Intrinsic Ion Transport Properties of Block Copolymer Electrolytes

Sharon, Daniel; Bennington, Peter; Dolejsi, Moshe; Webb, Michael A.; Dong, Ban Xuan; de Pablo, Juan J.; Nealey, Paul F.; Patel, Shrayesh N.

doi:10.1021/acsnano.0c03713

Title: Intrinsic Ion Transport Properties of Block Copolymer Electrolytes

Abstract

Knowledge of intrinsic properties is of central importance for materials design and assessing suitability for specific applications. Self-assembling block copolymer electrolytes (BCEs) are of great interest for applications in solid-state energy storage devices. A fundamental understanding of ion transport properties, however, is hindered by the difficulty in deconvoluting extrinsic factors, such as defects, from intrinsic factors, such as the presence of interfaces between the domains. Here, we quantify the intrinsic ion transport properties of a model BCE system consisting of poly(styrene-block-ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt using a generalizable strategy of depositing thin films on interdigitated electrodes and self-assembling fully connected parallel lamellar structures throughout the films. Comparison between conductivity in homopolymer poly(ethylene oxide) (PEO)-LiTFSI electrolytes and the analogous conducting material in SEO over a range of salt concentrations (r, molar ratio of lithium ion to ethylene oxide repeat units) and temperatures reveals that between 20% and 50% of the PEO in SEO is inactive. Using mean-field theory calculations of the domain structure and monomer concentration profiles at domain interfaces-both of which vary substantially with salt concentration-the fraction of inactive PEO in the SEO, as derived from conductivity measurements, can be quantitatively reconciled with the fraction of PEOmore »« less

Authors:

^[1];

^[2]; Dolejsi, Moshe ^[2];

^[3];

^[2];

^[1];

^[1]

Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Chicago, IL (United States)
Princeton Univ., Princeton, NJ (United States)

Publication Date:: Thu Jun 04 00:00:00 EDT 2020

Research Org.:: Ames Lab., Ames, IA (United States)

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

OSTI Identifier:: 1774336

Grant/Contract Number:: AC02-06CH11357; ECCS-1542205; DMR-1420709

Resource Type:: Accepted Manuscript

Journal Name:: ACS Nano

Additional Journal Information:: Journal Volume: 14; Journal Issue: 7; Journal ID: ISSN 1936-0851

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polymer electrolyte; block copolymer; ionic conductivity; lithium ion battery; nanomaterials

Citation Formats


                    Sharon, Daniel, Bennington, Peter, Dolejsi, Moshe, Webb, Michael A., Dong, Ban Xuan, de Pablo, Juan J., Nealey, Paul F., and Patel, Shrayesh N. Intrinsic Ion Transport Properties of Block Copolymer Electrolytes.  United States: N. p., 2020. 
Web.  doi:10.1021/acsnano.0c03713.

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                    Sharon, Daniel, Bennington, Peter, Dolejsi, Moshe, Webb, Michael A., Dong, Ban Xuan, de Pablo, Juan J., Nealey, Paul F., & Patel, Shrayesh N. Intrinsic Ion Transport Properties of Block Copolymer Electrolytes.  United States.  https://doi.org/10.1021/acsnano.0c03713

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                    Sharon, Daniel, Bennington, Peter, Dolejsi, Moshe, Webb, Michael A., Dong, Ban Xuan, de Pablo, Juan J., Nealey, Paul F., and Patel, Shrayesh N. Thu .  
"Intrinsic Ion Transport Properties of Block Copolymer Electrolytes".  United States.  https://doi.org/10.1021/acsnano.0c03713.  https://www.osti.gov/servlets/purl/1774336.

