Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide.

Zhang, Jin; Wang, Qinchao; Li, Shaofeng; Jiang, Zhisen; Tan, Sha; Wang, Xuelong; Zhang, Kai; Yuan, Qingxi et al. · Nat Commun · 2020

basic_science · Level V

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Abstract

Lithium-rich nickel-manganese-cobalt (LirNMC) layered material is a promising cathode for lithium-ion batteries thanks to its large energy density enabled by coexisting cation and anion redox activities. It however suffers from a voltage decay upon cycling, urging for an in-depth understanding of the particle-level structure and chemical complexity. In this work, we investigate the Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> particles morphologically, compositionally, and chemically in three-dimensions. While the composition is generally uniform throughout the particle, the charging induces a strong depth dependency in transition metal valence. Such a valence stratification phenomenon is attributed to the nature of oxygen redox which is very likely mostly associated with Mn. The depth-dependent chemistry could be modulated by the particles' core-multi-shell morphology, suggesting a structural-chemical interplay. These findings highlight the possibility of introducing a chemical gradient to address the oxygen-loss-induced voltage fade in LirNMC layered materials.