Reversible Ion Transport Through an Irreversibly Percolating Li ₂ S Interphase at the Li/Li ₆ PS ₅ Cl Interface
- 1Chemistry–School of Natural and Environmental Sciences
- 2Newcastle University
- 3Faraday Institution
Abstract
Interfacial resistance growth between Li metal and sulfide solid electrolytes is a leading cause of failure in solid-state batteries, yet the atomic-scale processes that govern this growth under an electrochemical driving force are poorly resolved. Herein, we combine a fine-tuned machine-learning interatomic potential with dynamically updated atomic charges to simulate the Li/Li 6 PS 5 Cl interface for nanoseconds under both field-free and electric-field-driven conditions. Without a field, the electrolyte decomposes spontaneously into a Li 2 S-rich interphase whose thickness follows square-root-of-time kinetics, consistent with diffusion-limited growth. Applying a field to the same initial interface accelerates this growth nearly seven-fold and converts the entire electrolyte slab within ∼100 ps. In both cases, the Li 2 S-like product forms a single connected network, while Li 3 P-and LiCl-like decomposition products remain confined to small, disconnected clusters. Although reversing the field reverses the direction of Li flux almost immediately, the percolating Li 2 S network persists unchanged and the argyrodite coordination does not recover. This decoupling shows that structural memory, not instantaneous transport direction, determines the interphase that Li ions actually cross. Because this connectivity survives stripping, our results suggest that anode-interface resistance and reactivity in solid-state batteries are set early in cycling and are not reset by current reversal.
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BibTeX
@misc{yuan2026reversible,
title = {{Reversible Ion Transport Through an Irreversibly Percolating Li ₂ S Interphase at the Li/Li ₆ PS ₅ Cl Interface}},
author = {Tianmu Yuan and Zhimin Chen and James A. Dawson},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010110/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010110/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Reversible Ion Transport Through an Irreversibly Percolating Li ₂ S Interphase at the Li/Li ₆ PS ₅ Cl Interface
AU - Tianmu Yuan
AU - Zhimin Chen
AU - James A. Dawson
PY - 2026
DA - 2026/10/08
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010110/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010110/v1
AB - Interfacial resistance growth between Li metal and sulfide solid electrolytes is a leading cause of failure in solid-state batteries, yet the atomic-scale processes that govern this growth under an electrochemical driving force are poorly resolved. Herein, we combine a fine-tuned machine-learning interatomic potential with dynamically updated atomic charges to simulate the Li/Li 6 PS 5 Cl interface for nanoseconds under both field-free and electric-field-driven conditions. Without a field, the electrolyte decomposes spontaneously into a Li 2 S-rich interphase whose thickness follows square-root-of-time kinetics, consistent with diffusion-limited growth. Applying a field to the same initial interface accelerates this growth nearly seven-fold and converts the entire electrolyte slab within ∼100 ps. In both cases, the Li 2 S-like product forms a single connected network, while Li 3 P-and LiCl-like decomposition products remain confined to small, disconnected clusters. Although reversing the field reverses the direction of Li flux almost immediately, the percolating Li 2 S network persists unchanged and the argyrodite coordination does not recover. This decoupling shows that structural memory, not instantaneous transport direction, determines the interphase that Li ions actually cross. Because this connectivity survives stripping, our results suggest that anode-interface resistance and reactivity in solid-state batteries are set early in cycling and are not reset by current reversal.
ER -