Structure and dynamics of short-chain polymerized ionic liquids

Wieland, Felix; Bocharova, Vera; Münzner, P.; Hiller, W.; Sakrowski, R.; Sternemann, Christian; Böhmer, Roland; Sokolov, Alexei P.; Gainaru, Catalin

doi:10.1063/1.5109228

Title: Structure and dynamics of short-chain polymerized ionic liquids

Abstract

Combining experimental results obtained with X-ray scattering and field-gradient nuclear magnetic resonance (NMR) and an assessment of new and previous dielectric and rheology data, our study focuses on the molecular weight (M_w) evolution of local structure and dynamics in a homologous series of covalently bonded ionic liquids. Performed on a family of electrolytes with a tailored degree of ionic decoupling, this study reveals the differences between monomeric and oligomeric melts with respect to their structural organization, mass and charge transport, and molecular diffusion. Our work demonstrates that for the monomeric compound, the broadband conductivity and mechanical spectra reflect the same underlying distribution of activation barriers and that the Random Barrier Model describes fairly well both the ionic and structural relaxation processes in these materials. Moreover, the oligomers with chains comprising ten segments only exhibit both structural and dynamical fingerprints of a genuine polymer. A comparison of conductivity levels estimated using the self-diffusion coefficients probed via NMR and those probed directly with dielectric spectroscopy reflects the emerging of ion correlations which are affecting the macroscopic charge transport in these materials in a chain-length dependent manner.

Authors:

^[1];

^[2];

^[1]; Hiller, W. ^[1];

^[1];

^[2];

^[1]

Technische Univ. of Dortmund (Germany)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Publication Date:: Tue Jul 16 00:00:00 EDT 2019

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; German Research Foundation (DFG)

OSTI Identifier:: 1558518

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 151; Journal Issue: 3; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

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

Citation Formats


                    Wieland, Felix, Bocharova, Vera, Münzner, P., Hiller, W., Sakrowski, R., Sternemann, Christian, Böhmer, Roland, Sokolov, Alexei P., and Gainaru, Catalin. Structure and dynamics of short-chain polymerized ionic liquids.  United States: N. p., 2019. 
Web.  doi:10.1063/1.5109228.

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                    Wieland, Felix, Bocharova, Vera, Münzner, P., Hiller, W., Sakrowski, R., Sternemann, Christian, Böhmer, Roland, Sokolov, Alexei P., & Gainaru, Catalin. Structure and dynamics of short-chain polymerized ionic liquids.  United States.  https://doi.org/10.1063/1.5109228

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                    Wieland, Felix, Bocharova, Vera, Münzner, P., Hiller, W., Sakrowski, R., Sternemann, Christian, Böhmer, Roland, Sokolov, Alexei P., and Gainaru, Catalin. Tue .  
"Structure and dynamics of short-chain polymerized ionic liquids".  United States.  https://doi.org/10.1063/1.5109228.  https://www.osti.gov/servlets/purl/1558518.

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@article{osti_1558518,

  title        = {Structure and dynamics of short-chain polymerized ionic liquids},

  author       = {Wieland, Felix and Bocharova, Vera and Münzner, P. and Hiller, W. and Sakrowski, R. and Sternemann, Christian and Böhmer, Roland and Sokolov, Alexei P. and Gainaru, Catalin},

  abstractNote = {Combining experimental results obtained with X-ray scattering and field-gradient nuclear magnetic resonance (NMR) and an assessment of new and previous dielectric and rheology data, our study focuses on the molecular weight (Mw) evolution of local structure and dynamics in a homologous series of covalently bonded ionic liquids. Performed on a family of electrolytes with a tailored degree of ionic decoupling, this study reveals the differences between monomeric and oligomeric melts with respect to their structural organization, mass and charge transport, and molecular diffusion. Our work demonstrates that for the monomeric compound, the broadband conductivity and mechanical spectra reflect the same underlying distribution of activation barriers and that the Random Barrier Model describes fairly well both the ionic and structural relaxation processes in these materials. Moreover, the oligomers with chains comprising ten segments only exhibit both structural and dynamical fingerprints of a genuine polymer. A comparison of conductivity levels estimated using the self-diffusion coefficients probed via NMR and those probed directly with dielectric spectroscopy reflects the emerging of ion correlations which are affecting the macroscopic charge transport in these materials in a chain-length dependent manner.},

  doi          = {10.1063/1.5109228},

  journal      = {Journal of Chemical Physics},

  number       = 3,

  volume       = 151,

  place        = {United States},

  year         = {Tue Jul 16 00:00:00 EDT 2019},

  month        = {Tue Jul 16 00:00:00 EDT 2019}

}

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FIG. 1: Molecular structure of polydimethyl-N-propionyloxyethylbutan-1ammonium bistriflimide systems investigated in this work. The monomeric unit containing the cation is shown on the left (with “Bu” representing a butane alkyl group). The TFSI^– anion is shown on the right.

