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Title: A mechanism of defect-enhanced phase transformation kinetics in lithium iron phosphate olivine

Abstract

Abstract Antisite defects are a type of point defect ubiquitously present in intercalation compounds for energy storage applications. While they are often considered a deleterious feature, here we elucidate a mechanism of antisite defects enhancing lithium intercalation kinetics in LiFePO 4 by accelerating the FePO 4  → LiFePO 4 phase transformation. Although Fe Li antisites block Li movement along the [010] migration channels in LiFePO 4 , phase-field modeling reveals that their ability to enhance Li diffusion in other directions significantly increases the active surface area for Li intercalation in the surface-reaction-limited kinetic regime, which results in order-of-magnitude improvement in the phase transformation rate compared to defect-free particles. Antisite defects also promote a more uniform reaction flux on (010) surface and prevent the formation of current hotspots under galvanostatic (dis)charging conditions. We analyze the scaling relation between the phase boundary speed, Li diffusivity and particle dimensions and derive the criteria for the co-optimization of defect content and particle geometry. A surprising prediction is that (100)-oriented LiFePO 4 plates could potentially deliver better performance than (010)-oriented plates when the Li intercalation process is surface-reaction-limited. Our work suggests tailoring antisite defects as a general strategy to improve the rate performance of phase-changing batterymore » compounds with strong diffusion anisotropy.« less

Authors:
; ; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1619665
Resource Type:
Published Article
Journal Name:
npj Computational Materials
Additional Journal Information:
Journal Name: npj Computational Materials Journal Volume: 5 Journal Issue: 1; Journal ID: ISSN 2057-3960
Publisher:
Nature Publishing Group
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Hong, Liang, Yang, Kaiqi, and Tang, Ming. A mechanism of defect-enhanced phase transformation kinetics in lithium iron phosphate olivine. United Kingdom: N. p., 2019. Web. https://doi.org/10.1038/s41524-019-0255-3.
Hong, Liang, Yang, Kaiqi, & Tang, Ming. A mechanism of defect-enhanced phase transformation kinetics in lithium iron phosphate olivine. United Kingdom. https://doi.org/10.1038/s41524-019-0255-3
Hong, Liang, Yang, Kaiqi, and Tang, Ming. Fri . "A mechanism of defect-enhanced phase transformation kinetics in lithium iron phosphate olivine". United Kingdom. https://doi.org/10.1038/s41524-019-0255-3.
@article{osti_1619665,
title = {A mechanism of defect-enhanced phase transformation kinetics in lithium iron phosphate olivine},
author = {Hong, Liang and Yang, Kaiqi and Tang, Ming},
abstractNote = {Abstract Antisite defects are a type of point defect ubiquitously present in intercalation compounds for energy storage applications. While they are often considered a deleterious feature, here we elucidate a mechanism of antisite defects enhancing lithium intercalation kinetics in LiFePO 4 by accelerating the FePO 4  → LiFePO 4 phase transformation. Although Fe Li antisites block Li movement along the [010] migration channels in LiFePO 4 , phase-field modeling reveals that their ability to enhance Li diffusion in other directions significantly increases the active surface area for Li intercalation in the surface-reaction-limited kinetic regime, which results in order-of-magnitude improvement in the phase transformation rate compared to defect-free particles. Antisite defects also promote a more uniform reaction flux on (010) surface and prevent the formation of current hotspots under galvanostatic (dis)charging conditions. We analyze the scaling relation between the phase boundary speed, Li diffusivity and particle dimensions and derive the criteria for the co-optimization of defect content and particle geometry. A surprising prediction is that (100)-oriented LiFePO 4 plates could potentially deliver better performance than (010)-oriented plates when the Li intercalation process is surface-reaction-limited. Our work suggests tailoring antisite defects as a general strategy to improve the rate performance of phase-changing battery compounds with strong diffusion anisotropy.},
doi = {10.1038/s41524-019-0255-3},
journal = {npj Computational Materials},
number = 1,
volume = 5,
place = {United Kingdom},
year = {2019},
month = {12}
}

Journal Article:
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https://doi.org/10.1038/s41524-019-0255-3

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