Colloid Electrolyte with Changed Li+ Solvation Structure for High‐Power, Low‐Temperature Lithium‐Ion Batteries

Lithium‐ion batteries currently suffer from low capacity and fast degradation under fast charging and/or low temperatures. In this work, a colloid liquid electrolyte (CLE) is designed, where the trace amount of lithium thiocarbonate (LTC) colloids in commercial carbonate electrolyte (1 m LiPF6 in ethylene carbonate/dimethyl carbonate) not only boosts up σLi+ but also improves the Li+ transfer kinetics at LiNi0.8Co0.15Al0.05O2 (NCA) cathode/electrolyte interface. The competitive coordination of LTCs with anions and solvents facilitates the dissociation of lithium salts and Li+ decoupling, dramatically enhancing the σLi+ (15 to 4.5 mS cm−1 at 30 and −20 °C, respectively); meanwhile, the desolvation process is accelerated. It demonstrates that LTC colloids induce an ≈5 nm ultrathin Li2CO3‐rich cathode electrolyte interface and infuse the grain boundary of NCA particles, enhancing interfacial Li+ transfer and inhibiting the particle cracks during cycling. Consequently, the Li||CLE||NCA battery delivers a maximum capacity of 135 mAh g−1 at a 10 C rate with 80% retention after 2000 cycles. Moreover, the fast‐charging capability under a sub‐zero environment is proved (122 mAh g−1 with 90% retention after 400 cycles at 2 C and −10 °C). This strategy for tailoring the interfacial charge transfer appears generalizable and can practically be extended to next‐generation energy‐storage systems. A novel colloid electrolyte constructs a weak Li+ solvation environment by introducing lithium thiocarbonate colloids to coordinate with solvents and anions competitively. Thus, the Li+ conductivity, desolvation process, and configuration of the cathode electrolyte interface are optimized. The enhanced interfacial Li+ transfer kinetics endow lithium‐ion batteries with excellent fast charging/discharging capability and long lifespan at room and low temperatures.