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Title: Structure and dynamics of short-chain polymerized ionic liquids

Abstract

Citation Formats

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Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids journal, June 2016

In situ synthesis of hierarchical poly(ionic liquid)-based solid electrolytes for high-safety lithium-ion and sodium-ion batteries journal, March 2017

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups journal, June 2015

Communication: Correlation of terminal relaxation rate and viscosity enhancement in supramolecular small-molecule liquids journal, June 2018

Diffusive Flux as a New Metric for Ion-Conducting Soft Materials journal, November 2016

Ionic aggregate dissolution and conduction in a plasticized single-ion polymer conductor journal, February 2015

Measurement of translational molecular diffusion using ultrahigh magnetic field gradient NMR journal, January 1998

Dynamics of Electrolyte Solutions journal, October 1980

Molecular dynamics of supercooled ionic liquids studied by light scattering and dielectric spectroscopy journal, September 2017

Fundamental parameters governing ion conductivity in polymer electrolytes journal, March 2019

Modern Room Temperature Ionic Liquids, a Simple Guide to Understanding Their Structure and How It May Relate to Dynamics journal, August 2015

Polymerized Ionic Liquids with Enhanced Static Dielectric Constants journal, January 2013

Supercooled Liquid Dynamics Studied via Shear-Mechanical Spectroscopy journal, December 2008

Dielectric Relaxation in Liquid Polypropylene Oxides journal, December 1965

Unveiling the Ion Conduction Mechanism in Imidazolium-Based Poly(ionic liquids): A Comprehensive Investigation of the Structure-to-Transport Interplay journal, May 2017

Fundamental questions relating to ion conduction in disordered solids journal, March 2009

Alkyl Chain Length Dependence of Backbone-to-Backbone Distance in Polymerized Ionic Liquids: An Atomistic Simulation Perspective on Scattering journal, March 2017

Poly(ionic liquid)s: Polymers expanding classical property profiles journal, March 2011

Molecular Volume Effects on the Dynamics of Polymerized Ionic Liquids and their Monomers journal, September 2015

Rotational and translational diffusion in glass-forming N,N,-diethyl-3-methylbenzamide (DEET) journal, January 2011

Poly(ionic liquid)s: An update journal, July 2013

Dynamics of reversible networks journal, August 1991

Impedance and modulus spectroscopy of “real” dispersive conductors journal, September 1983

Influence of Chain Rigidity and Dielectric Constant on the Glass Transition Temperature in Polymerized Ionic Liquids journal, December 2017

Synthesis and properties of polymerized ionic liquids journal, May 2017

Dielectric and Viscoelastic Responses of Imidazolium-Based Ionomers with Different Counterions and Side Chain Lengths journal, January 2014

Mobile Ions in Amorphous Solids journal, January 1992

Ion transport in glass: Influence of glassy structure on spatial extent of nonrandom ion hopping journal, May 2001

Importance of reorientational dynamics for the charge transport in ionic liquids journal, November 2018

Mechanism of Conductivity Relaxation in Liquid and Polymeric Electrolytes: Direct Link between Conductivity and Diffusivity journal, October 2016

Transient Nonlinear Response of Dynamically Decoupled Ionic Conductors journal, August 2018

Broadband Dielectric Spectroscopy book, January 2003

Charge Transport and Glassy Dynamics in Ionic Liquids journal, November 2011

Non-Debye relaxation in structurally disordered ionic conductors: Effect of Coulomb interaction journal, January 1991

Polymeric ionic liquids: Broadening the properties and applications of polyelectrolytes journal, December 2011

Characterization of the diffusion process in oxide glasses based on the correlation between electric conduction and dielectric relaxation journal, September 1975

Shear and dielectric responses of propylene carbonate, tripropylene glycol, and a mixture of two secondary amides journal, August 2012

Electrode polarization in dielectric measurements: a review journal, August 2013

Ion dynamics in glassy ionic conductors: Scaling of mean square displacement of mobile ions journal, October 2014

A Rayleighian approach for modeling kinetics of ionic transport in polymeric media journal, February 2017

