Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes

Pesko, Danielle M.; Webb, Michael A.; Jung, Yukyung; Zheng, Qi; Miller, Thomas F.; Coates, Geoffrey W.; Balsara, Nitash P.

doi:10.1021/acs.macromol.6b00851

Title: Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes

Abstract

In this paper, we perform a joint experimental and computational study of ion transport properties in a systematic set of linear polyethers synthesized via acyclic diene metathesis (ADMET) polymerization. We measure ionic conductivity, σ, and glass transition temperature, T_g, in mixtures of polymer and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. While T_g is known to be an important factor in the ionic conductivity of polymer electrolytes, recent work indicates that the number and proximity of lithium ion solvation sites in the polymer also play an important role, but this effect has yet to be systematically investigated. Here, adding aliphatic linkers to a poly(ethylene oxide) (PEO) backbone lowers T_g and dilutes the polar groups; both factors influence ionic conductivity. To isolate these effects, we introduce a two-step normalization scheme. In the first step, Vogel–Tammann–Fulcher (VTF) fits are used to calculate a temperature-dependent reduced conductivity, σ_r(T), which is defined as the conductivity of the electrolyte at a fixed value of T – T_g. In the second step, we compute a nondimensional parameter f_exp, defined as the ratio of the reduced molar conductivity of the electrolyte of interest to that of a reference polymer (PEO) at a fixed salt concentration. We find that f_exp dependsmore »« less

Authors:

Pesko, Danielle M. ^[1]; Webb, Michael A. ^[2]; Jung, Yukyung ^[3]; Zheng, Qi ^[3]; Miller, Thomas F. ^[2]; Coates, Geoffrey W. ^[3]; Balsara, Nitash P. ^[4]

Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology. Baker Lab.
Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division. Environmental Energy Technology Division

Publication Date:: Fri Jul 15 00:00:00 EDT 2016

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

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

OSTI Identifier:: 1474952

Grant/Contract Number:: AC02-05CH11231; CHE-1335486

Resource Type:: Accepted Manuscript

Journal Name:: Macromolecules

Additional Journal Information:: Journal Volume: 49; Journal Issue: 14; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Pesko, Danielle M., Webb, Michael A., Jung, Yukyung, Zheng, Qi, Miller, Thomas F., Coates, Geoffrey W., and Balsara, Nitash P. Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes.  United States: N. p., 2016. 
Web.  doi:10.1021/acs.macromol.6b00851.

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                    Pesko, Danielle M., Webb, Michael A., Jung, Yukyung, Zheng, Qi, Miller, Thomas F., Coates, Geoffrey W., & Balsara, Nitash P. Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes.  United States.  https://doi.org/10.1021/acs.macromol.6b00851

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                    Pesko, Danielle M., Webb, Michael A., Jung, Yukyung, Zheng, Qi, Miller, Thomas F., Coates, Geoffrey W., and Balsara, Nitash P. Fri .  
"Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes".  United States.  https://doi.org/10.1021/acs.macromol.6b00851.  https://www.osti.gov/servlets/purl/1474952.

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@article{osti_1474952,

  title        = {Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes},

  author       = {Pesko, Danielle M. and Webb, Michael A. and Jung, Yukyung and Zheng, Qi and Miller, Thomas F. and Coates, Geoffrey W. and Balsara, Nitash P.},

  abstractNote = {In this paper, we perform a joint experimental and computational study of ion transport properties in a systematic set of linear polyethers synthesized via acyclic diene metathesis (ADMET) polymerization. We measure ionic conductivity, σ, and glass transition temperature, Tg, in mixtures of polymer and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. While Tg is known to be an important factor in the ionic conductivity of polymer electrolytes, recent work indicates that the number and proximity of lithium ion solvation sites in the polymer also play an important role, but this effect has yet to be systematically investigated. Here, adding aliphatic linkers to a poly(ethylene oxide) (PEO) backbone lowers Tg and dilutes the polar groups; both factors influence ionic conductivity. To isolate these effects, we introduce a two-step normalization scheme. In the first step, Vogel–Tammann–Fulcher (VTF) fits are used to calculate a temperature-dependent reduced conductivity, σr(T), which is defined as the conductivity of the electrolyte at a fixed value of T – Tg. In the second step, we compute a nondimensional parameter fexp, defined as the ratio of the reduced molar conductivity of the electrolyte of interest to that of a reference polymer (PEO) at a fixed salt concentration. We find that fexp depends only on oxygen mole fraction, x0, and is to a good approximation independent of temperature and salt concentration. Molecular dynamics simulations are performed on neat polymers to quantify the occurrences of motifs that are similar to those obtained in the vicinity of isolated lithium ions. Finally, we show that fexp is a linear function of the simulation-derived metric of connectivity between solvation sites. From the relationship between σr and fexp we derive a universal equation that can be used to predict the conductivity of ether-based polymer electrolytes at any salt concentration and temperature.},

  doi          = {10.1021/acs.macromol.6b00851},

  journal      = {Macromolecules},

  number       = 14,

  volume       = 49,

  place        = {United States},

  year         = {Fri Jul 15 00:00:00 EDT 2016},

  month        = {Fri Jul 15 00:00:00 EDT 2016}

}

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Role of Molecular Architecture on Ion Transport in Ethylene oxide-Based Polymer Electrolytes

