Degradation Mechanism of Dimethyl Carbonate (DMC) Dissociation on the LiCoO2 Cathode Surface: A First-Principles Study

The degradation mechanism of dimethyl carbonate electrolyte dissociation on the (010) surfaces of LiCoO2 and delithiated Li1/3CoO2 were investigated by periodic density functional theory. The high-throughput Madelung matrix calculation was employed to screen possible Li1/3CoO2 supercells for models of the charged state at 4.5 V. The result shows that the Li1/3CoO2(010) surface presents much stronger attraction toward dimethyl carbonate molecule with the adsorption energy of −1.98 eV than the LiCoO2(010) surface does. The C–H bond scission is the most possible dissociation mechanism of dimethyl carbonate on both surfaces, whereas the C–O bond scission of carboxyl is unlikely to occur. The energy barrier for the C–H bond scission is slightly lower on Li1/3CoO2(010) surface. The kinetic analysis further shows that the reaction rate of the C–H bond scission is much higher than that of the C–O bond scission of methoxyl by a factor of about 103 on both surfaces in the temperature range of 283–333 K, indicating that the C–H bond scission is the exclusive dimethyl carbonate dissociation mechanism on the cycled LiCoO2(010) surface. This study provides the basis to understand and develop novel cathodes or electrolytes for improving the cathode–electrolyte interface.