Modeling phase transformations in Mn-rich disordered rocksalt cathodes with machine learning interatomic potentials

Fuente: arXiv
Saved in:
Bibliographic Details
Main Authors: Zhong, Peichen, Deng, Bowen, Anand, Shashwat, Mishra, Tara, Ceder, Gerbrand
Format: Preprint
Published: 2025
Subjects:
Online Access:
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1866911164594651136
author Zhong, Peichen
Deng, Bowen
Anand, Shashwat
Mishra, Tara
Ceder, Gerbrand
author_facet Zhong, Peichen
Deng, Bowen
Anand, Shashwat
Mishra, Tara
Ceder, Gerbrand
contents Mn-rich disordered rocksalt (DRX) cathode materials exhibit a phase transformation from a disordered to a partially disordered spinel-like structure ($δ$-phase) during electrochemical cycling. In this computational study, we used charge-informed molecular dynamics with a fine-tuned CHGNet foundation potential to investigate the phase transformation in Li$_{x}$Mn$_{0.8}$Ti$_{0.1}$O$_{1.9}$F$_{0.1}$. Our results indicate that transition metal migration occurs and reorders to form the spinel-like ordering in an FCC anion framework. The transformed structure contains a higher concentration of non-transition metal (0-TM) face-sharing channels, which are known to improve Li transport kinetics. Analysis of the Mn valence distribution suggests that the appearance of tetrahedral Mn$^{2+}$ is a consequence of spinel-like ordering, rather than the trigger for cation migration as previously suggested. Calculated equilibrium intercalation voltage profiles demonstrate that the $δ$-phase, unlike the ordered spinel, exhibits solid-solution signatures at low voltage. A higher Li capacity is obtained than in the DRX phase. This study provides atomic insights into solid-state phase transformation and its relation to experimental electrochemistry, highlighting the potential of machine learning interatomic potentials for understanding complex oxide materials.
format Preprint
id arxiv_https___arxiv_org_abs_2506_20605
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Modeling phase transformations in Mn-rich disordered rocksalt cathodes with machine learning interatomic potentials
Zhong, Peichen
Deng, Bowen
Anand, Shashwat
Mishra, Tara
Ceder, Gerbrand
Materials Science
Mn-rich disordered rocksalt (DRX) cathode materials exhibit a phase transformation from a disordered to a partially disordered spinel-like structure ($δ$-phase) during electrochemical cycling. In this computational study, we used charge-informed molecular dynamics with a fine-tuned CHGNet foundation potential to investigate the phase transformation in Li$_{x}$Mn$_{0.8}$Ti$_{0.1}$O$_{1.9}$F$_{0.1}$. Our results indicate that transition metal migration occurs and reorders to form the spinel-like ordering in an FCC anion framework. The transformed structure contains a higher concentration of non-transition metal (0-TM) face-sharing channels, which are known to improve Li transport kinetics. Analysis of the Mn valence distribution suggests that the appearance of tetrahedral Mn$^{2+}$ is a consequence of spinel-like ordering, rather than the trigger for cation migration as previously suggested. Calculated equilibrium intercalation voltage profiles demonstrate that the $δ$-phase, unlike the ordered spinel, exhibits solid-solution signatures at low voltage. A higher Li capacity is obtained than in the DRX phase. This study provides atomic insights into solid-state phase transformation and its relation to experimental electrochemistry, highlighting the potential of machine learning interatomic potentials for understanding complex oxide materials.
title Modeling phase transformations in Mn-rich disordered rocksalt cathodes with machine learning interatomic potentials
topic Materials Science
url https://arxiv.org/abs/2506.20605