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

Abstract 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 σ_Li+ but also improves the Li⁺ transfer kinetics at LiNi_0.8Co_0.15Al_0.05O₂ (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 σ_Li+ (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.