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@article{osti_1774336,

  title        = {Intrinsic Ion Transport Properties of Block Copolymer Electrolytes},

  author       = {Sharon, Daniel and Bennington, Peter and Dolejsi, Moshe and Webb, Michael A. and Dong, Ban Xuan and de Pablo, Juan J. and Nealey, Paul F. and Patel, Shrayesh N.},

  abstractNote = {Knowledge of intrinsic properties is of central importance for materials design and assessing suitability for specific applications. Self-assembling block copolymer electrolytes (BCEs) are of great interest for applications in solid-state energy storage devices. A fundamental understanding of ion transport properties, however, is hindered by the difficulty in deconvoluting extrinsic factors, such as defects, from intrinsic factors, such as the presence of interfaces between the domains. Here, we quantify the intrinsic ion transport properties of a model BCE system consisting of poly(styrene-block-ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt using a generalizable strategy of depositing thin films on interdigitated electrodes and self-assembling fully connected parallel lamellar structures throughout the films. Comparison between conductivity in homopolymer poly(ethylene oxide) (PEO)-LiTFSI electrolytes and the analogous conducting material in SEO over a range of salt concentrations (r, molar ratio of lithium ion to ethylene oxide repeat units) and temperatures reveals that between 20% and 50% of the PEO in SEO is inactive. Using mean-field theory calculations of the domain structure and monomer concentration profiles at domain interfaces-both of which vary substantially with salt concentration-the fraction of inactive PEO in the SEO, as derived from conductivity measurements, can be quantitatively reconciled with the fraction of PEO that is mixed with greater than a few volume percent of polystyrene. Despite the detrimental interfacial effects for ion transport in BCEs, the intrinsic conductivity of the SEO studied here (ca. 10-3 S/cm at 90 degrees C, r = 0.085) is an order of magnitude higher than reported values from bulk samples of similar molecular weight SEO (ca. 10-4 S/cm at 90 degrees C, r = 0.085). Finally, this work provides motivation and methods for pursuing improved BCE chemical design, interfacial engineering, and processing.},

  doi          = {10.1021/acsnano.0c03713},

  journal      = {ACS Nano},

  number       = 7,

  volume       = 14,

  place        = {United States},

  year         = {Thu Jun 04 00:00:00 EDT 2020},

  month        = {Thu Jun 04 00:00:00 EDT 2020}

}

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Title: Intrinsic Ion Transport Properties of Block Copolymer Electrolytes

Abstract

Citation Formats

Effect of Molecular Weight on the Mechanical and Electrical Properties of Block Copolymer Electrolytes journal, June 2007

The morphology of symmetric diblock copolymers as revealed by neutron reflectivity journal, May 1990

Salt Doping in PEO-Containing Block Copolymers: Counterion and Concentration Effects journal, April 2009

Ion Transport Properties of Self-Assembled Polymer Electrolytes: The Role of Confinement and Interface journal, June 2013

Enhanced Conductivity via Homopolymer-Rich Pathways in Block Polymer-Blended Electrolytes journal, December 2019

Determination of Lithium-Ion Distributions in Nanostructured Block Polymer Electrolyte Thin Films by X-ray Photoelectron Spectroscopy Depth Profiling journal, December 2014

Domain Spacing and Composition Profile Behavior in Salt-Doped Cyclic vs Linear Block Polymer Thin Films: A Joint Experimental and Simulation Study journal, September 2017

Phase Behavior of Lithium Perchlorate-Doped Poly(styrene- b -isoprene- b -ethylene oxide) Triblock Copolymers journal, April 2002

Effect of Interfaces on the Melting of PEO Confined in Triblock PS- b -PEO- b -PS Copolymers journal, August 2013

On the Interfacial Width in Triblock versus Diblock Copolymers: A Neutron Reflectivity Investigation journal, September 1998

Modeling of transport of small molecules in polymer blends: Application of effective medium theory journal, February 1983

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

On the Composition of the Top Layer of Microphase Separated Thin PS-PEO Films journal, July 2009

Charge Transport in Nanostructured PS–PEO–PS Triblock Copolymer Electrolytes journal, April 2014

Rubbery Block Copolymer Electrolytes for Solid-State Rechargeable Lithium Batteries journal, January 1999

Self-assembly of block copolymer thin films journal, June 2010

Effect of Tapering on Morphology and Interfacial Behavior of Diblock Copolymers from Molecular Dynamics Simulations journal, July 2015

Salt-doped block copolymers: ion distribution, domain spacing and effective χ parameter journal, January 2012

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

Block copolymer electrolytes for rechargeable lithium batteries journal, November 2013

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

Theory of block copolymer interfaces in the strong segregation limit journal, November 1993

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

Interrogation of Electrochemical Properties of Polymer Electrolyte Thin Films with Interdigitated Electrodes journal, January 2018