Journal Article Deng, Chuting ; Webb, Michael A. ; Bennington, Peter ; ... - Macromolecules

This work aims to develop a detailed mechanistic understanding of the role of a graft polymer architecture on lithium ion (Li⁺) transport in poly(ethylene oxide)-based polymer electrolytes. Specifically, we compare Li⁺ transport in poly-(ethylene oxide) (PEO) versus poly(oligo oxyethylene methacrylate) (POEM) polymers doped with lithium bis( trifluoromethanesulfonyl) (LiTFSI) salts, using both experimental electrochemical characterization and molecular dynamics (MD) simulations. Furthermore, our results indicate that POEM exhibits a range of relaxation processes that cannot be interpreted solely in terms of glass-transition temperature (T_g) effects. Due to its side-chain architecture, the segmental relaxation of POEM is nonuniform across ether oxygens (EOs) andmore »« less
https://doi.org/10.1021/acs.macromol.0c02424

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Lithium batteries: Status, prospects and future journal, May 2010

Issues and challenges facing rechargeable lithium batteries journal, November 2001

Polymer Electrolytes for Lithium-Ion Batteries journal, April 1998

Polymer Electrolytes: The Key to Lithium Polymer Batteries journal, March 2000

Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes journal, December 1994

The effect of molecular weight on cation mobility in polymer electrolytes journal, March 1993

Physical properties of solid polymer electrolyte PEO(LiTFSI) complexes journal, August 1995

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

Complexes of alkali metal ions with poly(ethylene oxide) journal, November 1973

Structure and ion transport in polymer-salt complexes journal, October 1981

Molecular Dynamics Simulations of Poly(ethylene oxide)/LiI Melts. 1. Structural and Conformational Properties journal, November 1998

Role of the ceramic fillers in enhancing the transport properties of composite polymer electrolytes journal, May 2001

The Influence of Inert Oxide Fillers on Poly(ethylene oxide) and Amorphous Poly(ethylene oxide) Based Polymer Electrolytes † journal, September 2001

Nanomaterials for Rechargeable Lithium Batteries journal, April 2008

Nanocomposite polymer electrolytes for lithium batteries journal, July 1998

Ionic conductivity of plasticized(PEO)-LiCF3SO3 electrolytes journal, April 1998

The effect of plasticizers on transport and electrochemical properties of PEO-based electrolytes for lithium rechargeable batteries journal, July 2002

Ionic liquids to the rescue? Overcoming the ionic conductivity limitations of polymer electrolytes journal, December 2003

Ionic conduction in plasticized blend polymer electrolytes journal, January 1997

Ionic conductivity of electrolytes formed from PEO-LiCF3SO3 complex low molecular weight poly(ethylene glycol) journal, May 1987

Ionic conduction in PEO–PAN blend polymer electrolytes journal, January 2000

Enhanced lithium ion transport in PEO-based solid polymer electrolytes employing a novel class of plasticizers journal, June 1997

Lithium ion conductivity in polyoxyethylene/polyethylenimine blends journal, March 2001

Structural, morphological and electrical characterization of polymer electrolytes based on PEO/PPO blends journal, May 1996

Suppression of Lithium Dendrite Growth Using Cross-Linked Polyethylene/Poly(ethylene oxide) Electrolytes: A New Approach for Practical Lithium-Metal Polymer Batteries journal, May 2014

Ion conductive characteristics of cross-linked network polysiloxane-based solid polymer electrolytes journal, May 2004

Polymer electrolytes derived from dendritic polyether macromonomers journal, June 2002

Quantum chemical studies of Li+ cation binding to polyalkyloxides journal, August 2002

Ionic Conductivity of Polymeric Solid Electrolytes Based on Poly(propylene oxide) or Poly(tetramethylene oxide) journal, November 1982

Effect of Molecular Weight of Polymeric Solvent on Ion Conductive Behavior in Poly(propylene oxide) Solution of LiClO4 journal, January 1983

High ionic conductivity in poly(dimethyl siloxane-co-ethylene oxide) dissolving lithium perchlorate journal, December 1984

Towards room-temperature performance for lithium–polymer batteries journal, June 2003

