Onsager Transport Coefficients and Transference Numbers in Polyelectrolyte Solutions and Polymerized Ionic Liquids

Fong, Kara D.; Self, Julian; McCloskey, Bryan D.; Persson, Kristin A.

doi:10.1021/acs.macromol.0c02001

Onsager Transport Coefficients and Transference Numbers in Polyelectrolyte Solutions and Polymerized Ionic Liquids

Journal Article · Wed Oct 21 00:00:00 EDT 2020 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.0c02001· OSTI ID:1766517

^[1]; ^[1]; ^[1]; ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Electrolytes featuring negatively charged polymers, such as nonaqueous polyelectrolyte solutions and polymerized ionic liquids, are currently under investigation as potential high cation transference number (t+) electrolytes for lithium-ion batteries. Herein, we use coarse-grained molecular dynamics simulations to characterize the Onsager transport coefficients of polyelectrolyte solutions as a function of chain length and concentration. For all the systems studied, we find that the rigorously computed transference number is substantially lower than that approximated by the ideal solution (Nernst-Einstein) equations typically used to characterize these systems due to the presence of strong anion-anion and cation-anion correlations. None of the polyelectrolyte solutions achieve t+ greater than that of the conventional binary salt electrolyte, with some solutions having negative t+. Overall, this work demonstrates that the Nernst-Einstein assumption does not provide a physically meaningful estimate of the transference number in these solutions and calls into question the expectation of polyelectrolytes to exhibit a high cation transference number.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1766517

