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Title: Use of phosphoranimines to reduce organic carbonate content in Li-ion battery electrolytes

In this study, the use of phosphoranimines (PAs), a class of linear, monomeric phosphazenes, as electrolytes for Li-ion battery applications has been investigated as a route to improve safety and stability for Li-ion batteries. Of the potential PAs for use in battery applications, this work focuses on the initial synthetic preparation and analysis of N-trimethylsilyl-P,P-bis((2-methoxyethoxy)ethoxy)-P-ethylphosphoranimine (PA-5). PA-5 has high LiPF6 solubility in excess of 2 M, high thermal stability with a melting point below -80°C and high thermal stability as a neat compound to at least 250°C. As part of electrolyte blends, the inclusion of PA-5 shifts the onset of thermal degradation by close to 40°C at 35% loading and by 20°C at a 10% loading, improves the low temperature performance of the electrolyte, and when used as a primary solvent leads to increases in the flash point (by 20°C) when compared to more traditional EC:EMC blends. Cycling capabilities of full-coin cells with graphite negative electrodes and Li 1+w[Ni 0.5Mn 0.3Co 0.2] 1-wO 2 positive electrodes using PA-5:EC:EMC electrolyte blends are comparable with the performance seen for traditional EC:EMC blends. Analysis of the impact of the use of additives such as vinylene carbonate in PA-5:EC:EMC blended electrolyte results in enhancedmore » capacity retention and improved coulombic efficiency.« less
Authors:
ORCiD logo [1] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Idaho National Lab. (INL), Idaho Falls, ID (United States)
Publication Date:
Report Number(s):
INL/JOU-15-37438
Journal ID: ISSN 0013-4686; PII: S001346861631091X
Grant/Contract Number:
AC07-05ID14517
Type:
Accepted Manuscript
Journal Name:
Electrochimica Acta
Additional Journal Information:
Journal Volume: 209; Journal Issue: C; Journal ID: ISSN 0013-4686
Publisher:
Elsevier
Research Org:
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; phosphoranimine; phosphazene; battery; electrolyte; lithium ion; safety
OSTI Identifier:
1259310
Alternate Identifier(s):
OSTI ID: 1324342

Dufek, Eric J., Klaehn, John R., McNally, Joshua S., Rollins, Harry W., and Jamison, David K.. Use of phosphoranimines to reduce organic carbonate content in Li-ion battery electrolytes. United States: N. p., Web. doi:10.1016/j.electacta.2016.05.038.
Dufek, Eric J., Klaehn, John R., McNally, Joshua S., Rollins, Harry W., & Jamison, David K.. Use of phosphoranimines to reduce organic carbonate content in Li-ion battery electrolytes. United States. doi:10.1016/j.electacta.2016.05.038.
Dufek, Eric J., Klaehn, John R., McNally, Joshua S., Rollins, Harry W., and Jamison, David K.. 2016. "Use of phosphoranimines to reduce organic carbonate content in Li-ion battery electrolytes". United States. doi:10.1016/j.electacta.2016.05.038. https://www.osti.gov/servlets/purl/1259310.
@article{osti_1259310,
title = {Use of phosphoranimines to reduce organic carbonate content in Li-ion battery electrolytes},
author = {Dufek, Eric J. and Klaehn, John R. and McNally, Joshua S. and Rollins, Harry W. and Jamison, David K.},
abstractNote = {In this study, the use of phosphoranimines (PAs), a class of linear, monomeric phosphazenes, as electrolytes for Li-ion battery applications has been investigated as a route to improve safety and stability for Li-ion batteries. Of the potential PAs for use in battery applications, this work focuses on the initial synthetic preparation and analysis of N-trimethylsilyl-P,P-bis((2-methoxyethoxy)ethoxy)-P-ethylphosphoranimine (PA-5). PA-5 has high LiPF6 solubility in excess of 2 M, high thermal stability with a melting point below -80°C and high thermal stability as a neat compound to at least 250°C. As part of electrolyte blends, the inclusion of PA-5 shifts the onset of thermal degradation by close to 40°C at 35% loading and by 20°C at a 10% loading, improves the low temperature performance of the electrolyte, and when used as a primary solvent leads to increases in the flash point (by 20°C) when compared to more traditional EC:EMC blends. Cycling capabilities of full-coin cells with graphite negative electrodes and Li1+w[Ni0.5Mn0.3Co0.2]1-wO2 positive electrodes using PA-5:EC:EMC electrolyte blends are comparable with the performance seen for traditional EC:EMC blends. Analysis of the impact of the use of additives such as vinylene carbonate in PA-5:EC:EMC blended electrolyte results in enhanced capacity retention and improved coulombic efficiency.},
doi = {10.1016/j.electacta.2016.05.038},
journal = {Electrochimica Acta},
number = C,
volume = 209,
place = {United States},
year = {2016},
month = {5}
}