Polymer Electrolytes Based on Unsaturated Ethylene Oxide-Segmented Polymers journal, September 1999

Performance limitations of polymer electrolytes based on ethylene oxide polymers journal, August 2000

Allyl Glycidyl Ether-Based Polymer Electrolytes for Room Temperature Lithium Batteries journal, November 2013

Diffusion coefficients in trimethyleneoxide containing comb branch polymer electrolytes journal, November 2004

Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes journal, July 2015

Chemically Specific Dynamic Bond Percolation Model for Ion Transport in Polymer Electrolytes journal, September 2015

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Catalysis at the Interface of Ruthenium Carbene and Ruthenium Hydride Chemistry: Organometallic Aspects and Applications to Organic Synthesis journal, April 2004

Effect of molecular weight on conductivity of polymer electrolytes journal, November 2011

Acyclic diene metathesis (ADMET) polymerization: synthesis of unsaturated polyethers journal, September 1991

CHARMM general force field: A force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields journal, January 2009

Transferable Potentials for Phase Equilibria. 6. United-Atom Description for Ethers, Glycols, Ketones, and Aldehydes journal, November 2004

Computational Investigation on the Role of Plasticizers on Ion Conductivity in Poly(ethylene oxide) LiTFSI Electrolytes journal, April 2010

Fast Parallel Algorithms for Short-Range Molecular Dynamics journal, March 1995

Implementing molecular dynamics on hybrid high performance computers – Particle–particle particle-mesh journal, March 2012

Implementing molecular dynamics on hybrid high performance computers – short range forces journal, April 2011

On finite‐size effects in computer simulations using the Ewald potential journal, October 1995

Cation Transport in Polymer Electrolytes: A Microscopic Approach journal, May 2007

Understanding the Lithium Transport within a Rouse-Based Model for a PEO/LiTFSI Polymer Electrolyte journal, February 2010

Conduction in Polymers: Dynamic Disorder Transport journal, February 1994

Computer Simulations of Ion Transport in Polymer Electrolyte Membranes journal, June 2016

Mechanism of ion transport in PEO/LiTFSI complexes: Effect of temperature, molecular weight and end groups journal, October 2012

Effect of monomer structure on ionic conductivity in a systematic set of polyester electrolytes journal, June 2016

Carrier transport and generation processes in polymer electrolytes based on poly(ethylene oxide) networks journal, March 1987

Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes journal, July 2009

Ionic Conductivity of Low Molecular Weight Block Copolymer Electrolytes journal, January 2013

Effect of Grain Size on the Ionic Conductivity of a Block Copolymer Electrolyte journal, July 2014

Temperature Dependence of Ion Transport: The Compensated Arrhenius Equation journal, April 2009

Computer simulation of a polymer electrolyte: Lithium iodide in amorphous poly(ethylene oxide) journal, September 1995

Designing solid-state electrolytes for safe, energy-dense batteries journal, February 2020

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

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New frontiers for the materials genome initiative journal, April 2019

Lithium batteries: Status, prospects and future
journal, May 2010

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

Polymer Electrolytes for Lithium-Ion Batteries
journal, April 1998

Polymer Electrolytes: The Key to Lithium Polymer Batteries
journal, March 2000

Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes
journal, December 1994

The effect of molecular weight on cation mobility in polymer electrolytes
journal, March 1993

Physical properties of solid polymer electrolyte PEO(LiTFSI) complexes
journal, August 1995

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

Complexes of alkali metal ions with poly(ethylene oxide)
journal, November 1973

Structure and ion transport in polymer-salt complexes
journal, October 1981

Molecular Dynamics Simulations of Poly(ethylene oxide)/LiI Melts. 1. Structural and Conformational Properties
journal, November 1998

Role of the ceramic fillers in enhancing the transport properties of composite polymer electrolytes
journal, May 2001

The Influence of Inert Oxide Fillers on Poly(ethylene oxide) and Amorphous Poly(ethylene oxide) Based Polymer Electrolytes ^†
journal, September 2001

Nanomaterials for Rechargeable Lithium Batteries
journal, April 2008

Nanocomposite polymer electrolytes for lithium batteries
journal, July 1998

Ionic conductivity of plasticized(PEO)-LiCF3SO3 electrolytes
journal, April 1998

The effect of plasticizers on transport and electrochemical properties of PEO-based electrolytes for lithium rechargeable batteries
journal, July 2002

Ionic liquids to the rescue? Overcoming the ionic conductivity limitations of polymer electrolytes
journal, December 2003

Ionic conduction in plasticized blend polymer electrolytes
journal, January 1997

Ionic conductivity of electrolytes formed from PEO-LiCF3SO3 complex low molecular weight poly(ethylene glycol)
journal, May 1987

