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Unlocking cell chemistry evolution with operando fibre optic infrared spectroscopy in commercial Na(Li)-ion batteries

Nature Energy volume 7, pages 1157–1169 (2022)Cite this article

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Abstract

Improvements to battery performance, reliability and lifetime are essential to meet the expansive demands for energy storage. As part of this, continuous monitoring of the dynamic chemistry inside cells offers an exciting path to minimizing parasitic reactions and maximizing sustainability. Building upon recent fibre-optic/battery innovations, we report the use of operando infrared fibre evanescent wave spectroscopy to monitor electrolyte evolution in 18650 Na-ion and Li-ion cells under real working conditions. This approach enables identification of chemical species and reveals electrolyte and additive decomposition mechanisms during cycling, thereby providing important insights into the growth and nature of the solid–electrolyte interphase, the dynamics of solvation and their complex interrelations. Moreover, by directly embedding fibres within the electrode material, we demonstrate simultaneous observations of both the material structural evolution and the Na(Li) inventory changes upon cycling. This illuminating sensing method has the power to reveal the otherwise opaque chemical phenomena occurring within each key battery component.

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Fig. 1: Integration of chalcogenide fibre into batteries.
Fig. 2: Online IR-FEWS measurement.
Fig. 3: Operando IR-FEWS measurements of NaPF6/DMC decomposition in 18650.
Fig. 4: Operando IR-FEWS measurements of NaPF6 in EC/DMC decomposition in 18650.
Fig. 5: Operando IR-FEWS measurements of NaPF6 in EC/DMC + 3 wt% VC decomposition in 18650.
Fig. 6: Operando IR-FEWS measurement of fibre coated and embedded in LFP.
Fig. 7: Operando IR-FEWS measurement of fibre embedded in NVPF.

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Data availability

The datasets generated during the current study are available in the article and its Supplementary Information.

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Acknowledgements

J.-M.T. acknowledges the International Balzan Prize Foundation and the LABEX STOREXII for funding. C.G.-M. and J.-M.T. acknowledge Brurker for the instrumental set-up. We thank Tiamat for providing the NVPF/HC 18650 cells and R. Dugas for his assistance in the cell fabrication. We thank R. Chometon for the scanning electron microscopy images. M.B.Y. acknowledges the support of the French Agence Nationale de la Recherche (ANR) under reference ANR-17-CE05-10 (project VASELinA). S.T.B. acknowledges the support from the ENERSENSE research initiative (68024013) at the Norwegian University of Science and Technology (NTNU), Norway. Finally, we gladly thank S. Mariyappan, P. Desai and D. Larcher for valuable discussions and comments.

Author information

Authors and Affiliations

  1. Chimie du Solide et de l’Energie, Collège de France, Paris, France

    C. Gervillié-Mouravieff, Jiaqiang Huang, C. Leau, L. Albero Blanquer & J.-M. Tarascon

  2. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), Amiens, France

    C. Gervillié-Mouravieff, Jiaqiang Huang, C. Leau, L. Albero Blanquer & J.-M. Tarascon

  3. Institut des Sciences Chimiques de Rennes (ISCR), Univ. Rennes, CNRS, Rennes, France

    C. Boussard-Plédel, X. H. Zhang & J. L. Adam

  4. Sustainable Energy and Environment Thrust, The Hong Kong University of Science and Technology (Guangzhou), Guangzhou, China

    Jiaqiang Huang

  5. Sorbonne Université–Université Pierre-et-Marie-Curie Paris (UPMC), Paris, France

    L. Albero Blanquer & J.-M. Tarascon

  6. Institute Charles Gerhardt of Montpellier (ICGM), Univ. Montpellier, CNRS, ENSCM, Montpellier, France

    M. Ben Yahia & M.-L. Doublet

  7. Department of Energy and Process Engineering, Faculty of Engineering, Norwegian University of Science and Technology (NTNU), Trondheim, Norway

    S. T. Boles

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Contributions

C.G.-M. and J.-M.T. conceived the idea and designed the experiments with the help of C.B.-P., J.L.A. and X.H.Z., who provided the adequate fibre. C.G.-M. performed the electrochemical tests, optical tests and data analysis. M.B.Y. and M.-L.D. conducted the theoretical analysis. C.B.-P., J.H., L.A.B., S.T.B., C.L., X.H.Z, J.L.A. and J.-M.T. conjointly discussed the data and their meaning. Finally, C.G.-M., M.-L.D., S.T.B. and J.-M.T. wrote the paper, with contributions from all authors.

Corresponding author

Correspondence to J.-M. Tarascon.

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Competing interests

A patent related to the work has been submitted (application no. PCT/EP2022/071395) by the Centre National de la Rercherche Scientifique, Collège de France, Sorbonne Université, Université de Rennes 1, Ecole Nationale Supérieure de Chimie de Rennes and Institut National des Sciences Appliquées de Rennes. The inventors are Jean-Marie Tarasco, Charlotte Gervillié, Catherine Boussard, Xiang-Hua Zhang and Jean-Luc Adam. The patent covers a method for operando characterization of chemical species within a battery using infrared fibre evanescent wave spectroscopy.

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Nature Energy thanks Yifei Yu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Gervillié-Mouravieff, C., Boussard-Plédel, C., Huang, J. et al. Unlocking cell chemistry evolution with operando fibre optic infrared spectroscopy in commercial Na(Li)-ion batteries. Nat Energy 7, 1157–1169 (2022). https://doi.org/10.1038/s41560-022-01141-3

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