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Title: First-principles study of the structures and redox mechanisms of Ni-rich lithium nickel manganese cobalt oxides
To reduce the cobalt (Co) content in lithium-ion batteries, Ni-rich (high-Ni) lithium nickel manganese cobalt oxides (NMC) are pursued as one of the next-generation cathode materials. However, there is still debate on the crystal and electronic structures of the baseline, LiNiO2. Density Functional Theory (DFT) calculations were performed to provide a theoretical understanding of Ni-rich NMC. First, it was found that the commonly used R m structure for LiNiO2 is metallic, contrary to the experimentally reported mix-conducting behavior. Among the four different space groups, R m, C2/m, P21/c, and P2/c, P2/c with charge disproportionation of Ni2+ and Ni4+ is the most energetically stable and semiconducting structure of LiNiO2. Therefore, the atomic structures of representative Ni-rich NMC were built by partially replacing Ni with Co or Mn in the P2/c LiNiO2 to form LixNiyMnzCo1-y-zO2. In the fully lithiated (x = 1.0) high Ni content NMC (y > 0.5), the oxidation state of all Mn ions becomes 4+, while Co ions still maintain 3+, and part of the Ni ions become 2+ to compensate for the charge. Upon delithiation, the local environment shows more variation of the charge states on the transition metal (TM) ions. The average oxidation on each TM follows a sequence of losing electrons that starts from Ni2+ to Ni3+, then oxidizing Ni3+ and Co3+, while Mn4+ remains electrochemically inactive till x = 0. A general relationship for the oxidation state change in each TM as a function of x and y is derived and shows agreement with both modeling and experimental data.  more » « less
Award ID(s):
2054441
PAR ID:
10506273
Author(s) / Creator(s):
; ; ;
Publisher / Repository:
Elsevier
Date Published:
Journal Name:
Solid State Ionics
Volume:
411
Issue:
C
ISSN:
0167-2738
Page Range / eLocation ID:
116556
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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