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Correlate phonon modes with ion transport via isotope substitution

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Abstract

Understanding the correlations between lattice dynamics (phonons) and ion transport is important for improving the ionic conductivity of solid-state electrolytes. This understanding largely hinges on selective tuning or excitation of specific phonon modes without changing the chemical environments of atoms, which is, however, challenging to be achieved. In this work, we used 6Li isotope substitution to selectively change the phonon properties associated with lithium, without introducing additional defects or disorders which would affect the ion transport properties. The changes in the phonon modes were then related to ion transport properties through impedance measurements and deep potential molecular dynamics simulations. Our results demonstrated that lower lithium vibration frequency leads to higher ionic conductivity and lower activation energy in the garnet solid-state electrolyte of Li6.4La3Zr1.4Ta0.6O12. We furthermore quantified the effect of lithium-related phonons on the migration entropy and attempt frequency, which would be difficult to be achieved otherwise. Our work suggests an effective isotope substitution method to decouple the effect of phonon modes to ion transport from that of other complex structural factors. The obtained insights can contribute to innovative understanding of ion transport in solids and strategies to optimize the ionic conductivity of solid-state electrolytes.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22222204). We also thank Prof. Qianli Chen and Zhijun Fan for their discussion on analysis of Raman spectra.

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Authors and Affiliations

  1. University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University, Shanghai, 200240, China

    Yirong Gao & Shou-Hang Bo

  2. State Key Laboratory of Physical Chemistry of Solid Surface, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

    Jianxing Huang & Jun Cheng

  3. Solid-State Battery Research Center, Global Institute of Future Technology, Shanghai Jiao Tong University, Shanghai, 200240, China

    Shou-Hang Bo

  4. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China

    Shou-Hang Bo

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  1. Yirong Gao
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  2. Jianxing Huang
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Correspondence to Jun Cheng or Shou-Hang Bo.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Gao, Y., Huang, J., Cheng, J. et al. Correlate phonon modes with ion transport via isotope substitution. Sci. China Chem. 66, 768–777 (2023). https://doi.org/10.1007/s11426-022-1488-9

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  • DOI: https://doi.org/10.1007/s11426-022-1488-9

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