Evaluating Transport Properties and Ionic Dissociation of LiPF 6 in Concentrated Electrolyte

Feng, Zhange; Higa, Kenneth; Han, Kee Sung; Srinivasan, Venkat

doi:10.1149/2.0941712jes

Evaluating Transport Properties and Ionic Dissociation of LiPF ₆ in Concentrated Electrolyte

Journal Article · Sat Dec 31 23:00:00 EST 2016 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.0941712jes· OSTI ID:1398176

Feng, Zhange; Higa, Kenneth; Han, Kee Sung; Srinivasan, Venkat

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 work, 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%. Transport properties are then calculated through concentrated solution theory with corrections for these significant levels of ion pairing.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (US)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1398176

Report Number(s):: PNNL-SA-128904; KP1704020

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 12 Vol. 164; ISSN 0013-4651

Publisher:: The Electrochemical Society

Country of Publication:: United States

Language:: English

References (25)

The Darken Relation for Multicomponent Diffusion in Liquid Mixtures of Linear Alkanes: An Investigation Using Molecular Dynamics (MD) Simulations Krishna, R.; van Baten, J. M. Industrial & Engineering Chemistry Research, Vol. 44, Issue 17 https://doi.org/10.1021/ie050146c	journal	August 2005
Concentration Effects on the Entropy of Electrochemical Lithium Deposition: Implications for Li ⁺ Solvation Schmid, Matthias J.; Xu, Junjie; Lindner, Jeannette The Journal of Physical Chemistry B, Vol. 119, Issue 42 https://doi.org/10.1021/acs.jpcb.5b07670	journal	October 2015
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 Hayamizu, Kikuko Journal of Chemical & Engineering Data, Vol. 57, Issue 7 https://doi.org/10.1021/je3003089	journal	June 2012
Competitive lithium solvation of linear and cyclic carbonates from quantum chemistry Borodin, Oleg; Olguin, Marco; Ganesh, P. Physical Chemistry Chemical Physics, Vol. 18, Issue 1 https://doi.org/10.1039/C5CP05121E	journal	January 2016
Microstructural Analysis and Mathematical Modeling of Electric Double-Layer Supercapacitors Verbrugge, Mark W.; Liu, Ping Journal of The Electrochemical Society, Vol. 152, Issue 5 https://doi.org/10.1149/1.1878052	journal	January 2005
Spectroscopic Measurements of Ionic Association in Solutions of LiPF ₆ Burba, Christopher M.; Frech, Roger The Journal of Physical Chemistry B, Vol. 109, Issue 31 https://doi.org/10.1021/jp058045f	journal	August 2005
Correlation factors for diffusion in solids. Part 2.—Indirect interstitial mechanism Compaan, K.; Haven, Y. Trans. Faraday Soc., Vol. 54, Issue 0 https://doi.org/10.1039/TF9585401498	journal	January 1958
Resolving a Discrepancy in Diffusion Potentials, with a Case Study for Li-Ion Batteries Bizeray, Adrien M.; Howey, David A.; Monroe, Charles W. Journal of The Electrochemical Society, Vol. 163, Issue 8 https://doi.org/10.1149/2.0451608jes	journal	January 2016
Measuring the Salt Activity Coefficient in Lithium-Battery Electrolytes Stewart, Sarah; Newman, John Journal of The Electrochemical Society, Vol. 155, Issue 6 https://doi.org/10.1149/1.2904526	journal	January 2008
Electrochemical Characterization and Temperature Dependency of Mass-Transport Properties of LiPF ₆ in EC:DEC Lundgren, Henrik; Behm, Mårten; Lindbergh, Göran Journal of The Electrochemical Society, Vol. 162, Issue 3 https://doi.org/10.1149/2.0641503jes	journal	December 2014
Spin Diffusion Measurements: Spin Echoes in the Presence of a Time‐Dependent Field Gradient Stejskal, E. O.; Tanner, J. E. The Journal of Chemical Physics, Vol. 42, Issue 1 https://doi.org/10.1063/1.1695690	journal	January 1965
Ion Transport Properties of Six Lithium Salts Dissolved in γ-Butyrolactone Studied by Self-Diffusion and Ionic Conductivity Measurements Aihara, Yuichi; Bando, Toshinori; Nakagawa, Hiroe Journal of The Electrochemical Society, Vol. 151, Issue 1 https://doi.org/10.1149/1.1630592	journal	January 2004
On the extraction of ion association data and transference numbers from ionic diffusivity and conductivity data in polymer electrolytes Stolwijk, Nicolaas A.; Kösters, Johannes; Wiencierz, Manfred Electrochimica Acta, Vol. 102 https://doi.org/10.1016/j.electacta.2013.04.028	journal	July 2013
Publisher's Note: Modeling and Simulation of Lithium-Ion Batteries from a Systems Engineering Perspective [ J. Electrochem. Soc. , 159, R31 (2012)] Ramadesigan, Venkatasailanathan; Northrop, Paul W. C.; De, Sumitava Journal of The Electrochemical Society, Vol. 159, Issue 5 https://doi.org/10.1149/2.086205jes	journal	January 2012
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 Krachkovskiy, Sergey A.; Bazak, J. David; Werhun, Peter Journal of the American Chemical Society, Vol. 138, Issue 25 https://doi.org/10.1021/jacs.6b04226	journal	June 2016
High Rate Capability of Li(Ni _1/3 Mn _1/3 Co _1/3 )O ₂ Electrode for Li-Ion Batteries Wu, Shao-Ling; Zhang, Wei; Song, Xiangyun Journal of The Electrochemical Society, Vol. 159, Issue 4 https://doi.org/10.1149/2.062204jes	journal	January 2012
A Method for Estimating Transport Properties of Concentrated Electrolytes from Self-Diffusion Data Kim, Sun Ung; Srinivasan, Venkat Journal of The Electrochemical Society, Vol. 163, Issue 14 https://doi.org/10.1149/2.0541614jes	journal	January 2016
Quantum Chemistry and Molecular Dynamics Simulation Study of Dimethyl Carbonate: Ethylene Carbonate Electrolytes Doped with LiPF ₆ Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry B, Vol. 113, Issue 6 https://doi.org/10.1021/jp809614h	journal	February 2009
Porous-electrode theory with battery applications Newman, John; Tiedemann, William AIChE Journal, Vol. 21, Issue 1 https://doi.org/10.1002/aic.690210103	journal	January 1975
A Critical Review of Thermal Issues in Lithium-Ion Batteries Bandhauer, Todd M.; Garimella, Srinivas; Fuller, Thomas F. Journal of The Electrochemical Society, Vol. 158, Issue 3, p. R1-R25 https://doi.org/10.1149/1.3515880	journal	January 2011
Multiscale modelling and analysis of lithium-ion battery charge and discharge Richardson, G.; Denuault, G.; Please, C. P. Journal of Engineering Mathematics, Vol. 72, Issue 1 https://doi.org/10.1007/s10665-011-9461-9	journal	May 2011
Electrolyte Solvation and Ionic Association III. Acetonitrile-Lithium Salt Mixtures–Transport Properties Seo, Daniel M.; Borodin, Oleg; Balogh, Daniel Journal of The Electrochemical Society, Vol. 160, Issue 8 https://doi.org/10.1149/2.018308jes	journal	January 2013
Determination of Mass Transfer Parameters and Ionic Association of LiPF ₆ : Organic Carbonates Solutions Krachkovskiy, Sergey A.; Bazak, J. David; Fraser, Sean Journal of The Electrochemical Society, Vol. 164, Issue 4 https://doi.org/10.1149/2.1531704jes	journal	January 2017
Measurement of transference numbers for lithium ion electrolytes via four different methods, a comparative study Zugmann, S.; Fleischmann, M.; Amereller, M. Electrochimica Acta, Vol. 56, Issue 11 https://doi.org/10.1016/j.electacta.2011.02.025	journal	April 2011
Transport Properties of LiPF[sub 6]-Based Li-Ion Battery Electrolytes Valo̸en, Lars Ole; Reimers, Jan N. Journal of The Electrochemical Society, Vol. 152, Issue 5 https://doi.org/10.1149/1.1872737	journal	January 2005

