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Title: Unraveling Na and F coupling effects in stabilizing Li, Mn-rich layered oxide cathodes via local ordering modification

Abstract

Regardless of the prevailing capacity and energy density of lithium, manganese-rich layered oxide (LMR-NMC) cathodes, continuous decay of voltage and overall energy density during cycling hinders this material from commercialization in Li-ion batteries. Although significant work focuses on single doping of Na and F, analysis in portraying the benefit of these ions in diminishing the structural distortion during activation cycle is in doubt. In this study, the effects of co-doping Na and F into the LMR-NMC structure in stabilizing the structure and mitigating oxygen loss during the first cycle are closely examined via in situ x-ray measurements. Na and F co-doping shows a 30% lower degree of Li+/Ni2+ mixing in the Li layer (C2/m structure), 50% reduced Debye-Waller factor of Mn-O bonding, increase reversible TM migration, and faster Li diffusion relative to the pristine material. Due to the utilization of Ni redox chemistry below 4.4 V, less oxygen redox is required for charge compensation at high voltage. This study offers the first instance to quantitatively evaluate the effects of co-doping Na and F in LMR-NMC cathode in order to minimize voltage degradation by altering the local ordering of O3-type structure, which may rationalize strategies to overcome the issues of themore » material.« less

Authors:
 [1];  [2];  [2];  [2];  [3];  [4];  [1]
+ Show Author Affiliations
  1. Worcester Polytechnic Institute, MA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Sustainable Energy Technologies Dept.
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1706599
Alternate Identifier(s):
OSTI ID: 1646909
Report Number(s):
BNL-220570-2020-JAAM
Journal ID: ISSN 2405-8297
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Energy Storage Materials
Additional Journal Information:
Journal Volume: 31; Journal ID: ISSN 2405-8297
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; co-dope; oxygen migration; voltage fading; in situ XRD; in situ XAS

Citation Formats

Vanaphuti, Panawan, Bai, Jianming, Ma, Lu, Ehrlich, Steven, Kisslinger, Kim, Wang, Feng, and Wang, Yan. Unraveling Na and F coupling effects in stabilizing Li, Mn-rich layered oxide cathodes via local ordering modification. United States: N. p., 2020. Web. doi:10.1016/j.ensm.2020.08.003.
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Vanaphuti, Panawan, Bai, Jianming, Ma, Lu, Ehrlich, Steven, Kisslinger, Kim, Wang, Feng, & Wang, Yan. Unraveling Na and F coupling effects in stabilizing Li, Mn-rich layered oxide cathodes via local ordering modification. United States. https://doi.org/10.1016/j.ensm.2020.08.003
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Vanaphuti, Panawan, Bai, Jianming, Ma, Lu, Ehrlich, Steven, Kisslinger, Kim, Wang, Feng, and Wang, Yan. Mon . "Unraveling Na and F coupling effects in stabilizing Li, Mn-rich layered oxide cathodes via local ordering modification". United States. https://doi.org/10.1016/j.ensm.2020.08.003. https://www.osti.gov/servlets/purl/1706599.
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@article{osti_1706599,
title = {Unraveling Na and F coupling effects in stabilizing Li, Mn-rich layered oxide cathodes via local ordering modification},
author = {Vanaphuti, Panawan and Bai, Jianming and Ma, Lu and Ehrlich, Steven and Kisslinger, Kim and Wang, Feng and Wang, Yan},
abstractNote = {Regardless of the prevailing capacity and energy density of lithium, manganese-rich layered oxide (LMR-NMC) cathodes, continuous decay of voltage and overall energy density during cycling hinders this material from commercialization in Li-ion batteries. Although significant work focuses on single doping of Na and F, analysis in portraying the benefit of these ions in diminishing the structural distortion during activation cycle is in doubt. In this study, the effects of co-doping Na and F into the LMR-NMC structure in stabilizing the structure and mitigating oxygen loss during the first cycle are closely examined via in situ x-ray measurements. Na and F co-doping shows a 30% lower degree of Li+/Ni2+ mixing in the Li layer (C2/m structure), 50% reduced Debye-Waller factor of Mn-O bonding, increase reversible TM migration, and faster Li diffusion relative to the pristine material. Due to the utilization of Ni redox chemistry below 4.4 V, less oxygen redox is required for charge compensation at high voltage. This study offers the first instance to quantitatively evaluate the effects of co-doping Na and F in LMR-NMC cathode in order to minimize voltage degradation by altering the local ordering of O3-type structure, which may rationalize strategies to overcome the issues of the material.},
doi = {10.1016/j.ensm.2020.08.003},
journal = {Energy Storage Materials},
number = ,
volume = 31,
place = {United States},
year = {Mon Aug 03 00:00:00 EDT 2020},
month = {Mon Aug 03 00:00:00 EDT 2020}
}
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https://doi.org/10.1016/j.ensm.2020.08.003
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