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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]
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  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.
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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. https://doi.org/10.1149/2.0951902jes
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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. https://doi.org/10.1149/2.0951902jes. https://www.osti.gov/servlets/purl/1494582.
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@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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https://doi.org/10.1149/2.0951902jes
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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Substituted Dioxaphosphinane as an Electrolyte Additive for High Voltage Lithium-Ion Cells with Overlithiated Layered Oxide
journal, January 2014

  • Chernyshov, Denis V.; Krachkovskiy, Sergey A.; Kapylou, Andrei V.
  • Journal of The Electrochemical Society, Vol. 161, Issue 4
  • DOI: 10.1149/2.100404jes

Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways
journal, February 2014

  • Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra
  • The Journal of Chemical Physics, Vol. 140, Issue 8
  • DOI: 10.1063/1.4865107

First-Principles Analysis of Phase Stability in Layered–Layered Composite Cathodes for Lithium-Ion Batteries
journal, March 2014

  • Iddir, Hakim; Benedek, Roy
  • Chemistry of Materials, Vol. 26, Issue 7
  • DOI: 10.1021/cm403256a

Why is tris(trimethylsilyl) phosphite effective as an additive for high-voltage lithium-ion batteries?
journal, January 2015

  • Han, Young-Kyu; Yoo, Jaeik; Yim, Taeeun
  • Journal of Materials Chemistry A, Vol. 3, Issue 20
  • DOI: 10.1039/C5TA01253H

Projector augmented-wave method
journal, December 1994

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Evaluation of Electrolyte Oxidation Stability on Charged LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Surface through Potentiostatic Holds
journal, January 2016

  • Tornheim, Adam; Trask, Stephen E.; Zhang, Zhengcheng
  • Journal of The Electrochemical Society, Vol. 163, Issue 8
  • DOI: 10.1149/2.1051608jes

Ab initio study of the operating mechanisms of tris(trimethylsilyl) phosphite as a multifunctional additive for Li-ion batteries
journal, July 2017

Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014

  • Lin, Feng; Markus, Isaac M.; Nordlund, Dennis
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4529

Mechanistic Insight in the Function of Phosphite Additives for Protection of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode in High Voltage Li-Ion Cells
journal, April 2016

  • He, Meinan; Su, Chi-Cheung; Peebles, Cameron
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 18
  • DOI: 10.1021/acsami.6b01544

Impact of Lithium Bis(oxalate)borate Electrolyte Additive on the Performance of High-Voltage Spinel/Graphite Li-Ion Batteries
journal, October 2013

  • Pieczonka, Nicholas P. W.; Yang, Li; Balogh, Michael P.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 44
  • DOI: 10.1021/jp408717x

Electrocatalysis Paradigm for Protection of Cathode Materials in High-Voltage Lithium-Ion Batteries
journal, July 2016

  • Shkrob, Ilya A.; Abraham, Daniel P.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 28
  • DOI: 10.1021/acs.jpcc.6b05756

Inorganic additives for passivation of high voltage cathode materials
journal, February 2011

The Role of Additives in Improving Performance in High Voltage Lithium-Ion Batteries with Potentiostatic Holds
journal, January 2017

  • Tornheim, Adam; He, Meinan; Su, Chi-Cheung
  • Journal of The Electrochemical Society, Vol. 164, Issue 1
  • DOI: 10.1149/2.0471701jes

Surface Structure, Morphology, and Stability of Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 Cathode Material
journal, April 2017

  • Garcia, Juan C.; Bareño, Javier; Yan, Jianhua
  • The Journal of Physical Chemistry C, Vol. 121, Issue 15
  • DOI: 10.1021/acs.jpcc.7b00896

Interpreting High Precision Coulometry Results on Li-ion Cells
journal, January 2011

  • Smith, A. J.; Burns, J. C.; Xiong, D.
  • Journal of The Electrochemical Society, Vol. 158, Issue 10
  • DOI: 10.1149/1.3625232

Methodology for understanding interactions between electrolyte additives and cathodes: a case of the tris(2,2,2-trifluoroethyl)phosphite additive
journal, January 2018

  • Sahore, Ritu; Tornheim, Adam; Peebles, Cameron
  • Journal of Materials Chemistry A, Vol. 6, Issue 1
  • DOI: 10.1039/C7TA08289D

Understanding the Degradation Mechanisms of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Material in Lithium Ion Batteries
journal, August 2013

  • Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun
  • Advanced Energy Materials, Vol. 4, Issue 1
  • DOI: 10.1002/aenm.201300787

Effects of vinylene carbonate on high temperature storage of high voltage Li-ion batteries
journal, November 2011

Li-ion battery materials: present and future
journal, June 2015

Ab initiomolecular dynamics for liquid metals
journal, January 1993

Functionality Selection Principle for High Voltage Lithium-ion Battery Electrolyte Additives
journal, August 2017

  • Su, Chi-Cheung; He, Meinan; Peebles, Cameron
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 36
  • DOI: 10.1021/acsami.7b08953

Lithium-cyclo-difluoromethane-1,1-bis(sulfonyl)imide as a stabilizing electrolyte additive for improved high voltage applications in lithium-ion batteries
journal, January 2015

  • Murmann, Patrick; Streipert, Benjamin; Kloepsch, Richard
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 14
  • DOI: 10.1039/C5CP00483G

SUBAT: An assessment of sustainable battery technology
journal, November 2006

Chemical “Pickling” of Phosphite Additives Mitigates Impedance Rise in Li Ion Batteries
journal, April 2018

  • Peebles, Cameron; Garcia, Juan; Tornheim, Adam P.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 18
  • DOI: 10.1021/acs.jpcc.8b02056

High-resolution X-ray luminescence extension imaging
journal, February 2021

Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020

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