Raman Signatures of Lithium Ion Dynamics in LLZO Garnet Electrolytes: Atomistic Insights from MD-Raman Calculations
Abstract
Lithium lanthanum zirconate (LLZO) garnets are among the most promising solid electrolytes for next-generation batteries owing to their high ionic conductivity, chemical stability, and compatibility with lithium metal. Raman spectroscopy is commonly employed to distinguish the highly conductive cubic phase from the poorly conductive tetragonal phase of LLZO, yet the atomistic origin of these spectral differences and their direct connection to Li-ion transport remain unresolved. Here, we close this gap by comparing computed and experimental Raman spectra for the tetragonal, cubic, and Ta-doped variants of LLZO, with the computed spectra obtained from the MD-Raman approach that combines machine-learning molecular dynamics with first-principles polarizability calculations. We show that the contrasting ionic transport behavior across these LLZO variants is encoded in the vibrational dynamics of the lithium sublattice and gives rise to distinct features in their Raman spectra. A symmetry-resolved analysis further reveals that experimentally observed Raman peaks do not correspond to individual normal modes, but instead arise from overlapping contributions of multiple symmetry channels, challenging conventional peak-assignment approaches. By explicitly connecting experimentally accessible Raman signatures to the underlying atomic-scale dynamics, our results show how Raman spectroscopy can move beyond empirical phase identification toward a microscopic probe of Li-ion dynamics in lithium garnet electrolytes.
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BibTeX
@misc{miyagawa2026raman,
title = {{Raman Signatures of Lithium Ion Dynamics in LLZO Garnet Electrolytes: Atomistic Insights from MD-Raman Calculations}},
author = {Takeru Miyagawa and Willis O'Leary and Manuel Grumet and Hyunwon Chu and Jennifer L. M. Rupp and Waldemar Kaiser and David A. Egger},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2608.04690},
eprint = {2608.04690},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2608.04690},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Raman Signatures of Lithium Ion Dynamics in LLZO Garnet Electrolytes: Atomistic Insights from MD-Raman Calculations
AU - Takeru Miyagawa
AU - Willis O'Leary
AU - Manuel Grumet
AU - Hyunwon Chu
AU - Jennifer L. M. Rupp
AU - Waldemar Kaiser
AU - David A. Egger
PY - 2026
DA - 2026/10/26
PB - arXiv
DO - 10.48550/arxiv.2608.04690
UR - https://arxiv.org/abs/2608.04690
AB - Lithium lanthanum zirconate (LLZO) garnets are among the most promising solid electrolytes for next-generation batteries owing to their high ionic conductivity, chemical stability, and compatibility with lithium metal. Raman spectroscopy is commonly employed to distinguish the highly conductive cubic phase from the poorly conductive tetragonal phase of LLZO, yet the atomistic origin of these spectral differences and their direct connection to Li-ion transport remain unresolved. Here, we close this gap by comparing computed and experimental Raman spectra for the tetragonal, cubic, and Ta-doped variants of LLZO, with the computed spectra obtained from the MD-Raman approach that combines machine-learning molecular dynamics with first-principles polarizability calculations. We show that the contrasting ionic transport behavior across these LLZO variants is encoded in the vibrational dynamics of the lithium sublattice and gives rise to distinct features in their Raman spectra. A symmetry-resolved analysis further reveals that experimentally observed Raman peaks do not correspond to individual normal modes, but instead arise from overlapping contributions of multiple symmetry channels, challenging conventional peak-assignment approaches. By explicitly connecting experimentally accessible Raman signatures to the underlying atomic-scale dynamics, our results show how Raman spectroscopy can move beyond empirical phase identification toward a microscopic probe of Li-ion dynamics in lithium garnet electrolytes.
ER -