A Theory of the Linear Viscoelastic Properties of Dilute Solutions of Coiling Polymers journal, July 1953

Hydroxyalkyl-Containing Imidazolium Homopolymers: Correlation of Structure with Conductivity journal, April 2013

Main-Chain Polyimidazolium Polymers by One-Pot Synthesis and Application as Nitrogen-Doped Carbon Precursors journal, March 2017

Dielectric normal mode relaxation journal, January 1993

Observation of the slow, Debye-like relaxation in hydrogen-bonded liquids by dynamic light scattering journal, March 2014

Deeply supercooled aqueous LiCl solution studied by frequency-resolved shear rheology journal, June 2019

Polyelectrolyte as Solvent and Reaction Medium journal, December 2013

Dynamic Viscoelastic Behaviour of Low-Molecular-Mass Polystyrene Melts journal, August 1977

Dielectric Relaxation and Viscoelastic Behavior of Polymerized Ionic Liquids with Various Counteranions journal, April 2012

Diffusion in ionic liquids: the interplay between molecular structure and dynamics journal, January 2011

Viscous Liquids and the Glass Transition. II. Secondary Relaxations in Glasses of Rigid Molecules journal, September 1970

Polymerized ionic liquids: Effects of counter-anions on ion conduction and polymerization kinetics journal, April 2018

The small-angle and wide-angle X-ray scattering set-up at beamline BL9 of DELTA journal, April 2007

Diffusion in ionic liquids: the interplay between molecular structure and dynamics text, January 2011

Solid-state Li NMR with applications to the translational dynamics in ion conductors text, January 2007

Fundamental questions relating to ion conduction in disordered solids text, January 2008

Supercooled Liquid Dynamics Studied via Shear-Mechanical Spectroscopy text, January 2008

Importance of reorientational dynamics for the charge transport in ionic liquids text, January 2018

Classification of secondary relaxation in glass-formers based on dynamic properties
journal, January 2004

Direct Comparison of Atomistic Molecular Dynamics Simulations and X-ray Scattering of Polymerized Ionic Liquids
journal, March 2016

Ion Transport in Cyclopropenium-Based Polymerized Ionic Liquids
journal, February 2018

Correlating backbone-to-backbone distance to ionic conductivity in amorphous polymerized ionic liquids
journal, December 2011

Fundamental Limitations of Ionic Conductivity in Polymerized Ionic Liquids
journal, October 2018

Suppression of Convection Artifacts in Stimulated-Echo Diffusion Experiments. Double-Stimulated-Echo Experiments
journal, April 1997

Solid-state Li NMR with applications to the translational dynamics in ion conductors
journal, March 2007

Viscoelastic Behavior of the Polymerized Ionic Liquid Poly(1-ethyl-3-vinylimidazolium bis(trifluoromethanesulfonylimide))
journal, October 2011

15th anniversary of polymerised ionic liquids
journal, August 2014

A simple model of ac hopping conductivity in disordered solids
journal, April 1985

Frequency-dependent fluidity and conductivity of an ionic liquid
journal, January 2009

Jump relaxation in solid electrolytes
journal, January 1993

Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids
journal, June 2016

In situ synthesis of hierarchical poly(ionic liquid)-based solid electrolytes for high-safety lithium-ion and sodium-ion batteries
journal, March 2017

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups
journal, June 2015

Communication: Correlation of terminal relaxation rate and viscosity enhancement in supramolecular small-molecule liquids
journal, June 2018

Diffusive Flux as a New Metric for Ion-Conducting Soft Materials
journal, November 2016

Ionic aggregate dissolution and conduction in a plasticized single-ion polymer conductor
journal, February 2015

Measurement of translational molecular diffusion using ultrahigh magnetic field gradient NMR
journal, January 1998

Dynamics of Electrolyte Solutions
journal, October 1980

Molecular dynamics of supercooled ionic liquids studied by light scattering and dielectric spectroscopy
journal, September 2017

Fundamental parameters governing ion conductivity in polymer electrolytes
journal, March 2019

Modern Room Temperature Ionic Liquids, a Simple Guide to Understanding Their Structure and How It May Relate to Dynamics
journal, August 2015

Polymerized Ionic Liquids with Enhanced Static Dielectric Constants
journal, January 2013

Supercooled Liquid Dynamics Studied via Shear-Mechanical Spectroscopy
journal, December 2008

Dielectric Relaxation in Liquid Polypropylene Oxides
journal, December 1965

Unveiling the Ion Conduction Mechanism in Imidazolium-Based Poly(ionic liquids): A Comprehensive Investigation of the Structure-to-Transport Interplay
journal, May 2017

