Lithium-ion batteries are widely used in electric vehicles and smart grids to facilitate fast and stable energy storage at different temperatures. However, the decreased Li + diffusion and poor electronic conductivity of commercial cathode materials inevitably lead to irreversible energy degradation at low temperature. Herein, we tame the relationship between diffusion and temperature of spinel LiNi 0.5 Mn 1.5 O 4 cathode by incorporating Co element into transition-metal sites. The Co element into the LiNi 0.5 Mn 1.5 O 4 lattice effectively improves the diffusion properties of lithium ions, enhances its electronic conductivity, and prevents the dissolution of Mn. Therefore, LiNi 0.4 Co 0.1 Mn 1.5 O 4 could deliver a capacity retention of 93.89% at 1 C after 200 cycles at 25 °C. Even at −20 °C, it delivers 88.43% of its room-temperature capacity. Moreover, the assembled LiNi 0.4 Co 0.1 Mn 1.5 O 4 /graphite and LiNi 0.4 Co 0.1 Mn 1.5 O 4 /Li 4 Ti 5 O 12 full cells both show a capacity retention of 98.03 and 86.61% at 1 C after 100 cycles, respectively. In particular, the LiNi 0.4 Co 0.1 Mn 1.5 O 4 / Li 4 Ti 5 O 12 full battery still exhibits a discharge capacity of 116.9 mA h g −1 at −20 °C, reaching 90.24% of its room-temperature capacity. These results not only pave the way for improving the electrochemical performance of 5 V-based cathode materials but also provide insightful guidance for their commercial applications at low temperature.