Assessing the magnetic states and the accuracy of first-principles Hubbard corrections for the battery cathode LixCoO2 (x=0,1)
Abstract
LixCoO2 is a prototypical layered cathode material for Li-ion batteries, yet its accurate description from first principles remains challenging because of self-interaction errors, weak interlayer interactions, and a complex magnetic energy landscape. Here, we present a systematic investigation of the structural, electronic, magnetic, and electrochemical properties of LixCoO2 (x=0,1) using density-functional theory augmented with self-consistent Hubbard corrections and long-range van der Waals interactions, together with a systematic exploration of possible magnetic states. The on-site interactions on Co-3d and O-2p states, as well as inter-site Co-O interactions, are determined from first principles using linear-response theory in the framework of density-functional perturbation theory, with Löwdin-orthogonalized atomic orbitals employed as Hubbard projectors. For LiCoO2, the inclusion of Hubbard corrections provides an accurate description of the structural properties, while the electronic structure is very sensitive to the choice of Hubbard projectors. In particular, frontier Wannier-function projectors substantially improve the description of the occupied electronic states compared with localized atomic orbitals. For CoO2, we demonstrate that a systematic exploration of the magnetic energy landscape is essential to identify the lowest-energy low-spin ground state. However, the resulting Hubbard-corrected electronic structure is insulating, consistent with the prediction of the HSE06 hybrid functional, but in contrast to the experimentally observed metallic behavior. Structural relaxation further drives the system toward a different metallic solution with an electronic configuration inconsistent with low-spin Co4+ character. Despite these limitations, the calculated intercalation voltages agree well with experiment, with deviations as small as 2%.
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BibTeX
@misc{sanella2026assessing,
title = {{Assessing the magnetic states and the accuracy of first-principles Hubbard corrections for the battery cathode Li$_x$CoO$_2$ ($x=0,1$)}},
author = {Valentina Sanella and Cristiano Malica and Alberto Carta and Maria Andolfatto and Nicola Marzari and Livia Giordano and Iurii Timrov},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.12984},
eprint = {2609.12984},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.12984},
}
RIS
TY - UNPB
TI - Assessing the magnetic states and the accuracy of first-principles Hubbard corrections for the battery cathode Li_xCoO_2 (x=0,1)
AU - Valentina Sanella
AU - Cristiano Malica
AU - Alberto Carta
AU - Maria Andolfatto
AU - Nicola Marzari
AU - Livia Giordano
AU - Iurii Timrov
PY - 2026
DA - 2026/09/11
PB - arXiv
DO - 10.48550/arxiv.2609.12984
UR - https://arxiv.org/abs/2609.12984
AB - Li_xCoO_2 is a prototypical layered cathode material for Li-ion batteries, yet its accurate description from first principles remains challenging because of self-interaction errors, weak interlayer interactions, and a complex magnetic energy landscape. Here, we present a systematic investigation of the structural, electronic, magnetic, and electrochemical properties of Li_xCoO_2 (x=0,1) using density-functional theory augmented with self-consistent Hubbard corrections and long-range van der Waals interactions, together with a systematic exploration of possible magnetic states. The on-site interactions on Co-3d and O-2p states, as well as inter-site Co-O interactions, are determined from first principles using linear-response theory in the framework of density-functional perturbation theory, with Löwdin-orthogonalized atomic orbitals employed as Hubbard projectors. For LiCoO_2, the inclusion of Hubbard corrections provides an accurate description of the structural properties, while the electronic structure is very sensitive to the choice of Hubbard projectors. In particular, frontier Wannier-function projectors substantially improve the description of the occupied electronic states compared with localized atomic orbitals. For CoO_2, we demonstrate that a systematic exploration of the magnetic energy landscape is essential to identify the lowest-energy low-spin ground state. However, the resulting Hubbard-corrected electronic structure is insulating, consistent with the prediction of the HSE06 hybrid functional, but in contrast to the experimentally observed metallic behavior. Structural relaxation further drives the system toward a different metallic solution with an electronic configuration inconsistent with low-spin Co^4+ character. Despite these limitations, the calculated intercalation voltages agree well with experiment, with deviations as small as 2%.
ER -