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Title: Evaluating Transport Properties and Ionic Dissociation of LiPF6 in Concentrated Electrolyte

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/2.0941712jes· OSTI ID:1436335
 [1];  [2];  [3];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Technologies Area
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab.
+ Show Author Affiliations

The presence of lithium hexafluorophosphate (LiPF6) ion pairs in carbonate-based electrolyte solutions is widely accepted in the field of battery electrolyte research and is expected to affect solution transport properties. No existing techniques are capable of directly quantifying salt dissociation in these solutions. Previous publications by others have provided estimates of dissociation degrees using dilute solution theory and pulsed field gradient nuclear magnetic resonance spectroscopy (PFG-NMR) measurements of self-diffusivity. However, the behavior of a concentrated electrolyte solution can deviate significantly from dilute solution theory predictions. This paper, for the first time, instead uses Onsager–Stefan–Maxwell concentrated solution theory and the generalized Darken relation with PFG-NMR measurements to quantify the degrees of dissociation in electrolyte solutions (LiPF6 in ethylene carbonate/diethyl carbonate, 1:1 by weight). At LiPF6 concentrations ranging from 0.1 M to 1.5 M, the salt dissociation degree is found to range from 61% to 37%. Finally, transport properties are then calculated through concentrated solution theory with corrections for these significant levels of ion pairing.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357
OSTI ID:
1436335
Journal Information:
Journal of the Electrochemical Society, Vol. 164, Issue 12; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

References (25)

Visualization of Steady-State Ionic Concentration Profiles Formed in Electrolytes during Li-Ion Battery Operation and Determination of Mass-Transport Properties by in Situ Magnetic Resonance Imaging journal June 2016
Quantum Chemistry and Molecular Dynamics Simulation Study of Dimethyl Carbonate: Ethylene Carbonate Electrolytes Doped with LiPF 6 journal February 2009
Spin Diffusion Measurements: Spin Echoes in the Presence of a Time‐Dependent Field Gradient journal January 1965
Transport Properties of LiPF[sub 6]-Based Li-Ion Battery Electrolytes journal January 2005
Measurement of transference numbers for lithium ion electrolytes via four different methods, a comparative study journal April 2011
A Critical Review of Thermal Issues in Lithium-Ion Batteries journal January 2011
Determination of Mass Transfer Parameters and Ionic Association of LiPF 6 : Organic Carbonates Solutions journal January 2017
Temperature Dependence of Self-Diffusion Coefficients of Ions and Solvents in Ethylene Carbonate, Propylene Carbonate, and Diethyl Carbonate Single Solutions and Ethylene Carbonate + Diethyl Carbonate Binary Solutions of LiPF 6 Studied by NMR journal June 2012
Resolving a Discrepancy in Diffusion Potentials, with a Case Study for Li-Ion Batteries journal January 2016
Measuring the Salt Activity Coefficient in Lithium-Battery Electrolytes journal January 2008
Microstructural Analysis and Mathematical Modeling of Electric Double-Layer Supercapacitors journal January 2005
Concentration Effects on the Entropy of Electrochemical Lithium Deposition: Implications for Li + Solvation journal October 2015
Multiscale modelling and analysis of lithium-ion battery charge and discharge journal May 2011
A Method for Estimating Transport Properties of Concentrated Electrolytes from Self-Diffusion Data journal January 2016
Electrochemical Characterization and Temperature Dependency of Mass-Transport Properties of LiPF 6 in EC:DEC journal December 2014
Competitive lithium solvation of linear and cyclic carbonates from quantum chemistry journal January 2016
Correlation factors for diffusion in solids. Part 2.—Indirect interstitial mechanism journal January 1958
The Darken Relation for Multicomponent Diffusion in Liquid Mixtures of Linear Alkanes:  An Investigation Using Molecular Dynamics (MD) Simulations journal August 2005
Spectroscopic Measurements of Ionic Association in Solutions of LiPF 6 journal August 2005
On the extraction of ion association data and transference numbers from ionic diffusivity and conductivity data in polymer electrolytes journal July 2013
Publisher's Note: Modeling and Simulation of Lithium-Ion Batteries from a Systems Engineering Perspective [ J. Electrochem. Soc. , 159, R31 (2012)] journal January 2012
Porous-electrode theory with battery applications journal January 1975
Electrolyte Solvation and Ionic Association III. Acetonitrile-Lithium Salt Mixtures–Transport Properties journal January 2013
High Rate Capability of Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 Electrode for Li-Ion Batteries journal January 2012
Ion Transport Properties of Six Lithium Salts Dissolved in γ-Butyrolactone Studied by Self-Diffusion and Ionic Conductivity Measurements journal January 2004

Cited By (4)

Time-dependent pair distribution functions based on Smoluchowski equation and application to an electrolyte solution journal March 2018
Fluorinated polysulfonamide based single ion conducting room temperature applicable gel-type polymer electrolytes for lithium ion batteries journal January 2019
Temperature and Concentration Dependence of the Ionic Transport Properties of Lithium-Ion Battery Electrolytes journal January 2019
Communication—Microscopic View of the Ethylene Carbonate Based Lithium-Ion Battery Electrolyte by X-ray Scattering journal January 2019

Figures / Tables (7)

Figure 1(p. 26)figure Figure 1
Figure 2(p. 27)figure Figure 2
Figure 3(p. 28)figure Figure 3
Figure 4(p. 29)figure Figure 4
Figure 5(p. 30)figure Figure 5
Figure 6(p. 31)figure Figure 6
Figure 7(p. 32)figure Figure 7

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
concentrated solution theory
electrolytes
ionic dissociation
lithium ion battery
pulsed field gradient NMR
transport properties