TY - JOUR
T1 - Valence study of Li(Ni0.5Mn0.5)1-xCox O2 and LiNi1-xCox O2
T2 - The role of charge transfer and charge disproportionation
AU - Takegami, Daisuke
AU - Kawai, Kosuke
AU - Ferreira-Carvalho, Miguel
AU - Rößler, Sahana
AU - Liu, Cheng En
AU - Kuo, Chang Yang
AU - Chang, Chun Fu
AU - Minamida, Atsusa
AU - Miyazaki, Tatsuya
AU - Okubo, Masashi
AU - Tjeng, Liu Hao
AU - Mizokawa, Takashi
N1 - Publisher Copyright:
© 2024 authors. Published by the American Physical Society. Published by the American Physical Society under the terms of the "https://creativecommons.org/licenses/by/4.0/"Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI. Open access publication funded by Max Planck Society.
PY - 2024/5
Y1 - 2024/5
N2 - The series of LiMO2 (M: transition metal) materials are highly relevant as cathode materials of Li-ion batteries. The stability of such systems remains an important factor for their usability in batteries, and depends strongly on the electronic configuration of the transition-metal ions. In particular, the promising class of multi-transition-metal systems exhibits complicated valence states due to intermetallic charge transfer and charge disproportionation. Here we perform a systematic study on the valence of the transition-metal ions using x-ray absorption spectroscopy on the M-L2,3 edges and O-K edges. In Li(Ni0.5Mn0.5)1-xCoxO2 we established that the valence is Co3+ and Ni0.52+Mn0.54+ throughout the whole series. Meanwhile, in LiNi1-xCoxO2 we found that the Ni displays a behavior consistent with a charge disproportionated negative charge transfer system, and that with increased concentration of Co3+, the disproportionation signal decreases. Since the number of O 2p holes also gets reduced, we infer that the material will also become more unstable.
AB - The series of LiMO2 (M: transition metal) materials are highly relevant as cathode materials of Li-ion batteries. The stability of such systems remains an important factor for their usability in batteries, and depends strongly on the electronic configuration of the transition-metal ions. In particular, the promising class of multi-transition-metal systems exhibits complicated valence states due to intermetallic charge transfer and charge disproportionation. Here we perform a systematic study on the valence of the transition-metal ions using x-ray absorption spectroscopy on the M-L2,3 edges and O-K edges. In Li(Ni0.5Mn0.5)1-xCoxO2 we established that the valence is Co3+ and Ni0.52+Mn0.54+ throughout the whole series. Meanwhile, in LiNi1-xCoxO2 we found that the Ni displays a behavior consistent with a charge disproportionated negative charge transfer system, and that with increased concentration of Co3+, the disproportionation signal decreases. Since the number of O 2p holes also gets reduced, we infer that the material will also become more unstable.
UR - http://www.scopus.com/inward/record.url?scp=85192681049&partnerID=8YFLogxK
U2 - 10.1103/PhysRevMaterials.8.055401
DO - 10.1103/PhysRevMaterials.8.055401
M3 - Article
AN - SCOPUS:85192681049
SN - 2475-9953
VL - 8
JO - Physical Review Materials
JF - Physical Review Materials
IS - 5
M1 - 055401
ER -