Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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

Journal Article · · Journal of the Electrochemical Society
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
+ Show Author Affiliations

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC)
Grant/Contract Number:
AC02-06CH11357; AC02-05CH11231
OSTI ID:
1494582
Journal Information:
Journal of the Electrochemical Society, Vol. 166, Issue 4; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

References (34)

Generalized Gradient Approximation Made Simple journal October 1996
Substituted Dioxaphosphinane as an Electrolyte Additive for High Voltage Lithium-Ion Cells with Overlithiated Layered Oxide journal January 2014
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways journal February 2014
First-Principles Analysis of Phase Stability in Layered–Layered Composite Cathodes for Lithium-Ion Batteries journal March 2014
Why is tris(trimethylsilyl) phosphite effective as an additive for high-voltage lithium-ion batteries? journal January 2015
Projector augmented-wave method journal December 1994
Improving cyclic stability of lithium nickel manganese oxide cathode for high voltage lithium ion battery by modifying electrode/electrolyte interface with electrolyte additive journal November 2014
Hybrid functionals based on a screened Coulomb potential journal May 2003
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
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
Tris(trimethylsilyl)phosphite as electrolyte additive for high voltage layered lithium nickel cobalt manganese oxide cathode of lithium ion battery journal November 2014
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
Impact of Lithium Bis(oxalate)borate Electrolyte Additive on the Performance of High-Voltage Spinel/Graphite Li-Ion Batteries journal October 2013
Electrocatalysis Paradigm for Protection of Cathode Materials in High-Voltage Lithium-Ion Batteries journal July 2016
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
Surface Structure, Morphology, and Stability of Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 Cathode Material journal April 2017
Interpreting High Precision Coulometry Results on Li-ion Cells journal January 2011
Tris(trimethylsilyl) Phosphite (TMSPi) and Triethyl Phosphite (TEPi) as Electrolyte Additives for Lithium Ion Batteries: Mechanistic Insights into Differences during LiNi 0.5 Mn 0.3 Co 0.2 O 2 -Graphite Full Cell Cycling journal January 2017
Methodology for understanding interactions between electrolyte additives and cathodes: a case of the tris(2,2,2-trifluoroethyl)phosphite additive journal January 2018
Decomposition Mechanism of Ethylene Carbonate and Fluoroethylene Carbonate through Hydrogen Abstraction under High Voltage Environment: An Ab-Initio Study journal January 2014
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
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
Enhanced high voltage performances of layered lithium nickel cobalt manganese oxide cathode by using trimethylboroxine as electrolyte additive journal September 2015
Functionality Selection Principle for High Voltage Lithium-ion Battery Electrolyte Additives journal August 2017
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
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
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

Similar Records

Related Subjects

36 MATERIALS SCIENCE
25 ENERGY STORAGE
Lithium-ion batteries
batteries - lithium
electrolytes
energy storage
high-voltage