Inorganic Chemistry, volume 60, issue 8, pages 5497-5506
Hydroxyl Defects in LiFePO4 Cathode Material: DFT+U and an Experimental Study
Publication type: Journal Article
Publication date: 2021-04-08
Journal:
Inorganic Chemistry
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 4.6
ISSN: 00201669, 1520510X
Inorganic Chemistry
Physical and Theoretical Chemistry
Abstract
Lithium iron phosphate, LiFePO4, a widely used cathode material in commercial Li-ion batteries, unveils a complex defect structure, which is still being deciphered. Using a combined computational and experimental approach comprising density functional theory (DFT)+U and molecular dynamics calculations and X-ray and neutron diffraction, we provide a comprehensive characterization of various OH point defects in LiFePO4, including their formation, dynamics, and localization in the interstitial space and at Li, Fe, and P sites. It is demonstrated that one, two, and four (five) OH groups can effectively stabilize Li, Fe, and P vacancies, respectively. The presence of D (H) at both Li and P sites for hydrothermally synthesized deuterium-enriched LiFePO4 is confirmed by joint X-ray and neutron powder diffraction structure refinement at 5 K that also reveals a strong deficiency of P of 6%. The P occupancy decrease is explained by the formation of hydrogarnet-like P/4H and P/5H defects, which have the lowest formation energies among all considered OH defects. Molecular dynamics simulation shows a rich structural diversity of these defects, with OH groups pointing both inside and outside vacant P tetrahedra creating numerous energetically close conformers, which hinders their explicit localization with diffraction-based methods solely. The discovered conformers include structural water molecules, which are only by 0.04 eV/atom H higher in energy than separate OH defects.
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Citations by publishers
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Elsevier
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7 publications, 50%
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American Chemical Society (ACS)
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1 publication, 7.14%
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Wiley
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1 publication, 7.14%
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The Electrochemical Society
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1 publication, 7.14%
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1 publication, 7.14%
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Multidisciplinary Digital Publishing Institute (MDPI)
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Multidisciplinary Digital Publishing Institute (MDPI)
1 publication, 7.14%
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7
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- We do not take into account publications that without a DOI.
- Statistics recalculated only for publications connected to researchers, organizations and labs registered on the platform.
- Statistics recalculated weekly.
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Aksyonov D. A. et al. Hydroxyl Defects in LiFePO4 Cathode Material: DFT+U and an Experimental Study // Inorganic Chemistry. 2021. Vol. 60. No. 8. pp. 5497-5506.
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Aksyonov D. A., Varlamova I., Trussov I. A., Savina A. A., Senyshyn A., Stevenson K. J., Abakumov A. M., Zhugayevych A., Fedotov S. S. Hydroxyl Defects in LiFePO4 Cathode Material: DFT+U and an Experimental Study // Inorganic Chemistry. 2021. Vol. 60. No. 8. pp. 5497-5506.
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TY - JOUR
DO - 10.1021/acs.inorgchem.0c03241
UR - https://doi.org/10.1021%2Facs.inorgchem.0c03241
TI - Hydroxyl Defects in LiFePO4 Cathode Material: DFT+U and an Experimental Study
T2 - Inorganic Chemistry
AU - Trussov, Ivan A
AU - Varlamova, Irina
AU - Aksyonov, D A
AU - Senyshyn, A.
AU - Stevenson, Keith J
AU - Abakumov, Artem M.
AU - Zhugayevych, A.Y.
AU - Fedotov, Stanislav S.
AU - Savina, Aleksandra A.
PY - 2021
DA - 2021/04/08 00:00:00
PB - American Chemical Society (ACS)
SP - 5497-5506
IS - 8
VL - 60
SN - 0020-1669
SN - 1520-510X
ER -
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@article{2021_Aksyonov,
author = {Ivan A Trussov and Irina Varlamova and D A Aksyonov and A. Senyshyn and Keith J Stevenson and Artem M. Abakumov and A.Y. Zhugayevych and Stanislav S. Fedotov and Aleksandra A. Savina},
title = {Hydroxyl Defects in LiFePO4 Cathode Material: DFT+U and an Experimental Study},
journal = {Inorganic Chemistry},
year = {2021},
volume = {60},
publisher = {American Chemical Society (ACS)},
month = {apr},
url = {https://doi.org/10.1021%2Facs.inorgchem.0c03241},
number = {8},
pages = {5497--5506},
doi = {10.1021/acs.inorgchem.0c03241}
}
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Aksyonov, D. A., et al. “Hydroxyl Defects in LiFePO4 Cathode Material: DFT+U and an Experimental Study.” Inorganic Chemistry, vol. 60, no. 8, Apr. 2021, pp. 5497-5506. https://doi.org/10.1021%2Facs.inorgchem.0c03241.
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