Revealing the Subzero‐Temperature Electrochemical Kinetics Behaviors in Ni‐Rich Cathode

The sluggish kinetics in Ni‐rich cathodes at subzero temperatures causes decreased specific capacity and poor rate capability, resulting in slow and unstable charge storage. So far, the driving force of this phenomenon remains a mystery. Herein, with the help of in‐situ X‐ray diffraction and time of flight secondary ion mass spectrometry techniques, the continuous accumulation of both the cathode electrolyte interphase (CEI) film formation and the incomplete structure evolution during cycling under subzero temperature are proposed. It is presented that excessively uniform and thick CEI film generated at subzero temperatures would block the diffusion of Li+‐ions, resulting in incomplete phase evolution and clear charge potential delay. The incomplete phase evolution throughout the Li+‐ion intercalation/de‐intercalation processes would further cause low depth of discharge and poor electrochemical reversibility with low initial Coulombic efficiency, as well. In addition, the formation of the thick and uniform CEI film would also consume Li+‐ions during the charging process. This discovery highlights the effects of the CEI film formation behavior and incomplete phase evolution in restricting electrochemical kinetics under subzero temperatures, which the authors believe would promote the further application of the Ni‐rich cathodes. This work proposes the mechanism of electrochemical kinetics and growth mechanism of the cathode electrolyte interphase (CEI) film of the Ni‐rich cathodes under subzero temperatures, and discoveries the growing Li2CO3 layer of the thick and uniform CEI film under subzero temperatures. This novel work can promote the further developments of Li‐ion batteries and devices in a wide application.