Operando Synchrotron X-ray Diffraction Study of Reference Electrode: Impact, Accuracy and Stability in Lithium-ion Pouch Cells
Abstract
The integration of reference electrodes (REs) into lithium‑ion batteries is essential for electrode‑resolved diagnostics and advanced battery management. However, their spatial localization and finite size can perturb local lithiation kinetics and compromise measurement accuracy. Here, we use high‑resolution operando synchrotron X-ray diffraction (XRD) on a 12 mAh three‑electrode graphite||LiNi0.6Mn0.2Co0.2O2 pouch cell to quantitatively assess the impact, accuracy, and stability of a mesh‑type LiFePO4 RE during battery cycling. Spatially resolved XRD shows that the graphite region facing the RE stays electrochemically active, but experiences reduced lithiation kinetics, with a lithiation delay that increases with the applied C-rate. Importantly, despite the locally reduced lithiation kinetics, the graphite electrode potential measured by the RE remains representative of the overall electrode, as evidenced by the detection of the LiC6 phase at the expected state of charge. In contrast, moving the RE outside the electrochemical core produces substantial potential artifacts by selectively probing the negative‑electrode overhang, highlighting the unsuitability of external RE configurations for commercial‑cell assembly. Finally, operando XRD confirms the RE holds a constant chemical composition throughout battery cycling, ensuring a stable reference potential. Collectively, these results establish guidelines for reliable three-electrode design and highlight key considerations for accurate electrode‑resolved diagnostics in practical batteries.
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BibTeX
@article{moyne2026operando,
title = {{Operando Synchrotron X-ray Diffraction Study of Reference Electrode: Impact, Accuracy and Stability in Lithium-ion Pouch Cells}},
author = {Xavier Moyne and Claire Villevieille and Fabien Mollica and Gilbert Chahine and Isabelle Morfin and Fannie Alloin and Pierre-Xavier Thivel},
journal = {EES Batteries},
year = {2026},
month = oct,
doi = {10.1039/d6eb00114a},
url = {https://hal.science/hal-05801511v2},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Operando Synchrotron X-ray Diffraction Study of Reference Electrode: Impact, Accuracy and Stability in Lithium-ion Pouch Cells
AU - Xavier Moyne
AU - Claire Villevieille
AU - Fabien Mollica
AU - Gilbert Chahine
AU - Isabelle Morfin
AU - Fannie Alloin
AU - Pierre-Xavier Thivel
PY - 2026
DA - 2026/10/12
JO - EES Batteries
DO - 10.1039/d6eb00114a
UR - https://hal.science/hal-05801511v2
AB - The integration of reference electrodes (REs) into lithium‑ion batteries is essential for electrode‑resolved diagnostics and advanced battery management. However, their spatial localization and finite size can perturb local lithiation kinetics and compromise measurement accuracy. Here, we use high‑resolution operando synchrotron X-ray diffraction (XRD) on a 12 mAh three‑electrode graphite||LiNi0.6Mn0.2Co0.2O2 pouch cell to quantitatively assess the impact, accuracy, and stability of a mesh‑type LiFePO4 RE during battery cycling. Spatially resolved XRD shows that the graphite region facing the RE stays electrochemically active, but experiences reduced lithiation kinetics, with a lithiation delay that increases with the applied C-rate. Importantly, despite the locally reduced lithiation kinetics, the graphite electrode potential measured by the RE remains representative of the overall electrode, as evidenced by the detection of the LiC6 phase at the expected state of charge. In contrast, moving the RE outside the electrochemical core produces substantial potential artifacts by selectively probing the negative‑electrode overhang, highlighting the unsuitability of external RE configurations for commercial‑cell assembly. Finally, operando XRD confirms the RE holds a constant chemical composition throughout battery cycling, ensuring a stable reference potential. Collectively, these results establish guidelines for reliable three-electrode design and highlight key considerations for accurate electrode‑resolved diagnostics in practical batteries.
SN - 3033-4071
ER -