First-principles study of the structures and redox mechanisms of Ni-rich lithium nickel manganese cobalt oxides

被引:2
作者
Hsieh, I-Ta [1 ]
Wu, Yuqin [1 ]
Li, Bin [2 ,3 ]
Qi, Yue [1 ]
机构
[1] Brown Univ, Sch Engn, Providence, RI 02912 USA
[2] Oak Ridge Natl Lab, Energy Sci & Technol Directorate, Oak Ridge, TN 37830 USA
[3] Univ Tennessee, Oak Ridge Innovat Inst, Knoxville, TN 37996 USA
关键词
Nickel -rich cathode; NMC; Lithium -ion batteries; Electronic structure; Redox activity; Density functional theory calculations; TOTAL-ENERGY CALCULATIONS; AB-INITIO CALCULATION; CATHODE MATERIALS; ELECTROCHEMICAL PROPERTIES; LOSS SPECTROSCOPY; OXIDATION-STATE; ABSORPTION; LINI0.5CO0.2MN0.3O2; DEGRADATION; BATTERY;
D O I
10.1016/j.ssi.2024.116556
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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 R3<overline>m structure for LiNiO2 is metallic, contrary to the experimentally reported mix-conducting behavior. Among the four different space groups, R3<overline>m, C2/m, P2(1)/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.
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页数:10
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