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Rate-dependent electrochemical strain generation in composite iron phosphate cathodes in Li-ion batteries

Journal of Materials Research volume 37, pages 3237–3248 (2022)Cite this article

Abstract

The performance of battery electrodes is significantly impacted by chemo-mechanical instabilities at faster charge/discharge rates. This study reports rate-dependent mechanical deformations in the LiFePO4 cathodes during battery cycling by synchronizing in situ digital image correlation and electrochemical techniques. The electrode undergoes larger mechanical deformations in the early cycles and irreversible strains become negligible in the subsequent cycles. Cumulative irreversible strains show a linear relationship with the square root of cycling time, and the slope of the cumulative irreversible strains is greater at faster rates. The study compares the irreversible strains in LiFePO4 for Li-ion batteries with its analogous NaFePO4 cathodes for Na-ion batteries. Rate-dependent mechanical deformations are reported as the LiFePO4 electrode undergoes larger strains per capacity at faster rates. Pulsed current charge/discharge experiments coupled with strain measurements suggest a delay in the phase transformations at faster rates. The study provides new insights into rate-dependent chemo-mechanical deformations in the LiFePO4 electrodes.

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Acknowledgments

All in situ strain and electrochemical measurements were carried out at Oklahoma State University and supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (Award Number DE-SC0021251). VM acknowledges funding as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the US Department of Energy, Office of Science, Basic Energy Science. Ö. Ö. Ç conceived the idea and supervised the work. B. Ö. performed in situ strain measurements and data analysis. All authors discussed the results. The authors declare that they have no competing interests. All data needed to evaluate the conclusions in the paper are present in the paper and/or in the Supplementary Materials. Additional data related to this paper may be requested from the authors.

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Authors and Affiliations

  1. The School of Chemical Engineering, Oklahoma State University, Stillwater, OK, 74078, USA

    Bertan Ozdogru & Ömer Özgür Çapraz

  2. Joint Center for Energy Storage Research, Pacific Northwestern National Laboratory, 902 Battelle Blvd, Richland, WA, 99354, USA

    Vijayakumar Murugesan

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  1. Bertan Ozdogru
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Correspondence to Ömer Özgür Çapraz.

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Ozdogru, B., Murugesan, V. & Çapraz, Ö.Ö. Rate-dependent electrochemical strain generation in composite iron phosphate cathodes in Li-ion batteries. Journal of Materials Research 37, 3237–3248 (2022). https://doi.org/10.1557/s43578-022-00649-4

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  • DOI: https://doi.org/10.1557/s43578-022-00649-4

Keywords

  • Rate-dependent deformations
  • Fast charging
  • Irreversible deformations
  • Digital image correlation
  • Lithium iron phosphate