Enabling the High‐Voltage Operation of Layered Ternary Oxide Cathodes via Thermally Tailored Interphase

Abstract Layered ternary oxides LiNi_xMn_yCo_zO₂ are promising cathode candidates for high‐energy lithium‐ion batteries (LIBs), but they usually suffer from the severe interfacial parasitic reactions at voltages above 4.3 V versus Li⁺/Li, which greatly limit their practical capacities. Herein, using LiNi_1/3Mn_1/3Co_1/3O₂ (NMC111) as the model system, a novel high‐temperature pre‐cycling strategy is proposed to realize its stable cycling in 3.0−4.5 V by constructing a robust cathode/electrolyte interphase (CEI). Specifically, performing the first five cycles of NMC111 at 55 °C helps to yield a uniform CEI layer enriched with fluorine‐containing species, Li₂CO₃ and poly(CO₃), which greatly suppresses the detrimental side reactions during extended cycling at 25 °C, endowing the cell with a capacity retention of 92.3% at 1C after 300 cycles, far surpassing 62.0% for the control sample without the thermally tailored CEI. This work highlights the critical role of temperature on manipulating the interfacial properties of cathode materials, opening a new avenue for developing high‐voltage cathodes for Li‐ion batteries.