Enabling Ether-Based Electrolytes for Long Cycle Life of Lithium-Ion Batteries at High Charge Voltage

Lithium-ion batteries (LIBs) with high-nickel (Ni) content LiNiMnCoO₂ (x + y + z = 1) (NMC with Ni ≥ 0.6) cathodes operated at high charge voltages have been considered as one of the most promising candidates for addressing the challenge of increasing energy density demand. Conventional LiPF₆-organocarbonate electrolytes exhibit incompatibility with such cell chemistries under certain testing conditions because of the instability of electrode/electrolyte interphases. In response to this challenge, ether-based electrolytes with finely tuned structure and composition of solvation sheaths were developed and evaluated in graphite (Gr)∥NMC811 cell chemistry in 2.5-4.4 V, despite ethers being conventionally considered to be unfavorable electrolyte solvents for LIBs because of their anodic instability above 4.0 V and cointercalation into Gr electrodes. The functional ether-based electrolytes in this work enable both excellent cycle life and high rate capability of Gr∥NMC811 cells. Mechanistic studies reveal that the unique structure and composition of the solvation sheath of the functional ether electrolytes are the main reasons behind their excellent anodic stability and effective protection of the Gr electrode and, consequently, the extraordinary cell performances when operated at high charge cutoff voltages. This work also provides a feasible approach in developing highly stable functional electrolytes for high-energy density LIBs.