Insights into LiMXO₄F (M–X = Al–P and Mg–S) as Cathode Coatings for High-Performance Lithium-Ion Batteries

Cathode coatings have received extensive attention due to their ability to delay electrochemical performance degradation in lithium-ion batteries. However, the development of cathode coatings possessing high ionic conductivity and good interfacial stability with cathode materials has proven to be a challenge. Here, we performed first-principles computational studies on the phase stability, thermodynamic stability, and ionic transport properties of LiMXO4F (M–X = Al–P and Mg–S) used as cathode coatings. We find that the candidate coatings are thermodynamically metastable and can be synthesized experimentally. The coating materials possess high oxidative stability, with the materials predicted to decompose above 4.2 V, suggesting that they have good electrochemical stability under a high-voltage cathode. In addition, the candidate coatings exhibit significant chemical stability when in contact with oxide cathodes. Finally, we have studied the Li-ion transport paths and migration barriers of LiMXO4F (M–X = Al–P and Mg–S) and calculated the low migration barriers to be 0.19 and 0.09 eV, respectively. Our findings indicate that LiMXO4F (M–X = Al–P and Mg–S) are promising cathode coatings, among which LiAlPO4F has been experimentally confirmed. The theoretical cathode coating computational methods presented here can be extended to the solid-state battery system.