High‐Safety Lithium‐Ion Batteries with Silicon‐Based Anodes Enabled by Electrolyte Design

Abstract

High‐energy‐density lithium‐ion batteries (LIBs) with high safety have long been pursued for extending the cruise range of electric vehicles. Owing to the high gravimetric capacity, silicon is a promising alternative to the convention graphite anode for high‐energy LIBs. However, it suffers from intrinsic poor interfacial stability with liquid electrolytes, inevitably increasing the risk of thermal runaway and posing serious safety challenges. In this review, we will focus on mitigating thermal runaway of silicon anodes‐based LIBs from the perspective of electrolyte design. First, the thermal runaway mechanism of LIBs is briefly introduced, while the specific thermal failure reactions associated with silicon anodes and electrolytes are discussed in detail. We then summarize the safety countermeasures (e.g., thermally stable solid electrolyte interphase, nonflammable electrolytes, highly stable lithium salts, mitigating electrode crosstalk, and solid‐state electrolytes) enabled by customized electrolyte design to address these triggers of thermal runaway. Finally, the remaining unanswered questions regarding the thermal runaway mechanism are presented, and future directions to achieve intrinsically safe electrolytes for silicon‐based anodes are prospected. This review is expected to provide insightful knowledge for improving the safety of LIBs with silicon‐based anodes.