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Title: Synergistic Effect of LiPF6 and LiBF4 as Electrolyte Salts in Lithium-Ion Cells

Abstract

Recent work shows promise for LiBF4 as an electrolyte salt for high voltage lithium-ion batteries. LiBF4 is more hydrolytically stable than LiPF6, and in some cases has proved to be more stable at high voltage. This work shows that 1.0 M electrolytes consisting of equal parts LiBF4 and LiPF6 have better performance in certain high voltage (4.35 V) lithium-ion cells than electrolytes with LiPF6 or LiBF4 alone. This is shown using long-term cycling and ultra-high precision coulometry on lithium-ion cells, with and without electrolyte additives. Ultra-high precision coulometry showed that electrolyte with 1:1 LiPF6:LiBF4 and no other additives performed as well as electrolyte with LiPF6 and state-of-the-art additive blends in these cells. The synergism between LiPF6 and LiBF4 was explored using XPS, symmetric cells and EIS analysis. These show that LiBF4 reduces impedance growth at the positive electrode, while LiPF6 improves passivation at the negative electrode.

Authors:
 [1];  [2];  [3];  [4]
+ Show Author Affiliations
  1. Dalhousie Univ., Halifax (Canada). Dept. of Chemistry
  2. Dalhousie Univ., Halifax (Canada). Dept. of Physics and Atmospheric Science
  3. Idaho National Lab. (INL), Idaho Falls, ID (United States)
  4. Dalhousie Univ., Halifax (Canada). Dept. of Chemistry; Dalhousie Univ., Halifax (Canada). Dept. of Physics and Atmospheric Science
Publication Date:
Research Org.:
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1469349
Grant/Contract Number:  
AC07-05ID14517
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 164; Journal Issue: 12; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; additives; electrolyte; high voltage; Li-ion cells; LiBF4; LiPF6; mixtures; synergy

Citation Formats

Ellis, L. D., Hill, I. G., Gering, Kevin L., and Dahn, J. R. Synergistic Effect of LiPF6 and LiBF4 as Electrolyte Salts in Lithium-Ion Cells. United States: N. p., 2017. Web. doi:10.1149/2.0811712jes.
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Ellis, L. D., Hill, I. G., Gering, Kevin L., & Dahn, J. R. Synergistic Effect of LiPF6 and LiBF4 as Electrolyte Salts in Lithium-Ion Cells. United States. https://doi.org/10.1149/2.0811712jes
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Ellis, L. D., Hill, I. G., Gering, Kevin L., and Dahn, J. R. Thu . "Synergistic Effect of LiPF6 and LiBF4 as Electrolyte Salts in Lithium-Ion Cells". United States. https://doi.org/10.1149/2.0811712jes. https://www.osti.gov/servlets/purl/1469349.
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@article{osti_1469349,
title = {Synergistic Effect of LiPF6 and LiBF4 as Electrolyte Salts in Lithium-Ion Cells},
author = {Ellis, L. D. and Hill, I. G. and Gering, Kevin L. and Dahn, J. R.},
abstractNote = {Recent work shows promise for LiBF4 as an electrolyte salt for high voltage lithium-ion batteries. LiBF4 is more hydrolytically stable than LiPF6, and in some cases has proved to be more stable at high voltage. This work shows that 1.0 M electrolytes consisting of equal parts LiBF4 and LiPF6 have better performance in certain high voltage (4.35 V) lithium-ion cells than electrolytes with LiPF6 or LiBF4 alone. This is shown using long-term cycling and ultra-high precision coulometry on lithium-ion cells, with and without electrolyte additives. Ultra-high precision coulometry showed that electrolyte with 1:1 LiPF6:LiBF4 and no other additives performed as well as electrolyte with LiPF6 and state-of-the-art additive blends in these cells. The synergism between LiPF6 and LiBF4 was explored using XPS, symmetric cells and EIS analysis. These show that LiBF4 reduces impedance growth at the positive electrode, while LiPF6 improves passivation at the negative electrode.},
doi = {10.1149/2.0811712jes},
journal = {Journal of the Electrochemical Society},
number = 12,
volume = 164,
place = {United States},
year = {Thu Aug 17 00:00:00 EDT 2017},
month = {Thu Aug 17 00:00:00 EDT 2017}
}
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https://doi.org/10.1149/2.0811712jes
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Cited by: 23 works
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Works referenced in this record:

Dilution of Highly Concentrated LiBF 4 /Propylene Carbonate Electrolyte Solution with Fluoroalkyl Ethers for 5-V LiNi 0.5 Mn 1.5 O 4 Positive Electrodes
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Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries
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    Works referencing / citing this record:

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    Concentrated Dual-Salt Electrolyte to Stabilize Li Metal and Increase Cycle Life of Anode Free Li-Metal Batteries
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    • Beyene, Tamene Tadesse; Bezabh, Hailemariam Kassa; Weret, Misganaw Adigo
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    Determining Parasitic Reaction Enthalpies in Lithium-Ion Cells Using Isothermal Microcalorimetry
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    • Glazier, S. L.; Odom, S. A.; Kaur, A. P.
    • Journal of The Electrochemical Society, Vol. 165, Issue 14
    • DOI: 10.1149/2.0761814jes

    Ion Association Constants for Lithium Ion Battery Electrolytes from First-Principles Quantum Chemistry
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    • Self, Julian; Fong, Kara D.; Logan, E. R.
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    Long-Term Chemothermal Stability of Delithiated NCA in Polymer Solid-State Batteries
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