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Title: Using the Charge-Discharge Cycling of Positive Electrode Symmetric Cells to Find Electrolyte/Electrode Combinations with Minimum Reactivity

Abstract

The effects of solvents, salts, electrolyte additives and surface coatings on LiNi 0.4Mn 0.4Co 0.2O 2 (NMC442) or LiNi 0.6Mn 0.2Co 0.2O 2 (NMC622) have been probed using positive electrode Li-ion symmetric cells coupled with dV/dQ analysis. A robust symmetric cell design is presented which prevents hardware corrosion for over at least 800 hours of testing to 4.5 V vs. Li/Li + at 40°C. Positive electrode symmetric cells using uncoated positive electrode materials and 1M LiPF 6 EC:EMC 3:7 or 1M LiPF 6 EMC electrolyte rapidly developed high impedance and showed poor capacity retention. However, if 1% pyridine boron trifluoride (PBF) was added to these electrolytes, cell performance was dramatically improved. Replacing LiPF 6 by LiBF 4 in the electrolytes above, with or without PBF, yielded positive electrode symmetric cells with good capacity retention. Two types of surface coatings were explored on NMC622 positive electrodes. Cells using surface-coated positive electrodes demonstrated better capacity retention for all electrolytes compared to cells without surface coatings. Finally, this work can be used as a guide by those attempting to find electrolyte/electrode pairs suitable for use in NMC/graphite cells that can operate with long lifetime to 4.5 V.

Authors:
 [1];  [2];  [2];  [3];  [4];  [5]
  1. Xiamen Univ., Xiamen, (China). Dept. of Chemistry; Dalhousie Univ., Halifax (Canada). Dept. of Physics and Atmospheric Science
  2. Dalhousie Univ., Halifax (Canada). Dept. of Chemistry
  3. Idaho National Lab. (INL), Idaho Falls, ID (United States)
  4. Xiamen Univ., Xiamen, (China). Dept. of Chemistry
  5. Dalhousie Univ., Halifax (Canada). Dept. of Physics and Atmospheric Science; Dalhousie Univ., Halifax (Canada). Dept. of Chemistry
Publication Date:
Research Org.:
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1469346
Grant/Contract Number:  
[AC07-05ID14517]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
[ Journal Volume: 164; Journal Issue: 13]; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; electrolyte/electrode reactions; high voltage Li-ion cells; symmetric cells

Citation Formats

Shen, Chongheng, Xiong, Deijun, Ellis, L. D., Gering, Kevin L., Huang, Ling, and Dahn, J. R. Using the Charge-Discharge Cycling of Positive Electrode Symmetric Cells to Find Electrolyte/Electrode Combinations with Minimum Reactivity. United States: N. p., 2017. Web. doi:10.1149/2.1711713jes.
Shen, Chongheng, Xiong, Deijun, Ellis, L. D., Gering, Kevin L., Huang, Ling, & Dahn, J. R. Using the Charge-Discharge Cycling of Positive Electrode Symmetric Cells to Find Electrolyte/Electrode Combinations with Minimum Reactivity. United States. doi:10.1149/2.1711713jes.
Shen, Chongheng, Xiong, Deijun, Ellis, L. D., Gering, Kevin L., Huang, Ling, and Dahn, J. R. Thu . "Using the Charge-Discharge Cycling of Positive Electrode Symmetric Cells to Find Electrolyte/Electrode Combinations with Minimum Reactivity". United States. doi:10.1149/2.1711713jes. https://www.osti.gov/servlets/purl/1469346.
@article{osti_1469346,
title = {Using the Charge-Discharge Cycling of Positive Electrode Symmetric Cells to Find Electrolyte/Electrode Combinations with Minimum Reactivity},
author = {Shen, Chongheng and Xiong, Deijun and Ellis, L. D. and Gering, Kevin L. and Huang, Ling and Dahn, J. R.},
abstractNote = {The effects of solvents, salts, electrolyte additives and surface coatings on LiNi0.4Mn0.4Co0.2O2 (NMC442) or LiNi0.6Mn0.2Co0.2O2 (NMC622) have been probed using positive electrode Li-ion symmetric cells coupled with dV/dQ analysis. A robust symmetric cell design is presented which prevents hardware corrosion for over at least 800 hours of testing to 4.5 V vs. Li/Li+ at 40°C. Positive electrode symmetric cells using uncoated positive electrode materials and 1M LiPF6 EC:EMC 3:7 or 1M LiPF6 EMC electrolyte rapidly developed high impedance and showed poor capacity retention. However, if 1% pyridine boron trifluoride (PBF) was added to these electrolytes, cell performance was dramatically improved. Replacing LiPF6 by LiBF4 in the electrolytes above, with or without PBF, yielded positive electrode symmetric cells with good capacity retention. Two types of surface coatings were explored on NMC622 positive electrodes. Cells using surface-coated positive electrodes demonstrated better capacity retention for all electrolytes compared to cells without surface coatings. Finally, this work can be used as a guide by those attempting to find electrolyte/electrode pairs suitable for use in NMC/graphite cells that can operate with long lifetime to 4.5 V.},
doi = {10.1149/2.1711713jes},
journal = {Journal of the Electrochemical Society},
number = [13],
volume = [164],
place = {United States},
year = {2017},
month = {11}
}

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Cited by: 4 works
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