Understanding the Degradation Mechanisms of LiNi0.5Co0.2Mn0.3O2 Cathode Material in Lithium Ion Batteries

LiNixCoyMnzO2 (NCM, 0 ≤ x,y,z 4.3 V) required for high capacity is inevitably accompanied by a more rapid capacity fade over numerous cycles. Here, the degradation mechanisms of LiNi0.5Co0.2Mn0.3O2 are investigated during cycling under various cutoff voltage conditions. The surface lattice structures of LiNi0.5Co0.2Mn0.3O2 are observed to suffer from an irreversible transformation; the type of transformation depends on the cutoff voltage conditions. The surface of the pristine rhombohedral phase tends to transform into a mixture of spinel and rock salt phases. Moreover, the formation of the rock salt phase is more dominant under a higher voltage operation (≈4.8 V), which is attributable to the highly oxidative environment that triggers the oxygen loss from the surface of the material. The presence of the ionically insulating rock salt phase may result in sluggish kinetics, thus deteriorating the capacity retention. This implies that the prevention of surface structural degradation can provide the means to produce and retain high capacity, as well as stabilize the cycle life of LiNi0.5Co0.2Mn0.3O2 during high-voltage operations.

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