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Structural and electrochemical properties of Cr-substituted lithium manganese oxide thin films

  • Original Paper: Sol-gel and hybrid materials for dielectric, electronic, magnetic and ferroelectric applications
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Abstract

The advantages of Cr substitution in lithium manganese oxide (LiMn2O4) for cathode of rechargeable battery were investigated. LiCrxMn2-xO4 (x ≤ 0.3) thin films were deposited on Pt/Ti/SiO2/Si substrates via a sol–gel process. The LiCrxMn2-xO4 specimens were found to have the spinel structure of pristine LiMn2O4 with no detectable secondary phase. The Cr ions were found to be trivalent and to occupy the octahedral sites of the spinel lattice. The Cr-substituted specimens exhibited a new phonon mode near 570 cm−1 in the Raman spectrum. It is ascribed to octahedral Cr3+−O bonding (T2g) that is located close to the mode due to octahedral Mn3+−O bonding (580 cm−1). According to charge-discharge (C-D) cycling data on the LiCrxMn2-xO4 cathodes, the specimens of x = 0.02 and 0.05 kept larger capacities than that of the pristine LiMn2O4 cathode up to 700 cycles. The x = 0.05 cathode showed initial capacity close to that of x = 0.02. Above 100th cycle, the x = 0.05 cathode showed better capacity retention than that of x = 0.02. Possible reason for the improved capacity retention by the Cr substitution was discussed.

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Highlights

  • LiCrxMn2−xO4 (x ≤ 0.3) thin films were fabricated on Pt/Ti/SiO2/Si substrates by using a sol–gel technique and post-annealing in air for 6 h at 700 °C.

  • The LiCrxMn2-xO4 specimens were found to have the spinel structure of pristine LiMn2O4 with no detectable secondary phase.

  • The Cr ions were found to be trivalent and to occupy the octahedral sites of the spinel lattice.

  • A new phonon mode (δ) near 570 cm−1 observed in the Raman spectra of the Cr-substituted specimens confirms the octahedral Cr3+ occupation in the spinel lattice.

  • The LiCrxMn2-xO4 cathodes with small Cr3+ compositions (x < 0.1) exhibited better capacity retention than the pristine LiMn2O4 cathode.

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Acknowledgements

This research was supported by the Korea Basic Science Institute under the R&D program (Project No. D37700) supervised by the Ministry of Science and ICT.

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  1. Department of Physics, Konkuk University, Seoul, 05029, South Korea

    Kwang Joo Kim & Jongho Park

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  1. Kwang Joo Kim
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Correspondence to Kwang Joo Kim.

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Kim, K.J., Park, J. Structural and electrochemical properties of Cr-substituted lithium manganese oxide thin films. J Sol-Gel Sci Technol 106, 775–781 (2023). https://doi.org/10.1007/s10971-023-06107-9

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  • DOI: https://doi.org/10.1007/s10971-023-06107-9

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