DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Low-Temperature Characterization of a Nonaqueous Liquid Electrolyte for Lithium Batteries

Journal Article · · Journal of the Electrochemical Society

Rechargeable batteries exhibit poor performance at low temperatures due to sluggish ion transport through the electrolytic phase. Ion transport is governed by three transport parameters—conductivity, diffusion coefficient, and the cation transference number with respect to the solvent velocity—and the thermodynamic factor. Understanding how these parameters change with temperature is necessary for designing improved electrolytes. In this work, we combine electrochemical techniques with electrophoretic NMR to determine the temperature dependence of these parameters for a liquid electrolyte, LiTFSI salt dissolved in tetraglyme between −20 and 45 °C. At colder temperatures, all species in the electrolyte tend to move more slowly due to increasing viscosity, which translates to a monotonic decrease in conductivity and diffusion coefficient with decreasing temperature. Surprisingly, we find that the field-induced velocity of solvent molecules at a particular salt concentration is a nonmonotonic function of temperature. The cation transference number with respect to the solvent velocity thus exhibits a complex dependence on temperature and salt concentration. The measured thermodynamic and transport properties are used to predict concentration gradients that will form in a lithium-lithium symmetric cell under a constant applied potential as a function of temperature using concentrated solution theory. The calculated steady current at −20 °C is lower than that at 45 °C by roughly two orders of magnitude.

Sponsoring Organization:
USDOE
OSTI ID:
2323571
Journal Information:
Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 3 Vol. 171; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (67)

