Improving dual electrodes compatibility through tailoring solvation structures enabling high-performance and low-temperature Li||LiFePO4 batteries

Abstract

Li||LiFePO4 (LFP) batteries have good stability and high energy density. However, they exhibit unsatisfactory low-temperature electrochemical performance. Due to the fragile interfacial passivation layers and sluggish kinetics, commercial electrolytes fail to simultaneously achieve acceptable stabilization with dual electrodes in low-temperature Li||LFP batteries. Herein, a novel localized high-concentration electrolyte (LHCE) with great dual-electrodes compatibility is proposed to match with the low-temperature Li||LFP batteries. With increasing local concentration, the FSI- sequentially replaces the solvent molecules and enters the first solvation sheath, forming the anion-dominated solvation structures. This effectively suppresses free solvents decomposition and constructs the anion-derived passivation layers with inorganic-rich components, further contributing to the rapid transport kinetics and endowing the LHCE with great dual electrodes compatibility. These dual-electrodes co-stabilization effects of the LHCE are originally clarified in the low-temperature Li||LFP batteries. The designed LHCE also delivers low freezing point (-99.8 ℃), high ionic conductivity (2.4 mS cm−1 at −40 ℃), and superior stability (>4.7 V vs. Li/Li+). Hence, the Li||LFP batteries with LHCE possess superb cyclic stability at low temperatures, delivering a high discharge capacity of 120 mAh g−1 over 300 cycles at −20 ℃. Moreover, compared to commercial electrolytes, LHCE endows the Li||LFP batteries with superior low-temperature performances under practical conditions, including limited Li anode (3 mAh cm−2) and a wide temperature range (30 ℃ to −40 ℃).