LiMgPO₄‐Coating‐Induced Phosphate Shell and Bulk Mg‐Doping Enables Stable Ultra‐High‐Voltage Cycling of LiCoO₂ Cathode

Abstract Stable cycling of LiCoO₂ (LCO) cathode at high voltage is extremely challenging due to the notable structural instability in deeply delithiated states. Here, using the sol–gel coating method, LCO materials (LMP‐LCO) are obtained with bulk Mg‐doping and surface LiMgPO₄/Li₃PO₄ (LMP/LPO) coating. The experimental results suggest that the simultaneous modification in the bulk and at the surface is demonstrated to be highly effective in improving the high‐voltage performance of LCO. LMP‐LCO cathodes deliver 149.8 mAh g⁻¹@4.60 V and 146.1 mAh g⁻¹@4.65 V after 200 cycles at 1 C. For higher cut‐off voltages, 4.70 and 4.80 V, LMP‐LCO cathodes still achieve 144.9 mAh g⁻¹ after 150 cycles and 136.8 mAh g⁻¹ after 100 cycles at 1 C, respectively. Bulk Mg‐dopants enhance the ionicity of CoO bond by tailoring the band centers of Co 3d and O 2p, promoting stable redox on O²⁻, and thus enhancing stable cycling at high cut‐off voltages. Meanwhile, LMP/LPO surface coating suppresses detrimental surface side reactions while allowing facile Li‐ion diffusion. The mechanism of high‐voltage cycling stability is investigated by combining experimental characterizations and theoretical calculations. This study proposes a strategy of surface‐to‐bulk simultaneous modification to achieve superior structural stability at high voltages.