Insights on the volume variation of LiCoxMn2-xO4 electrode upon cycling: a correlative operando XRD and XAS…

Abstract

Understanding volume changes in high-voltage spinel cathodes is essential for mitigating mechanical degradation and improving cycling stability. However, linking these changes to cation-specific redox processes remains challenging. Here, we combine operando X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) to investigate the LiCoxMn2-xO4 spinel system, which exhibits a cubic structure and isotropic lattice response, in order to correlate the evolution of the local and long-range structure. Five compositions (x = 0, 0.25, 0.5, 0.75, and 1.0) were synthesized and electrochemically characterized, with x = 0, 0.5, and 1.0 examined in detail under identical cycling conditions. XAS at the Mn and Co K-edges reveals distinct Mn4+/Mn3+ and Co4+/Co3+ redox processes, with Mn redox activity dominating below 4.7 V and Co redox triggered at higher potentials. Chemometric tools for XAS data analysis further resolve the evolution of local structure during cycling. Both XRD and XAS capture consistent trends in volume evolution, despite probing different structural length scales. Increasing Co content progressively decreases the overall volume change, from 5.0 % to 1.6 % by XAS and from 5.8 % to 2.1 % by XRD. These results demonstrate that Co substitution suppresses electrochemically induced structural strain and establish a direct link between cation-specific redox activity and volumetric evolution. The correlative operando XRD/XAS approach provides a framework to investigate newly designed low-strain, high-energy cathodes with improved cycling stability.

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BibTeX RIS

BibTeX

@misc{mahayoni2026insights,
  title = {{Insights on the volume variation of LiCoxMn2-xO4 electrode upon cycling: a correlative operando XRD and XAS study}},
  author = {Eunike Mahayoni and Louiza Larbi and Romain Batiot and Anatole Weill and Damien Brégiroux and Antonella Iadecola and Arnaud Perez},
  howpublished = {arXiv},
  year = {2026},
  month = oct,
  doi = {10.48550/arxiv.2610.13189},
  eprint = {2610.13189},
  archivePrefix = {arXiv},
  url = {https://arxiv.org/abs/2610.13189},
  note = {CC BY 4.0},
}

RIS

TY  - UNPB
TI  - Insights on the volume variation of LiCoxMn2-xO4 electrode upon cycling: a correlative operando XRD and XAS study
AU  - Eunike Mahayoni
AU  - Louiza Larbi
AU  - Romain Batiot
AU  - Anatole Weill
AU  - Damien Brégiroux
AU  - Antonella Iadecola
AU  - Arnaud Perez
PY  - 2026
DA  - 2026/10/09
PB  - arXiv
DO  - 10.48550/arxiv.2610.13189
UR  - https://arxiv.org/abs/2610.13189
AB  - Understanding volume changes in high-voltage spinel cathodes is essential for mitigating mechanical degradation and improving cycling stability. However, linking these changes to cation-specific redox processes remains challenging. Here, we combine operando X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) to investigate the LiCoxMn2-xO4 spinel system, which exhibits a cubic structure and isotropic lattice response, in order to correlate the evolution of the local and long-range structure. Five compositions (x = 0, 0.25, 0.5, 0.75, and 1.0) were synthesized and electrochemically characterized, with x = 0, 0.5, and 1.0 examined in detail under identical cycling conditions. XAS at the Mn and Co K-edges reveals distinct Mn4+/Mn3+ and Co4+/Co3+ redox processes, with Mn redox activity dominating below 4.7 V and Co redox triggered at higher potentials. Chemometric tools for XAS data analysis further resolve the evolution of local structure during cycling. Both XRD and XAS capture consistent trends in volume evolution, despite probing different structural length scales. Increasing Co content progressively decreases the overall volume change, from 5.0 % to 1.6 % by XAS and from 5.8 % to 2.1 % by XRD. These results demonstrate that Co substitution suppresses electrochemically induced structural strain and establish a direct link between cation-specific redox activity and volumetric evolution. The correlative operando XRD/XAS approach provides a framework to investigate newly designed low-strain, high-energy cathodes with improved cycling stability.
ER  -

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