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 21 Vol. 53; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Transport phenomena in electrolyte solutions: Nonequilibrium thermodynamics and statistical mechanics Fong, Kara D.; Bergstrom, Helen K.; McCloskey, Bryan D. AIChE Journal, Vol. 66, Issue 12 https://doi.org/10.1002/aic.17091	journal	November 2020
Polyelectrolyte properties of biopolymers: Conductivity and secondary structure of polyriboadenylic acid and its salts in solutions Kuznetsov, I. A.; Vorontsova, O. V.; Kozlov, A. G. Biopolymers, Vol. 31, Issue 1 https://doi.org/10.1002/bip.360310107	journal	January 1991
Single Alkaline-Ion (Li+, Na+) Conductors by Ion Exchange of Proton-Conducting Ionomers and Polyelectrolytes Kreuer, Klaus-Dieter; Wohlfarth, Andreas; de Araujo, Carla C. ChemPhysChem, Vol. 12, Issue 14 https://doi.org/10.1002/cphc.201100506	journal	July 2011
PACKMOL: A package for building initial configurations for molecular dynamics simulations Martínez, L.; Andrade, R.; Birgin, E. G. Journal of Computational Chemistry, Vol. 30, Issue 13 https://doi.org/10.1002/jcc.21224	journal	October 2009
MDAnalysis: A toolkit for the analysis of molecular dynamics simulations Michaud-Agrawal, Naveen; Denning, Elizabeth J.; Woolf, Thomas B. Journal of Computational Chemistry, Vol. 32, Issue 10 https://doi.org/10.1002/jcc.21787	journal	April 2011
Relaxation Time Spectrum and Dynamics of Stretched Polymer Chain in Dilute θ Solution: Implicit Solvent Model versus Explicit Solvent Model Yao, Ning; Li, Jiangtao; Gu, Fang Macromolecular Theory and Simulations, Vol. 29, Issue 3 https://doi.org/10.1002/mats.201900064	journal	February 2020
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
On the way to high-conductivity single lithium-ion conductors Strauss, E.; Menkin, S.; Golodnitsky, D. Journal of Solid State Electrochemistry, Vol. 21, Issue 7 https://doi.org/10.1007/s10008-017-3638-8	journal	June 2017
Ewald summation techniques in perspective: a survey Toukmaji, Abdulnour Y.; Board, John A. Computer Physics Communications, Vol. 95, Issue 2-3 https://doi.org/10.1016/0010-4655(96)00016-1	journal	June 1996
The importance of the lithium ion transference number in lithium/polymer cells Doyle, Marc; Fuller, Thomas F.; Newman, John Electrochimica Acta, Vol. 39, Issue 13 https://doi.org/10.1016/0013-4686(94)85091-7	journal	September 1994
Transference numbers, polyion mobilities, and charge fractions in aqueous solutions of lithium, sodium, and potassium dextransulfate Joshi, Y. M.; C. T. Kwak, Jan Biophysical Chemistry, Vol. 12, Issue 3-4 https://doi.org/10.1016/0301-4622(80)80010-x	journal	December 1980
Multicomponent diffusion—A brief review Bird, R. Byron; Klingenberg, Daniel J. Advances in Water Resources, Vol. 62 https://doi.org/10.1016/j.advwatres.2013.05.010	journal	December 2013
Fundamental parameters governing ion conductivity in polymer electrolytes Kisliuk, A.; Bocharova, V.; Popov, I. Electrochimica Acta, Vol. 299 https://doi.org/10.1016/j.electacta.2018.12.143	journal	March 2019
Exploring the interactions in binary mixtures of polyelectrolytes: Influence of mixture composition, concentration, and temperature on counterion condensation De, Ranjit; Lee, Hohjai; Das, Bijan Journal of Molecular Liquids, Vol. 251 https://doi.org/10.1016/j.molliq.2017.12.088	journal	February 2018
Velocity correlation functions and partial conductivities of molten AgI–AgBr by molecular dynamics simulation Matsunaga, Shigeki; Koishi, Takahiro; Tamaki, Shigeru Materials Science and Engineering: A, Vol. 449-451 https://doi.org/10.1016/j.msea.2005.12.097	journal	March 2007
Electrochemically Stable, High Transference Number Lithium Bis(malonato)borate Polymer Solution Electrolytes Dewing, Beth L.; Bible, Nicholas G.; Ellison, Christopher J. Chemistry of Materials, Vol. 32, Issue 9 https://doi.org/10.1021/acs.chemmater.9b05219	journal	April 2020
Mechanism of Conductivity Relaxation in Liquid and Polymeric Electrolytes: Direct Link between Conductivity and Diffusivity Gainaru, C.; Stacy, E. W.; Bocharova, V. The Journal of Physical Chemistry B, Vol. 120, Issue 42 https://doi.org/10.1021/acs.jpcb.6b08567	journal	October 2016
Ion Correlation and Collective Dynamics in BMIM/BF ₄ -Based Organic Electrolytes: From Dilute Solutions to the Ionic Liquid Limit McDaniel, Jesse G.; Son, Chang Yun The Journal of Physical Chemistry B, Vol. 122, Issue 28 https://doi.org/10.1021/acs.jpcb.8b04886	journal	June 2018
Counterion Transport and Transference Number in Aqueous and Nonaqueous Short-Chain Polyelectrolyte Solutions Diederichsen, Kyle M.; Terrell, Rickey C.; McCloskey, Bryan D. The Journal of Physical Chemistry B, Vol. 123, Issue 50 https://doi.org/10.1021/acs.jpcb.9b09517	journal	November 2019
