Effect of the oxygen vacancy electronic state on Ni migration in Li0.5(Ni0.8Mn0.1Co0.1)O2 cathode material

Ravanny W M Komalig; Ganes Shukri; Mohammad Kemal Agusta; Muhammad Haris Mahyuddin; Afriyanti Sumboja; Adhitya Gandaryus Saputro; Ryo Maezono; Ahmad Nuruddin; Hermawan Kresno Dipojono

doi:10.1039/d3cp03396a

Effect of the oxygen vacancy electronic state on Ni migration in Li_0.5(Ni_0.8Mn_0.1Co_0.1)O₂ cathode material

Phys Chem Chem Phys. 2023 Nov 22;25(45):31374-31381. doi: 10.1039/d3cp03396a.

Authors

Ravanny W M Komalig¹, Ganes Shukri^{1

2}, Mohammad Kemal Agusta^{1

2}, Muhammad Haris Mahyuddin^{1

2}, Afriyanti Sumboja³, Adhitya Gandaryus Saputro^{1

2}, Ryo Maezono⁴, Ahmad Nuruddin^{1

2}, Hermawan Kresno Dipojono^{1

2}

Affiliations

¹ Advanced Functional Materials Research Group, Faculty of Industrial Technology, Bandung Institute of Technology, Bandung 40132, West Java, Indonesia. ganes_tf07@itb.ac.id.
² Research Centre for Nanosciences and Nanotechnology, Bandung Institute of Technology, Bandung 40132, West Java, Indonesia.
³ Material Science and Engineering Research Group, Faculty of Mechanical and Aerospace Engineering, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia.
⁴ School of Information Science, Japan Advanced Institute of Science and Technology, Asahidai 1-1, Nomi, Ishikawa 923-1292, Japan.

PMID: 37961857
DOI: 10.1039/d3cp03396a

Abstract

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 Li_0.5Ni_0.8Mn_0.1Co_0.1O₂ (hence Li_0.5NMC811) 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.