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Title: Decomposition of Phosphorus-Containing Additives at a Charged NMC Surface through Potentiostatic Holds

Abstract

In this work, multiple phosphorus-containing compounds were evaluated as electrolyte additives for their reactivity at the cathode surface using LiNi0.5Mn0.3Co0.2O2 (NMC532) // Li4Ti5O12 (LTO) cells with both cycling and high voltage potentiostatic holds. Additives surveyed include phosphite and phosphate derivatives with either trifluoroethyl, ethyl, or trimethylsilyl groups. With the same substituents, phosphite additives showed lower Coulombic efficiency (CE) and higher oxidation current during the potentiostatic hold. Regardless of substitution group, all phosphates showed slightly higher CE than the additive-free electrolyte (baseline), although no additive significantly decreases oxidation reactions over the course of the potentiostatic hold. Post-mortem X-ray photoelectron spectroscopy analysis of the cathodes indicates that the additive with trimethylsilyl group leads to significantly higher incidence of oxygen and phosphorus on the cathode surface for both phosphites and phosphates. Atomistic simulations indicate the susceptibility of these additives to electrochemical and chemical oxidation, showing chemical oxidation to be much more likely with the phosphite additives. Lastly, the identity of the ligands on the phosphorus-containing additive can dramatically affect both the decomposition current as well as cathode surface after the potentiostatic hold.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC)
OSTI Identifier:
1494582
Grant/Contract Number:  
AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 166; Journal Issue: 4; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; Lithium-ion batteries; batteries - lithium; electrolytes; energy storage; high-voltage

Citation Formats

Tornheim, Adam, Garcia, Juan C., Sahore, Ritu, Iddir, Hakim, Bloom, Ira, and Zhang, Zhengcheng. Decomposition of Phosphorus-Containing Additives at a Charged NMC Surface through Potentiostatic Holds. United States: N. p., 2019. Web. doi:10.1149/2.0951902jes.
Tornheim, Adam, Garcia, Juan C., Sahore, Ritu, Iddir, Hakim, Bloom, Ira, & Zhang, Zhengcheng. Decomposition of Phosphorus-Containing Additives at a Charged NMC Surface through Potentiostatic Holds. United States. doi:10.1149/2.0951902jes.
Tornheim, Adam, Garcia, Juan C., Sahore, Ritu, Iddir, Hakim, Bloom, Ira, and Zhang, Zhengcheng. Thu . "Decomposition of Phosphorus-Containing Additives at a Charged NMC Surface through Potentiostatic Holds". United States. doi:10.1149/2.0951902jes. https://www.osti.gov/servlets/purl/1494582.
@article{osti_1494582,
title = {Decomposition of Phosphorus-Containing Additives at a Charged NMC Surface through Potentiostatic Holds},
author = {Tornheim, Adam and Garcia, Juan C. and Sahore, Ritu and Iddir, Hakim and Bloom, Ira and Zhang, Zhengcheng},
abstractNote = {In this work, multiple phosphorus-containing compounds were evaluated as electrolyte additives for their reactivity at the cathode surface using LiNi0.5Mn0.3Co0.2O2 (NMC532) // Li4Ti5O12 (LTO) cells with both cycling and high voltage potentiostatic holds. Additives surveyed include phosphite and phosphate derivatives with either trifluoroethyl, ethyl, or trimethylsilyl groups. With the same substituents, phosphite additives showed lower Coulombic efficiency (CE) and higher oxidation current during the potentiostatic hold. Regardless of substitution group, all phosphates showed slightly higher CE than the additive-free electrolyte (baseline), although no additive significantly decreases oxidation reactions over the course of the potentiostatic hold. Post-mortem X-ray photoelectron spectroscopy analysis of the cathodes indicates that the additive with trimethylsilyl group leads to significantly higher incidence of oxygen and phosphorus on the cathode surface for both phosphites and phosphates. Atomistic simulations indicate the susceptibility of these additives to electrochemical and chemical oxidation, showing chemical oxidation to be much more likely with the phosphite additives. Lastly, the identity of the ligands on the phosphorus-containing additive can dramatically affect both the decomposition current as well as cathode surface after the potentiostatic hold.},
doi = {10.1149/2.0951902jes},
journal = {Journal of the Electrochemical Society},
number = 4,
volume = 166,
place = {United States},
year = {2019},
month = {2}
}

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