Effect of the oxygen vacancy electronic state on Ni migration in Li0.5(Ni0.8Mn0.1Co0.1)O2 cathode material
Literature Information
Ravanny W. M. Komalig, Afriyanti Sumboja, Ryo Maezono
Cation migration coupled with oxygen vacancy formation is known to drive the layered to disordered spinel/rock-salt phase transformation in the high-Ni layered oxide cathodes of Li-ion batteries. However, the effect of different electronic states of oxygen vacancies on the cation migration still remains elusive. Here, we investigate Ni migration in delithiated Ni-rich Li0.5Ni0.8Mn0.1Co0.1O2 (hence Li0.5NMC811) in the presence of neutral and charged oxygen vacancies by means of first-principles density functional theory (DFT) calculations coupled with the nudged elastic band (NEB) method. We find that oxygen vacancies with neutral or +2 charge favor the Ni migration to Li tetrahedral and/or octahedral sites, both thermodynamically and kinetically. As for the case of +1 charged oxygen vacancies, while they thermodynamicaly favor the Ni migration to the Li site, the relatively high migration barrier suggests that they kinetically prohibit the Ni migration. Our results suggest that controlling the formation of oxygen vacancies is the key to enhancing the Ni-rich NMC structural stability in particular in their charged states.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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