Metal-Ion Chelating Gel Polymer Electrolyte for Ni-Rich Layered Cathode Materials at a High Voltage and an Elevated Temperature

Nickel-rich layered oxides (LiNi_1-x-yCo_xMn_yO₂; (1 - x - y) ≥ 0.6), the high-energy-density cathode materials of lithium-ion batteries (LIBs), are seriously unstable at voltages higher than 4.5 V versus Li/Li⁺ and temperatures higher than 50 °C. Herein, we demonstrated that the failure mechanism of a nickel-rich layered oxide (LiNi_0.6Co_0.2Mn_0.2O₂) behind the instability was successfully suppressed by employing cyanoethyl poly(vinyl alcohol) having pyrrolidone moieties (Pyrd-PVA-CN) as a metal-ion-chelating gel polymer electrolyte (GPE). The metal-ion-chelating GPE blocked the plating of transition-metal ions dissolved from the cathode by capturing the ions (anode protection). High-concentration metal-ion environments developed around the cathode surface by the GPE suppressed the irreversible phase transition of the cathode material from the layered structure to the rock-salt structure (cathode protection). Resultantly, the capacity retention was significantly improved at a high voltage and a high temperature. Capacity retention and coulombic efficiency of a full-cell configuration of a nickel-rich layered oxide with graphite were significantly improved in the presence of the GPE especially at a high cutoff voltage (4.4 V) and an elevated temperature (55 °C).