. Finally, we propose perspectives and future challenges to realize the practical application of Si anodes in LIB systems.

High-capacity Si-embedded anodes and Li-rich cathodes are considered key compartments for post lithium-ion batteries with high energy densities. However, the significant volume changes of Si and the irreversible phase transformation of Li-rich cathodes prevent their practical application. Here we report lithium fluoromalonato(difluoro)borate (LiFMDFB) as an unusual dual-function additive to resolve these structural instability issues of the electrodes. This molecularly engineered borate additive protects the Li-rich cathode by generating a stable cathode electrolyte interphase (CEI) while simultaneously tuning the fluoroethylene carbonate (FEC)-oriented solid electrolyte interphase (SEI) on the Si–graphite composite (SGC) anode. The complementary electrolyte design utilizing both LiFMDFB and FEC exhibited an improved capacity retention of 85%, a high Coulombic efficiency of ∼99.5%, and an excellent energy density of ∼400 W h kg⁻¹ in Li-rich/SGC full cells at a practical mass loading after 100 cycles. This dual-function additive approach offers a way to develop electrolyte additives to build a more favorable SEI for high-capacity electrodes.