Dielectric Constants for Quantum Chemistry and Li-Ion Batteries: Solvent Blends of Ethylene Carbonate and Ethyl Methyl Carbonate Hall, David S.; Self, Julian; Dahn, J. R. The Journal of Physical Chemistry C, Vol. 119, Issue 39 https://doi.org/10.1021/acs.jpcc.5b06022	journal	September 2015
50th Anniversary Perspective : A Perspective on Polyelectrolyte Solutions Muthukumar, M. Macromolecules, Vol. 50, Issue 24 https://doi.org/10.1021/acs.macromol.7b01929	journal	December 2017
Investigation of Solvent Type and Salt Addition in High Transference Number Nonaqueous Polyelectrolyte Solutions for Lithium Ion Batteries Diederichsen, Kyle M.; Fong, Kara D.; Terrell, Rickey C. Macromolecules, Vol. 51, Issue 21 https://doi.org/10.1021/acs.macromol.8b01696	journal	October 2018
Perspectives for Polymer Electrolytes: A View from Fundamentals of Ionic Conductivity Bocharova, V.; Sokolov, A. P. Macromolecules, Vol. 53, Issue 11 https://doi.org/10.1021/acs.macromol.9b02742	journal	April 2020
Control of Ionic Mobility via Charge Size Asymmetry in Random Ionomers Ma, Boran; Nguyen, Trung Dac; Olvera de la Cruz, Monica Nano Letters, Vol. 20, Issue 1 https://doi.org/10.1021/acs.nanolett.9b02743	journal	November 2019
Ion Transport and the True Transference Number in Nonaqueous Polyelectrolyte Solutions for Lithium Ion Batteries Fong, Kara D.; Self, Julian; Diederichsen, Kyle M. ACS Central Science, Vol. 5, Issue 7 https://doi.org/10.1021/acscentsci.9b00406	journal	June 2019
Nonaqueous Polyelectrolyte Solutions as Liquid Electrolytes with High Lithium Ion Transference Number and Conductivity Buss, Hilda G.; Chan, Sophia Y.; Lynd, Nathaniel A. ACS Energy Letters, Vol. 2, Issue 2 https://doi.org/10.1021/acsenergylett.6b00724	journal	January 2017
Promising Routes to a High Li ⁺ Transference Number Electrolyte for Lithium Ion Batteries Diederichsen, Kyle M.; McShane, Eric J.; McCloskey, Bryan D. ACS Energy Letters, Vol. 2, Issue 11 https://doi.org/10.1021/acsenergylett.7b00792	journal	October 2017
Transport in Superconcentrated LiPF ₆ and LiBF ₄ /Propylene Carbonate Electrolytes Self, Julian; Fong, Kara D.; Persson, Kristin A. ACS Energy Letters, Vol. 4, Issue 12 https://doi.org/10.1021/acsenergylett.9b02118	journal	October 2019
Ion Mobilities, Transference Numbers, and Inverse Haven Ratios of Polymeric Ionic Liquids Zhang, Zidan; Wheatle, Bill K.; Krajniak, Jakub ACS Macro Letters, Vol. 9, Issue 1 https://doi.org/10.1021/acsmacrolett.9b00908	journal	December 2019
Ionic Aggregate Structure in Ionomer Melts: Effect of Molecular Architecture on Aggregates and the Ionomer Peak Hall, Lisa M.; Seitz, Michelle E.; Winey, Karen I. Journal of the American Chemical Society, Vol. 134, Issue 1 https://doi.org/10.1021/ja209142b	journal	December 2011
Li ⁺ Cation Environment, Transport, and Mechanical Properties of the LiTFSI Doped N -Methyl- N -alkylpyrrolidinium ⁺ TFSI ^- Ionic Liquids Borodin, Oleg; Smith, Grant D.; Henderson, Wesley The Journal of Physical Chemistry B, Vol. 110, Issue 34 https://doi.org/10.1021/jp061930t	journal	August 2006
How Is Charge Transport Different in Ionic Liquids and Electrolyte Solutions? Kashyap, Hemant K.; Annapureddy, Harsha V. R.; Raineri, Fernando O. The Journal of Physical Chemistry B, Vol. 115, Issue 45 https://doi.org/10.1021/jp204182c	journal	November 2011
Strongly Charged, Flexible Polyelectrolytes in Poor Solvents: Molecular Dynamics Simulations ^† Micka, Uwe; Holm, Christian; Kremer, Kurt Langmuir, Vol. 15, Issue 12 https://doi.org/10.1021/la981191a	journal	June 1999
Dilute Solutions of Strongly Charged Flexible Polyelectrolytes in Poor Solvents: Molecular Dynamics Simulations with Explicit Solvent Chang, Rakwoo; Yethiraj, Arun Macromolecules, Vol. 39, Issue 2 https://doi.org/10.1021/ma051095y	journal	January 2006
Dynamics of Model Ionomer Melts of Various Architectures Hall, Lisa M.; Stevens, Mark J.; Frischknecht, Amalie L. Macromolecules, Vol. 45, Issue 19 https://doi.org/10.1021/ma301308n	journal	September 2012
Explicit Solvent Simulations of Friction between Brush Layers of Charged and Neutral Bottle-Brush Macromolecules Carrillo, Jan-Michael Y.; Brown, W. Michael; Dobrynin, Andrey V. Macromolecules, Vol. 45, Issue 21 https://doi.org/10.1021/ma3015849	journal	October 2012
Counterion Condensation in Solutions of Rigid Polyelectrolytes Nyquist, Rebecca M.; Ha, Bae-Yeun; Liu, Andrea J. Macromolecules, Vol. 32, Issue 10 https://doi.org/10.1021/ma9811021	journal	May 1999
Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries Bouchet, Renaud; Maria, Sébastien; Meziane, Rachid Nature Materials, Vol. 12, Issue 5 https://doi.org/10.1038/nmat3602	journal	March 2013
