Building Negative‐Thermal‐Expansion Protective Layers on the Grain Boundary of Ni‐rich Cathodes Enables Safe and Durable High Voltage Lithium‐Ion Batteries

Abstract Ni‐rich layered oxide cathode materials demonstrate high energy densities for Li‐ion batteries, but the electrochemically driven thermal runaway and mechanical degradation remain their long‐standing challenges in practical applications. Herein, it presents a novel ZrV 2 O 7 (ZVO) coating with negative thermal expansion properties along the secondary particles and primary particle grain boundaries (GBs), to simultaneously enhance the structural and thermal stability of LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811). It unveils that, such an architecture can significantly enhance the electronic conductivity, suppress the microcracks of GBs, alleviate the layered to spinel/rock‐salt phase transformation, and meanwhile relieve the lattice oxygen loss by increasing the oxygen vacancy formation energy increased (1.43 vs 1.90 eV). Consequently, the ZVO‐coated NCM811 material demonstrates a remarkable cyclability with 86.5% capacity retention after 100 cycles, and an outstanding rate performance of 30 C under a high‐voltage of 4.6 V, outperforming the state‐of‐the‐art literature. More importantly, the Li + transportation can be readily blocked at 120 °C by the negative‐thermal‐expansion ZVO coating, thus avoiding the high‐temperature thermal runaway.