Characterizing Ion Transport in Electrolytes via Concentration and Velocity Profiles journal January 2023
Toward Low‐Temperature Lithium Batteries: Advances and Prospects of Unconventional Electrolytes journal June 2021
Restricted diffusion in binary solutions journal March 1973
On experimental aspects of electrophoretic NMR: Experimental Electrophoretic NMR journal June 2004
Convection Compensation in Gradient Enhanced Nuclear Magnetic Resonance Spectroscopy journal May 1998
Convection Compensated Electrophoretic NMR journal June 2001
Steady state current flow in solid binary electrolyte cells journal June 1987
Electrochemical measurement of transference numbers in polymer electrolytes journal December 1987
Estimation of Li+ transport number in polymer electrolytes by the combination of complex impedance and potentiostatic polarization measurements journal September 1988
The low temperature performance of Li-ion batteries journal March 2003
Nonaqueous electrolytes for wide-temperature-range operation of Li-ion cells journal June 2003
Electrochemical characterisation and modelling of the mass transport phenomena in LiPF6–EC–EMC electrolyte journal September 2008
The use of ethyl acetate and methyl propanoate in combination with vinylene carbonate as ethylene carbonate-free solvent blends for electrolytes in Li-ion batteries journal February 2015
A study of highly conductive ester co-solvents in Li[Ni0.5Mn0.3Co0.2]O2/Graphite pouch cells journal April 2018
Composition-dependent thermodynamic and mass-transport characterization of lithium hexafluorophosphate in propylene carbonate journal February 2020
Comparing measurement of limiting current in block copolymer electrolytes as a function of salt concentration with theoretical predictions journal March 2022
Dynamic Heterogeneity of Solvent Motion and Ion Transport in Concentrated Electrolytes journal February 2023
Solvate Cation Migration and Ion Correlations in Solvate Ionic Liquids journal January 2020
Dielectric Constants for Quantum Chemistry and Li-Ion Batteries: Solvent Blends of Ethylene Carbonate and Ethyl Methyl Carbonate journal September 2015
Comparing Measurements of Limiting Current of Electrolytes with Theoretical Predictions up to the Solubility Limit journal September 2019
Single-Ion versus Dual-Ion Conducting Electrolytes: The Relevance of Concentration Polarization in Solid-State Batteries journal February 2022
Li + -Desolvation Dictating Lithium-Ion Battery’s Low-Temperature Performances journal November 2017
Toward Bottom-Up Understanding of Transport in Concentrated Battery Electrolytes journal June 2022
Promising Routes to a High Li + Transference Number Electrolyte for Lithium Ion Batteries journal October 2017
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries journal October 2004
Quantifying Mass Transport during Polarization in a Li Ion Battery Electrolyte by in Situ 7 Li NMR Imaging journal August 2012
Fractional Walden Rule for Ionic Liquids: Examples from Recent Measurements and a Critique of the So-Called Ideal KCl Line for the Walden Plot journal May 2010
Glyme–Lithium Salt Equimolar Molten Mixtures: Concentrated Solutions or Solvate Ionic Liquids? journal August 2012
Chelate Effects in Glyme/Lithium Bis(trifluoromethanesulfonyl)amide Solvate Ionic Liquids. I. Stability of Solvate Cations and Correlation with Electrolyte Properties journal May 2014
Limiting Conductances of Electrolytes and the Walden Product in Mixed Solvents in a Phenomenological Approach journal May 2008
Direct determination of ionic transference numbers in ionic liquids by electrophoretic NMR journal January 2015
Difference between approximate and rigorously measured transference numbers in fluorinated electrolytes journal January 2019
Liquid electrolyte development for low-temperature lithium-ion batteries journal January 2022
Complete characterization of a lithium battery electrolyte using a combination of electrophoretic NMR and electrochemical methods journal January 2022
Lithium transference in electrolytes with star-shaped multivalent anions measured by electrophoretic NMR journal January 2023
Electrophoretic NMR journal January 1994
Ohm’s law for ion conduction in lithium and beyond-lithium battery electrolytes journal July 2019
Effect of temperature on concentrated electrolytes for advanced lithium ion batteries journal June 2021
Correlations from Ion Pairing and the Nernst-Einstein Equation journal April 2019
Electric-Field-Induced Spatially Dynamic Heterogeneity of Solvent Motion and Cation Transference in Electrolytes journal May 2022
Low-Temperature Behavior of Li-Ion Cells journal January 2001
Anion and Cation Transference Numbers Determined by Electrophoretic NMR of Polymer Electrolytes Sum to Unity journal January 1999
Electrolytes for Low‐Temperature Lithium Batteries Based on Ternary Mixtures of Aliphatic Carbonates journal February 1999
The Limits of Low-Temperature Performance of Li-Ion Cells journal January 2000
Change of Conductivity with Salt Content, Solvent Composition, and Temperature for Electrolytes of LiPF[sub 6] in Ethylene Carbonate-Ethyl Methyl Carbonate journal January 2001
Low-Temperature Characterization of Lithium-Ion Carbon Anodes via Microperturbation Measurement journal January 2002
Transport Properties of LiPF[sub 6]-Based Li-Ion Battery Electrolytes journal January 2005
Mobility and Ionic Association of Lithium Salts in a Propylene Carbonate-Ethyl Methyl Carbonate Mixed Solvent journal January 1995
Conductivity and Viscosity of Solutions of LiCF3 SO 3, Li (  CF 3 SO 2 ) 2 N  , and Their Mixtures journal September 1991
Differential Diffusion Coefficients of Sodium Polysulfide Melts journal January 1989
Electrolytes for Low Temperature Operations of Li-Ion Batteries conference January 2007
Measuring the Salt Activity Coefficient in Lithium-Battery Electrolytes journal January 2008
Determination of Electrolyte Transport Properties with a Multi-Reference-Electrode Cell journal June 2021
Transport Phenomena in Low Temperature Lithium-Ion Battery Electrolytes journal August 2021
A Guide to Ethylene Carbonate-Free Electrolyte Making for Li-Ion Cells journal November 2016
A Study of the Physical Properties of Li-Ion Battery Electrolytes Containing Esters journal January 2018
Comparing Experimental Measurements of Limiting Current in Polymer Electrolytes with Theoretical Predictions journal January 2019
A Study of Three Ester Co-Solvents in Lithium-Ion Cells journal January 2017
Temperature and Concentration Dependence of the Ionic Transport Properties of Lithium-Ion Battery Electrolytes journal January 2019
Theoretical Interpretation of Ion Velocities in Concentrated Electrolytes Measured by Electrophoretic NMR journal January 2019
Carbonate Free Electrolyte for Lithium Ion Batteries Containing γ-Butyrolactone and Methyl Butyrate journal January 2015
Electrochemical Characterization and Temperature Dependency of Mass-Transport Properties of LiPF 6 in EC:DEC journal December 2014
Relationship between Steady-State Current in Symmetric Cells and Transference Number of Electrolytes Comprising Univalent and Multivalent Ions journal January 2015
Comparing Cycling Characteristics of Symmetric Lithium-Polymer-Lithium Cells with Theoretical Predictions journal January 2018
Determination of Mass Transfer Parameters and Ionic Association of LiPF 6 : Organic Carbonates Solutions journal January 2017
Determination of Transport Parameters in Liquid Binary Electrolytes: Part II. Transference Number journal January 2017
Über organische Lösungs- und Ionisierungsmittel: III. Teil: Innere Reibung und deren Zusammenhang mit dem Leitvermögen journal March 1906