Cited By (4)

Temperature and Concentration Dependence of the Ionic Transport Properties of Lithium-Ion Battery Electrolytes Landesfeind, Johannes; Gasteiger, Hubert A. Journal of The Electrochemical Society, Vol. 166, Issue 14 https://doi.org/10.1149/2.0571912jes	journal	January 2019
Communication—Microscopic View of the Ethylene Carbonate Based Lithium-Ion Battery Electrolyte by X-ray Scattering Feng, Zhange; Sarnello, Erik; Li, Tao Journal of The Electrochemical Society, Vol. 166, Issue 2 https://doi.org/10.1149/2.0971816jes	journal	January 2019
Fluorinated polysulfonamide based single ion conducting room temperature applicable gel-type polymer electrolytes for lithium ion batteries Borzutzki, K.; Thienenkamp, J.; Diehl, M. Journal of Materials Chemistry A, Vol. 7, Issue 1 https://doi.org/10.1039/c8ta08391f	journal	January 2019
Time-dependent pair distribution functions based on Smoluchowski equation and application to an electrolyte solution Kasahara, Kento; Sato, Hirofumi Journal of Computational Chemistry, Vol. 39, Issue 20 https://doi.org/10.1002/jcc.25219	journal	March 2018

Similar Records

Evaluating Transport Properties and Ionic Dissociation of LiPF₆ in Concentrated Electrolyte

Journal Article · Thu Aug 17 00:00:00 EDT 2017 · Journal of the Electrochemical Society · OSTI ID:1436335

Role of Solution Structure in Solid Electrolyte Interphase Formation on Graphite with LiPF ₆ in Propylene Carbonate

Journal Article · Thu Nov 21 23:00:00 EST 2013 · Journal of Physical Chemistry. C · OSTI ID:1395010

Anisotropic Ion Diffusion and Electrochemically Driven Transport in Nanostructured Block Copolymer Electrolytes

Journal Article · Sun Jan 21 23:00:00 EST 2018 · Journal of Physical Chemistry. B · OSTI ID:1601170

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY