Continuum Description of the Role of Negative Transference Numbers on Ion Motion in Polymer Electrolytes

Kim, Hong-Keun; Balsara, Nitash P.; Srinivasan, Venkat

doi:10.1149/1945-7111/aba790

Title: Continuum Description of the Role of Negative Transference Numbers on Ion Motion in Polymer Electrolytes

Abstract

New experimental techniques such as electrophoretic NMR (eNMR) are emerging as powerful methods for directly measuring ion velocities in electrolytes under applied electric fields. The aim of this theoretical study is to predict the spatial- and temporal-dependence of these velocities of ions as a function of the magnitude of the applied field and salt concentration. It has recently been shown that mixtures of poly(ethylene oxide)-based (PEO) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) electrolytes exhibit negative cation transference numbers in a certain salt concentration range. In this range, the cation motion at early times is directed to the positive electrode at all locations in the cell; ion migration dominates in this regime. As time progresses, the cation velocity in finite zones near both the electrodes changes sign. These zones grow rapidly with time, reflecting the increasing importance of diffusion, and a point in time is reached beyond which the cation velocity in the entire cell is directed toward the negative electrode. Overall, our work reveals the limited time window over which the results of eNMR can be used to determine the transference number. More importantly, it shows how to account for the effect of diffusional flux in such experiments.

Authors:

^[1];

^[2]; Srinivasan, Venkat ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States). Joint Center for Energy Storage Research (JCESR)
Argonne National Lab. (ANL), Lemont, IL (United States). Joint Center for Energy Storage Research (JCESR); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: Wed Jul 29 00:00:00 EDT 2020

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1660906

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the Electrochemical Society (Online)

Additional Journal Information:: Journal Name: Journal of the Electrochemical Society (Online); Journal Volume: 167; Journal Issue: 11; Journal ID: ISSN 1945-7111

Publisher:: IOP Publishing

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; concentrated solution theory; ion transport; mathematical model; solid polymer electrolytes

Citation Formats


                    Kim, Hong-Keun, Balsara, Nitash P., and Srinivasan, Venkat. Continuum Description of the Role of Negative Transference Numbers on Ion Motion in Polymer Electrolytes.  United States: N. p., 2020. 
Web.  doi:10.1149/1945-7111/aba790.

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                    Kim, Hong-Keun, Balsara, Nitash P., & Srinivasan, Venkat. Continuum Description of the Role of Negative Transference Numbers on Ion Motion in Polymer Electrolytes.  United States.  https://doi.org/10.1149/1945-7111/aba790

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                    Kim, Hong-Keun, Balsara, Nitash P., and Srinivasan, Venkat. Wed .  
"Continuum Description of the Role of Negative Transference Numbers on Ion Motion in Polymer Electrolytes".  United States.  https://doi.org/10.1149/1945-7111/aba790.  https://www.osti.gov/servlets/purl/1660906.

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@article{osti_1660906,

  title        = {Continuum Description of the Role of Negative Transference Numbers on Ion Motion in Polymer Electrolytes},

  author       = {Kim, Hong-Keun and Balsara, Nitash P. and Srinivasan, Venkat},

  abstractNote = {New experimental techniques such as electrophoretic NMR (eNMR) are emerging as powerful methods for directly measuring ion velocities in electrolytes under applied electric fields. The aim of this theoretical study is to predict the spatial- and temporal-dependence of these velocities of ions as a function of the magnitude of the applied field and salt concentration. It has recently been shown that mixtures of poly(ethylene oxide)-based (PEO) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) electrolytes exhibit negative cation transference numbers in a certain salt concentration range. In this range, the cation motion at early times is directed to the positive electrode at all locations in the cell; ion migration dominates in this regime. As time progresses, the cation velocity in finite zones near both the electrodes changes sign. These zones grow rapidly with time, reflecting the increasing importance of diffusion, and a point in time is reached beyond which the cation velocity in the entire cell is directed toward the negative electrode. Overall, our work reveals the limited time window over which the results of eNMR can be used to determine the transference number. More importantly, it shows how to account for the effect of diffusional flux in such experiments.},

  doi          = {10.1149/1945-7111/aba790},

  journal      = {Journal of the Electrochemical Society (Online)},

  number       = 11,

  volume       = 167,

  place        = {United States},

  year         = {Wed Jul 29 00:00:00 EDT 2020},

  month        = {Wed Jul 29 00:00:00 EDT 2020}

}

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Title: Continuum Description of the Role of Negative Transference Numbers on Ion Motion in Polymer Electrolytes

Abstract

Citation Formats

Polymer solid electrolytes - an overview journal, December 1983

The Measurement of a Complete Set of Transport Properties for a Concentrated Solid Polymer Electrolyte Solution journal, January 1995

Steady state current flow in solid binary electrolyte cells journal, January 1989

Transport Properties of LiPF[sub 6]-Based Li-Ion Battery Electrolytes journal, January 2005

High Ion Conducting Polymer Nanocomposite Electrolytes Using Hybrid Nanofillers journal, February 2012

Relationship between Steady-State Current in Symmetric Cells and Transference Number of Electrolytes Comprising Univalent and Multivalent Ions journal, January 2015

Comparing Measurements of Limiting Current of Electrolytes with Theoretical Predictions up to the Solubility Limit journal, September 2019

Comparing Cycling Characteristics of Symmetric Lithium-Polymer-Lithium Cells with Theoretical Predictions journal, January 2018

Effect of Salt Concentration on Ion Clustering and Transport in Polymer Solid Electrolytes: A Molecular Dynamics Study of PEO–LiTFSI journal, August 2018

Vibrational spectroscopy and structure of polymer electrolytes, poly(ethylene oxide) complexes of alkali metal salts journal, January 1981

Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries journal, March 2013

Mixed-alkali effect and short-range interactions in amorphous poly(ethylene oxide) electrolytes journal, October 1995

Negative effective Li transference numbers in Li salt/ionic liquid mixtures: does Li drift in the “Wrong” direction? journal, January 2018

Lithium Transference Numbers in PEO/LiTFSA Electrolytes Determined by Electrophoretic NMR journal, January 2019

Mechanism of Ion Transport in Amorphous Poly(ethylene oxide)/LiTFSI from Molecular Dynamics Simulations journal, February 2006

Theoretical Interpretation of Ion Velocities in Concentrated Electrolytes Measured by Electrophoretic NMR journal, January 2019

Nanomaterials for Rechargeable Lithium Batteries journal, April 2008

Steady state current flow in solid binary electrolyte cells journal, June 1987

Effect of Polymer Polarity on Ion Transport: A Competition between Ion Aggregation and Polymer Segmental Dynamics journal, September 2018

Dynamic bond percolation theory: A microscopic model for diffusion in dynamically disordered systems. I. Definition and one‐dimensional case journal, September 1983

Negative Transference Numbers in Poly(ethylene oxide)-Based Electrolytes journal, January 2017

Observation of separate cation and anion electrophoretic mobilities in pure ionic liquids journal, February 2014

Diffusion and migration in polymer electrolytes journal, April 2020

Negative Stefan-Maxwell Diffusion Coefficients and Complete Electrochemical Transport Characterization of Homopolymer and Block Copolymer Electrolytes journal, January 2018

Effect of Chemical Variations in the Structure of Poly(ethylene oxide)-Based Polymers on Lithium Transport in Concentrated Electrolytes journal, November 2019

Toward standardizing the measurement of electrochemical properties of solid-state electrolytes in lithium batteries journal, August 2000

Limiting current density in bis(trifluoromethylsulfonyl)amide-based ionic liquid for lithium batteries journal, February 2011

Polymer solid electrolytes - an overview
journal, December 1983

The Measurement of a Complete Set of Transport Properties for a Concentrated Solid Polymer Electrolyte Solution
journal, January 1995

Steady state current flow in solid binary electrolyte cells
journal, January 1989

Transport Properties of LiPF[sub 6]-Based Li-Ion Battery Electrolytes
journal, January 2005

High Ion Conducting Polymer Nanocomposite Electrolytes Using Hybrid Nanofillers
journal, February 2012

Relationship between Steady-State Current in Symmetric Cells and Transference Number of Electrolytes Comprising Univalent and Multivalent Ions
journal, January 2015

Comparing Measurements of Limiting Current of Electrolytes with Theoretical Predictions up to the Solubility Limit
journal, September 2019

Comparing Cycling Characteristics of Symmetric Lithium-Polymer-Lithium Cells with Theoretical Predictions
journal, January 2018

Effect of Salt Concentration on Ion Clustering and Transport in Polymer Solid Electrolytes: A Molecular Dynamics Study of PEO–LiTFSI
journal, August 2018

Vibrational spectroscopy and structure of polymer electrolytes, poly(ethylene oxide) complexes of alkali metal salts
journal, January 1981

Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries
journal, March 2013

Mixed-alkali effect and short-range interactions in amorphous poly(ethylene oxide) electrolytes
journal, October 1995

Negative effective Li transference numbers in Li salt/ionic liquid mixtures: does Li drift in the “Wrong” direction?
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Lithium Transference Numbers in PEO/LiTFSA Electrolytes Determined by Electrophoretic NMR
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Mechanism of Ion Transport in Amorphous Poly(ethylene oxide)/LiTFSI from Molecular Dynamics Simulations
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Theoretical Interpretation of Ion Velocities in Concentrated Electrolytes Measured by Electrophoretic NMR
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Dynamic bond percolation theory: A microscopic model for diffusion in dynamically disordered systems. I. Definition and one‐dimensional case
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