TY - JOUR

T1 - Thermal evolution of LiCoO2 structure and Raman spectra below 400 °C

AU - Ryabin, Alexander

AU - Krylov, Alexander

AU - Krylova, Svetlana

AU - Kiselev, Evgeny

AU - Pelegov, Dmitry

N1 - The research was funded by the Russian Science Foundation (Project No. 22-22-00350, https://rscf.ru/project/22-22-00350 ). The Raman spectra measurements were made using equipment of the Ural Center for Shared Use “Modern nanotechnology” Ural Federal University (Reg. No. 2968), supported by the Ministry of Science and Higher Education of the Russian Federation (Project No. 075-15-2021-677). Authors warmly thank Professor Jongwoo Lim (Seoul National University) for samples, reading the manuscript, and providing his valuable comments.

PY - 2023/8/28

Y1 - 2023/8/28

N2 - Lithium cobalt oxide is a convenient model material for the vast family of cathode materials with a layered structure and still retains some commercial perspectives for microbatteries and some other applications. In this work, we have used ab initio calculations, x-ray diffraction, Raman spectroscopy, and a theoretical physical model, based on quasi-harmonic approximation with anharmonic contributions of the three-phonon and four-phonon processes, to study a temperature-induced change of Raman spectra for LiCoO2. The obtained values of shift and broadening for Eg and A1g bands can be used for quantitative characterization of temperature change, for example, due to laser-induced heating during Raman spectra measurements. The theoretical analysis of the experimental results lets us conclude that Raman spectra changes for LiCoO2 can be explained by the combination of thermal expansion of the crystal lattice and phonon damping by anharmonic coupling with comparable contributions of the three-phonon and four-phonon processes. The obtained results can be further used to develop Raman-based quality control tools.

AB - Lithium cobalt oxide is a convenient model material for the vast family of cathode materials with a layered structure and still retains some commercial perspectives for microbatteries and some other applications. In this work, we have used ab initio calculations, x-ray diffraction, Raman spectroscopy, and a theoretical physical model, based on quasi-harmonic approximation with anharmonic contributions of the three-phonon and four-phonon processes, to study a temperature-induced change of Raman spectra for LiCoO2. The obtained values of shift and broadening for Eg and A1g bands can be used for quantitative characterization of temperature change, for example, due to laser-induced heating during Raman spectra measurements. The theoretical analysis of the experimental results lets us conclude that Raman spectra changes for LiCoO2 can be explained by the combination of thermal expansion of the crystal lattice and phonon damping by anharmonic coupling with comparable contributions of the three-phonon and four-phonon processes. The obtained results can be further used to develop Raman-based quality control tools.

UR - http://www.scopus.com/inward/record.url?partnerID=8YFLogxK&scp=85168745351

UR - https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=tsmetrics&SrcApp=tsm_test&DestApp=WOS_CPL&DestLinkType=FullRecord&KeyUT=001054684500002

U2 - 10.1063/5.0164135

DO - 10.1063/5.0164135

M3 - Article

VL - 159

JO - The Journal of chemical physics

JF - The Journal of chemical physics

SN - 0021-9606

IS - 8

M1 - 084706

ER -