Fundamental questions relating to ion conduction in disordered solids
journal, March 2009

Alkyl Chain Length Dependence of Backbone-to-Backbone Distance in Polymerized Ionic Liquids: An Atomistic Simulation Perspective on Scattering
journal, March 2017

Poly(ionic liquid)s: Polymers expanding classical property profiles
journal, March 2011

Molecular Volume Effects on the Dynamics of Polymerized Ionic Liquids and their Monomers
journal, September 2015

Rotational and translational diffusion in glass-forming N,N,-diethyl-3-methylbenzamide (DEET)
journal, January 2011

Poly(ionic liquid)s: An update
journal, July 2013

Dynamics of reversible networks
journal, August 1991

Impedance and modulus spectroscopy of “real” dispersive conductors
journal, September 1983

Influence of Chain Rigidity and Dielectric Constant on the Glass Transition Temperature in Polymerized Ionic Liquids
journal, December 2017

Synthesis and properties of polymerized ionic liquids
journal, May 2017

Dielectric and Viscoelastic Responses of Imidazolium-Based Ionomers with Different Counterions and Side Chain Lengths
journal, January 2014

Mobile Ions in Amorphous Solids
journal, January 1992

Ion transport in glass: Influence of glassy structure on spatial extent of nonrandom ion hopping
journal, May 2001

Importance of reorientational dynamics for the charge transport in ionic liquids
journal, November 2018

Mechanism of Conductivity Relaxation in Liquid and Polymeric Electrolytes: Direct Link between Conductivity and Diffusivity
journal, October 2016

Transient Nonlinear Response of Dynamically Decoupled Ionic Conductors
journal, August 2018

Broadband Dielectric Spectroscopy
book, January 2003

Charge Transport and Glassy Dynamics in Ionic Liquids
journal, November 2011

Non-Debye relaxation in structurally disordered ionic conductors: Effect of Coulomb interaction
journal, January 1991

Polymeric ionic liquids: Broadening the properties and applications of polyelectrolytes
journal, December 2011

Characterization of the diffusion process in oxide glasses based on the correlation between electric conduction and dielectric relaxation
journal, September 1975

Shear and dielectric responses of propylene carbonate, tripropylene glycol, and a mixture of two secondary amides
journal, August 2012

Electrode polarization in dielectric measurements: a review
journal, August 2013

Ion dynamics in glassy ionic conductors: Scaling of mean square displacement of mobile ions
journal, October 2014

A Rayleighian approach for modeling kinetics of ionic transport in polymeric media
journal, February 2017

A Theory of the Linear Viscoelastic Properties of Dilute Solutions of Coiling Polymers
journal, July 1953

Hydroxyalkyl-Containing Imidazolium Homopolymers: Correlation of Structure with Conductivity
journal, April 2013

Main-Chain Polyimidazolium Polymers by One-Pot Synthesis and Application as Nitrogen-Doped Carbon Precursors
journal, March 2017

Dielectric normal mode relaxation
journal, January 1993

Observation of the slow, Debye-like relaxation in hydrogen-bonded liquids by dynamic light scattering
journal, March 2014

Deeply supercooled aqueous LiCl solution studied by frequency-resolved shear rheology
journal, June 2019

Polyelectrolyte as Solvent and Reaction Medium
journal, December 2013

Dynamic Viscoelastic Behaviour of Low-Molecular-Mass Polystyrene Melts
journal, August 1977

Dielectric Relaxation and Viscoelastic Behavior of Polymerized Ionic Liquids with Various Counteranions
journal, April 2012

Diffusion in ionic liquids: the interplay between molecular structure and dynamics
journal, January 2011

Viscous Liquids and the Glass Transition. II. Secondary Relaxations in Glasses of Rigid Molecules
journal, September 1970

Polymerized ionic liquids: Effects of counter-anions on ion conduction and polymerization kinetics
journal, April 2018

The small-angle and wide-angle X-ray scattering set-up at beamline BL9 of DELTA
journal, April 2007

Diffusion in ionic liquids: the interplay between molecular structure and dynamics
text, January 2011

Solid-state Li NMR with applications to the translational dynamics in ion conductors
text, January 2007

Fundamental questions relating to ion conduction in disordered solids
text, January 2008

Supercooled Liquid Dynamics Studied via Shear-Mechanical Spectroscopy
text, January 2008

Importance of reorientational dynamics for the charge transport in ionic liquids
text, January 2018