Confronting the Challenges of Next‐Generation Silicon Anode‐Based Lithium‐Ion Batteries: Role of Designer Electrolyte Additives and Polymeric Binders

Abstract Silicon has emerged as the next‐generation anode material for high‐capacity lithium‐ion batteries (LIBs). It is currently of scientific and practical interest to encounter increasingly growing demands for high energy/power density electrochemical energy‐storage devices for use in electric vehicles (xEVs), renewable energy sources, and smart grid/utility applications. Improvements to existing conventional LIBs are required to provide higher energy, longer cycle lives. This is attributed to its unparalleled theoretical capacity (4200 mAh g −1 for Li 4.4 Si), which is approximately 10 times higher than that of a state‐of‐the‐art graphitic anode (372 mAh g −1 for LiC 6 ), with a suitable operating voltage, natural abundance, environmental benignity, nontoxicity, high safety, and so forth. However, despite the overwhelming beneficial features, the practical integration of LIBs containing a silicon anode beyond the commercial niche is hampered by unavoidable challenges, such as excessive volume changes during the (de‐)alloying process, inherently low electrical and ionic conductivities, an unstable solid–electrolyte interphase, and electrolyte drying out. Among various extenuating strategies, non‐electrode factors encompassing electrolyte additives and polymeric binders are regarded as the most economical, and effective approaches towards circumventing these disadvantages are in short supply. With the aim of providing an in‐depth insight into rapidly growing accounts of electrolyte additives and binders for use with silicon anode‐based LIBs, this Review assesses the current state of the art of research and thereby examines opportunities to open up new avenues for the practical realization of these silicon anode‐based LIBs.