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Title: Effect of Fluorination on Lithium Transport and Short-Range Order in Disordered-Rocksalt-Type Lithium-Ion Battery Cathodes

Abstract

Fluorine substitution is a critical enabler for improving the cycle life and energy density of disordered rocksalt (DRX) Li-ion battery cathode materials which offer prospects for high energy density cathodes, without the reliance on limited mineral resources. Due to the strong Li–F interaction, fluorine also is expected to modify the short-range cation order in these materials which is critical for Li-ion transport. In this work, density functional theory and Monte Carlo simulations are combined to investigate the impact of Li–F short-range ordering on the formation of Li percolation and diffusion in DRX materials. Additionally, the modeling reveals that F substitution is always beneficial at sufficiently high concentrations and can, surprisingly, even facilitate percolation in compounds without Li excess, giving them the ability to incorporate more transition metal redox capacity and thereby higher energy density. It is found that for F levels below 15%, its effect can be beneficial or disadvantageous depending on the intrinsic short-range order in the unfluorinated oxide, while for high fluorination levels the effects are always beneficial. Using extensive simulations, a map is also presented showing the trade-off between transition-metal capacity, Li-transport, and synthetic accessibility, and two of the more extreme predictions are experimentally confirmed.

Authors:
 [1];  [1];  [1];  [1];  [2];  [1];  [3];  [1]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Santa Barbara, CA (United States)
  3. Columbia Univ., New York, NY (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Vehicle Technologies Office (VTO); National Science Foundation (NSF)
OSTI Identifier:
1765558
Alternate Identifier(s):
OSTI ID: 1596881
Grant/Contract Number:  
AC02-05CH11231; ACI-1053575; DGE 1752814; AC02‐05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 10; Journal Issue: 10; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Cluster expansion; lithium batteries; percolation; theory; short-range order; transition metal oxides

Citation Formats

Ouyang, Bin, Artrith, Nongnuch, Lun, Zhengyan, Jadidi, Zinab, Kitchaev, Daniil A., Ji, Huiwen, Urban, Alexander, and Ceder, Gerbrand. Effect of Fluorination on Lithium Transport and Short-Range Order in Disordered-Rocksalt-Type Lithium-Ion Battery Cathodes. United States: N. p., 2020. Web. doi:10.1002/aenm.201903240.
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Ouyang, Bin, Artrith, Nongnuch, Lun, Zhengyan, Jadidi, Zinab, Kitchaev, Daniil A., Ji, Huiwen, Urban, Alexander, & Ceder, Gerbrand. Effect of Fluorination on Lithium Transport and Short-Range Order in Disordered-Rocksalt-Type Lithium-Ion Battery Cathodes. United States. https://doi.org/10.1002/aenm.201903240
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Ouyang, Bin, Artrith, Nongnuch, Lun, Zhengyan, Jadidi, Zinab, Kitchaev, Daniil A., Ji, Huiwen, Urban, Alexander, and Ceder, Gerbrand. Tue . "Effect of Fluorination on Lithium Transport and Short-Range Order in Disordered-Rocksalt-Type Lithium-Ion Battery Cathodes". United States. https://doi.org/10.1002/aenm.201903240. https://www.osti.gov/servlets/purl/1765558.
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@article{osti_1765558,
title = {Effect of Fluorination on Lithium Transport and Short-Range Order in Disordered-Rocksalt-Type Lithium-Ion Battery Cathodes},
author = {Ouyang, Bin and Artrith, Nongnuch and Lun, Zhengyan and Jadidi, Zinab and Kitchaev, Daniil A. and Ji, Huiwen and Urban, Alexander and Ceder, Gerbrand},
abstractNote = {Fluorine substitution is a critical enabler for improving the cycle life and energy density of disordered rocksalt (DRX) Li-ion battery cathode materials which offer prospects for high energy density cathodes, without the reliance on limited mineral resources. Due to the strong Li–F interaction, fluorine also is expected to modify the short-range cation order in these materials which is critical for Li-ion transport. In this work, density functional theory and Monte Carlo simulations are combined to investigate the impact of Li–F short-range ordering on the formation of Li percolation and diffusion in DRX materials. Additionally, the modeling reveals that F substitution is always beneficial at sufficiently high concentrations and can, surprisingly, even facilitate percolation in compounds without Li excess, giving them the ability to incorporate more transition metal redox capacity and thereby higher energy density. It is found that for F levels below 15%, its effect can be beneficial or disadvantageous depending on the intrinsic short-range order in the unfluorinated oxide, while for high fluorination levels the effects are always beneficial. Using extensive simulations, a map is also presented showing the trade-off between transition-metal capacity, Li-transport, and synthetic accessibility, and two of the more extreme predictions are experimentally confirmed.},
doi = {10.1002/aenm.201903240},
journal = {Advanced Energy Materials},
number = 10,
volume = 10,
place = {United States},
year = {Tue Mar 03 00:00:00 EST 2020},
month = {Tue Mar 03 00:00:00 EST 2020}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1002/aenm.201903240
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