Polyelectrolytes in electric fields: measuring the dynamical effective charge and effective friction Grass, Kai; Holm, Christian Soft Matter, Vol. 5, Issue 10 https://doi.org/10.1039/b822276b	journal	January 2009
Counter-ion distribution around flexible polyelectrolytes having different molecular architecture Chremos, Alexandros; Douglas, Jack F. Soft Matter, Vol. 12, Issue 11 https://doi.org/10.1039/c5sm02873f	journal	January 2016
Single lithium-ion conducting solid polymer electrolytes: advances and perspectives Zhang, Heng; Li, Chunmei; Piszcz, Michal Chemical Society Reviews, Vol. 46, Issue 3 https://doi.org/10.1039/c6cs00491a	journal	January 2017
Frontiers in poly(ionic liquid)s: syntheses and applications Qian, Wenjing; Texter, John; Yan, Feng Chemical Society Reviews, Vol. 46, Issue 4 https://doi.org/10.1039/c6cs00620e	journal	January 2017
Single lithium-ion polymer electrolytes based on poly(ionic liquid)s for lithium-ion batteries Yu, Yang; Lu, Fei; Sun, Na Soft Matter, Vol. 14, Issue 30 https://doi.org/10.1039/c8sm00907d	journal	January 2018
Revisiting polymeric single lithium-ion conductors as an organic route for all-solid-state lithium ion and metal batteries Jeong, Kihun; Park, Sodam; Lee, Sang-Young Journal of Materials Chemistry A, Vol. 7, Issue 5 https://doi.org/10.1039/c8ta09056d	journal	January 2019
Electrolyte additives to enable nonaqueous polyelectrolyte solutions for lithium ion batteries Diederichsen, Kyle M.; McCloskey, Bryan D. Molecular Systems Design & Engineering, Vol. 5, Issue 1 https://doi.org/10.1039/c9me00067d	journal	January 2020
Comparative physical chemical study of isotactic and atactic poly(styrene sulphonic acid) solutions. Part 2.—Electrical conductance and transference measurements in salt-free aqueous solutions Jordan, D. O.; Kurucsev, T.; Martin, M. L. Trans. Faraday Soc., Vol. 65, Issue 0 https://doi.org/10.1039/tf9696500606	journal	January 1969
Strongly charged flexible polyelectrolytes in poor solvents: Molecular dynamics simulations with explicit solvent Chang, Rakwoo; Yethiraj, Arun The Journal of Chemical Physics, Vol. 118, Issue 14 https://doi.org/10.1063/1.1558312	journal	April 2003
Dynamics of entangled linear polymer melts: A molecular‐dynamics simulation Kremer, Kurt; Grest, Gary S. The Journal of Chemical Physics, Vol. 92, Issue 8 https://doi.org/10.1063/1.458541	journal	April 1990
A joint theoretical/experimental study of the structure, dynamics, and Li ⁺ transport in bis([tri]fluoro[methane]sulfonyl)imide [T]FSI-based ionic liquids Solano, C. J. F.; Jeremias, S.; Paillard, E. The Journal of Chemical Physics, Vol. 139, Issue 3 https://doi.org/10.1063/1.4813413	journal	July 2013
The solvation and ion condensation properties for sulfonated polyelectrolytes in different solvents—a computational study Smiatek, J.; Wohlfarth, A.; Holm, C. New Journal of Physics, Vol. 16, Issue 2 https://doi.org/10.1088/1367-2630/16/2/025001	journal	February 2014
Molecular dynamics simulation for polymers in the presence of a heat bath Grest, Gary S.; Kremer, Kurt Physical Review A, Vol. 33, Issue 5 https://doi.org/10.1103/physreva.33.3628	journal	May 1986
Topological analysis of polymeric melts: Chain-length effects and fast-converging estimators for entanglement length Hoy, Robert S.; Foteinopoulou, Katerina; Kröger, Martin Physical Review E, Vol. 80, Issue 3 https://doi.org/10.1103/physreve.80.031803	journal	September 2009
Dynamical Clustering of Counterions on Flexible Polyelectrolytes Lo, Tak Shing; Khusid, Boris; Koplik, Joel Physical Review Letters, Vol. 100, Issue 12 https://doi.org/10.1103/physrevlett.100.128301	journal	March 2008
Partial Conductivities of a Molten Salt Based on Langevin Equation Koishi, Takahiro; Tamaki, Shigeru Journal of the Physical Society of Japan, Vol. 68, Issue 3 https://doi.org/10.1143/jpsj.68.964	journal	March 1999
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
MDAnalysis: A Python Package for the Rapid Analysis of Molecular Dynamics Simulations Gowers, Richard; Linke, Max; Barnoud, Jonathan Proceedings of the Python in Science Conference https://doi.org/10.25080/Majora-629e541a-00e	conference	January 2016

Similar Records

Simplified Universal Equations for Ionic Conductivity and Transference Number

Journal Article · Sun Jun 30 20:00:00 EDT 2024 · Journal of the Electrochemical Society · OSTI ID:2580122

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Charge transport
cations
electrolytes
ions
polyelectrolytes

Onsager Transport Coefficients and Transference Numbers in Polyelectrolyte Solutions and Polymerized Ionic Liquids

Citation Formats

References (56)

Similar Records

Related Subjects