Despite decades of study, the identity of the dominant \ce{Li+}-conducting phase within the inorganic SEI of Li-ion batteries remains unresolved. While the mosaic model describes LiF/\ce{Li2O}/\ce{Li2CO3} nanocrystallites within a disordered matrix, these crystalline phases inherently offer limited ionic conductivity. Growing evidence suggests that interfaces, grain boundaries, and amorphous phases may instead host the primary fast-ion pathways. Using diffusion-based generative structure prediction and machine-learning interatomic potentials (MLIPs), we investigate lithium difluorophosphate (\ce{LiPO2F2}), a key mixed-anion decomposition product of phosphorus- and fluorine-containing electrolytes. We identify a stable crystalline polymorph and demonstrate that the amorphous counterpart is conductive, with projected room-temperature σ≈0.18 mS cm−1 and Ea≈0.40 eV. This enhancement stems from structural disorder flattening the Li site-energy landscape and a low formation energy for Li-interstitial defects, which supplies additional mobile carriers. We propose amorphous mixed-anion Li--P--O--F phases as a promising conducting medium in the SEI, offering a specific target for engineering improved battery interfaces.
@article{arxiv.2510.22912,
title = {Machine-Learning-Guided Insights into Solid-Electrolyte Interphase Conductivity: Are Amorphous Lithium Fluorophosphates the Key?},
author = {Peichen Zhong and Kristin A. Persson},
journal= {arXiv preprint arXiv:2510.22912},
year = {2025}
}