Ionic conduction in PEO–PAN blend polymer electrolytes
journal, January 2000

Enhanced lithium ion transport in PEO-based solid polymer electrolytes employing a novel class of plasticizers
journal, June 1997

Lithium ion conductivity in polyoxyethylene/polyethylenimine blends
journal, March 2001

Structural, morphological and electrical characterization of polymer electrolytes based on PEO/PPO blends
journal, May 1996

Suppression of Lithium Dendrite Growth Using Cross-Linked Polyethylene/Poly(ethylene oxide) Electrolytes: A New Approach for Practical Lithium-Metal Polymer Batteries
journal, May 2014

Ion conductive characteristics of cross-linked network polysiloxane-based solid polymer electrolytes
journal, May 2004

Polymer electrolytes derived from dendritic polyether macromonomers
journal, June 2002

Quantum chemical studies of Li+ cation binding to polyalkyloxides
journal, August 2002

Ionic Conductivity of Polymeric Solid Electrolytes Based on Poly(propylene oxide) or Poly(tetramethylene oxide)
journal, November 1982

Effect of Molecular Weight of Polymeric Solvent on Ion Conductive Behavior in Poly(propylene oxide) Solution of LiClO4
journal, January 1983

High ionic conductivity in poly(dimethyl siloxane-co-ethylene oxide) dissolving lithium perchlorate
journal, December 1984

Towards room-temperature performance for lithium–polymer batteries
journal, June 2003

Polymer Electrolytes Based on Unsaturated Ethylene Oxide-Segmented Polymers
journal, September 1999

Performance limitations of polymer electrolytes based on ethylene oxide polymers
journal, August 2000

Allyl Glycidyl Ether-Based Polymer Electrolytes for Room Temperature Lithium Batteries
journal, November 2013

Diffusion coefficients in trimethyleneoxide containing comb branch polymer electrolytes
journal, November 2004

Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes
journal, July 2015

Chemically Specific Dynamic Bond Percolation Model for Ion Transport in Polymer Electrolytes
journal, September 2015

Poly(ether–thioethers) by Thiol–Ene Click and Their Oxidized Analogues as Lithium Polymer Electrolytes
journal, February 2016

Catalysis at the Interface of Ruthenium Carbene and Ruthenium Hydride Chemistry: Organometallic Aspects and Applications to Organic Synthesis
journal, April 2004

Effect of molecular weight on conductivity of polymer electrolytes
journal, November 2011

Acyclic diene metathesis (ADMET) polymerization: synthesis of unsaturated polyethers
journal, September 1991

CHARMM general force field: A force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields
journal, January 2009

Transferable Potentials for Phase Equilibria. 6. United-Atom Description for Ethers, Glycols, Ketones, and Aldehydes
journal, November 2004

Computational Investigation on the Role of Plasticizers on Ion Conductivity in Poly(ethylene oxide) LiTFSI Electrolytes
journal, April 2010

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995

Implementing molecular dynamics on hybrid high performance computers – Particle–particle particle-mesh
journal, March 2012

Implementing molecular dynamics on hybrid high performance computers – short range forces
journal, April 2011

On finite‐size effects in computer simulations using the Ewald potential
journal, October 1995

Cation Transport in Polymer Electrolytes: A Microscopic Approach
journal, May 2007

Understanding the Lithium Transport within a Rouse-Based Model for a PEO/LiTFSI Polymer Electrolyte
journal, February 2010

Conduction in Polymers: Dynamic Disorder Transport
journal, February 1994

Computer Simulations of Ion Transport in Polymer Electrolyte Membranes
journal, June 2016

Mechanism of ion transport in PEO/LiTFSI complexes: Effect of temperature, molecular weight and end groups
journal, October 2012

Effect of monomer structure on ionic conductivity in a systematic set of polyester electrolytes
journal, June 2016

Carrier transport and generation processes in polymer electrolytes based on poly(ethylene oxide) networks
journal, March 1987

Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes
journal, July 2009

Ionic Conductivity of Low Molecular Weight Block Copolymer Electrolytes
journal, January 2013

Effect of Grain Size on the Ionic Conductivity of a Block Copolymer Electrolyte
journal, July 2014

Temperature Dependence of Ion Transport: The Compensated Arrhenius Equation
journal, April 2009

Computer simulation of a polymer electrolyte: Lithium iodide in amorphous poly(ethylene oxide)
journal, September 1995

Designing solid-state electrolytes for safe, energy-dense batteries
journal, February 2020

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

Designing polymers for advanced battery chemistries
journal, April 2019

Comparing Two Electrochemical Approaches for Measuring Transference Numbers in Concentrated Electrolytes
journal, January 2018

Difference between approximate and rigorously measured transference numbers in fluorinated electrolytes
journal, January 2019

New frontiers for the materials genome initiative
journal, April 2019