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Nanosecond solvation dynamics in a polymer electrolyte for lithium batteries

Nature Materials (2024)Cite this article

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Abstract

Solvation dynamics critically affect charge transport. Spectroscopic experiments and computer simulations show that these dynamics in aqueous systems occur on a picosecond timescale. In the case of organic electrolytes, however, conflicting values ranging from 1 to several 100 picoseconds have been reported. We resolve this conflict by studying mixtures of an organic polymer and a lithium salt. Lithium ions coordinate with multiple polymer chains, resulting in temporary crosslinks. Relaxation of these crosslinks, detected by quasielastic neutron scattering, are directly related to solvation dynamics. Simulations reveal a broad spectrum of relaxation times. The average timescale for solvation dynamics in both experiment and simulation is one nanosecond. We present the direct measurement of ultraslow dynamics of solvation shell break-up in an electrolyte.

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Fig. 1: PPM polymer and Li+ solvation structure.
Fig. 2: Structure factors obtained by QENS.
Fig. 3: Segmental dynamics determined by QENS and simulation.
Fig. 4: Solvation dynamics in the presence of temporary Li+ crosslinks.

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Data availability

The Supplementary Information contains details of QENS and simulation. Further data are available from the corresponding authors upon request. Source data are presented in this paper.

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Acknowledgements

This work was supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the US Department of Energy, Office of Science, Office of Basic Energy Science, under contract no. DE-AC02-06CH11357. This research used resources at the Spallation Neutron Source, a US Department of Energy, Office of Science User Facility operated by Oak Ridge National Laboratory. The computations were performed at the Lawrencium cluster at Lawrence Berkeley National Laboratory.

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Author notes

  1. These authors contributed equally: Neel J. Shah, Chao Fang.

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, USA

    Neel J. Shah, Chao Fang, Rui Wang & Nitash P. Balsara

  2. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Neel J. Shah, Chao Fang, Xiaopeng Yu, Jaeyong Lee, Rui Wang & Nitash P. Balsara

  3. Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Naresh C. Osti & Eugene Mamontov

  4. Institute for Chemical Research, Kyoto University, Uji, Japan

    Hiroshi Watanabe

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Contributions

This project was conceived by N.P.B. and R.W.; N.J.S. designed and conducted the major experiments. C.F. performed the simulation study and all theoretical analysis. N.J.S., N.C.O. and E.M. performed the QENS measurements. X.Y. synthesized the PPM polymer. J.L. prepared the PPM/LiTFSI samples. H.W. guided the analysis of experimental data. The manuscript was written by C.F., N.J.S., R.W. and N.P.B. All authors reviewed the manuscript and approved the final version. The two first authors, N.J.S. and C.F., contributed equally to this work.

Corresponding authors

Correspondence to Rui Wang or Nitash P. Balsara.

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Nature Materials thanks Bogdan Dereka and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Shah, N.J., Fang, C., Osti, N.C. et al. Nanosecond solvation dynamics in a polymer electrolyte for lithium batteries. Nat. Mater. (2024). https://doi.org/10.1038/s41563-024-01834-y

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