Hyperbolic tangent variational approximation for interfacial profiles of binary polymer blends journal, September 1995

An Ambient Temperature Electrolyte with Superior Lithium Ion Conductivity based on a Self-Assembled Block Copolymer journal, April 2018

Isolating the Effect of Molecular Weight on Ion Transport of Non-Ionic Diblock Copolymer/Ionic Liquid Mixtures journal, March 2016

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

Surface Reconstruction Limited Conductivity in Block‐Copolymer Li Battery Electrolytes journal, September 2019

Unifying Weak- and Strong-Segregation Block Copolymer Theories journal, January 1996

Effect of Nanoscale Morphology on the Conductivity of Polymerized Ionic Liquid Block Copolymers journal, July 2011

Monte Carlo Simulations of Asymmetric Diblock Copolymer Thin Films Confined between Two Homogeneous Surfaces journal, May 2001

Quantifying Lithium Salt and Polymer Density Distributions in Nanostructured Ion-Conducting Block Polymers journal, February 2018

Anisotropic Ionic Conductivity in Block Copolymer Membranes by Magnetic Field Alignment journal, December 2010

Anisotropic Proton Conduction in Aligned Block Copolymer Electrolyte Membranes at Equilibrium with Humid Air journal, January 2010

Theoretical and experimental determination of cell constants of planar-interdigitated electrolyte conductivity sensors journal, March 1995

Ion Correlation Effects in Salt-Doped Block Copolymers journal, March 2018

Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes journal, July 2016

Ionic Liquids as Additives to Polystyrene- Block -Poly(Methyl Methacrylate) Enabling Directed Self-Assembly of Patterns with Sub-10 nm Features journal, April 2018

Probing-models for interdigitated electrode systems with ferroelectric thin films journal, April 2018

Effect of Molecular Weight and Salt Concentration on Ion Transport and the Transference Number in Polymer Electrolytes journal, October 2015

Organizing thermodynamic data obtained from multicomponent polymer electrolytes: Salt‐containing polymer blends and block copolymers journal, February 2019

Impedance study of (PEO)10LiClO4–Al2O3 composite polymer electrolyte with blocking electrodes journal, March 2001

Ionic Conductivities of Block Copolymer Electrolytes with Various Conducting Pathways: Sample Preparation and Processing Considerations journal, May 2012

Characterizing the Interface Scaling of High χ Block Copolymers near the Order–Disorder Transition journal, December 2017

Arrhenius-type temperature dependence of the segmental relaxation below Tg journal, June 1999

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

Designing Polymer Electrolytes for Safe and High Capacity Rechargeable Lithium Batteries journal, March 2017

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

Leveraging Molecular Architecture To Design New, All-Polymer Solid Electrolytes with Simultaneous Enhancement in Modulus and Ionic Conductivity journal, March 2018

Solid Polymer Electrolytes with Excellent High-Temperature Properties Based on Brush Block Copolymers Having Rigid Side Chains journal, February 2017

Structure–Conductivity Relationships in Ordered and Disordered Salt-Doped Diblock Copolymer/Homopolymer Blends journal, September 2016

Broadly Accessible Self-Consistent Field Theory for Block Polymer Materials Discovery journal, June 2016

Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies journal, January 2020

Interfacial Interaction Dependence of Microdomain Orientation in Diblock Copolymer Thin Films journal, April 2005

Anisotropic Ion Diffusion and Electrochemically Driven Transport in Nanostructured Block Copolymer Electrolytes journal, January 2018

Structure and Ionic Conductivity of Polystyrene- block -poly(ethylene oxide) Electrolytes in the High Salt Concentration Limit journal, February 2016

Influence of molecular weight and degree of segregation on local segmental dynamics of ordered block copolymers journal, January 2016

Gyroid and Other Ordered Morphologies in Single-Ion Conducting Polymers and Their Impact on Ion Conductivity journal, December 2019

Thermodynamics of Block Copolymers with and without Salt journal, December 2013

Role of Defects in Ion Transport in Block Copolymer Electrolytes journal, June 2019

Effect of Molecular Weight on the Mechanical and Electrical Properties of Block Copolymer Electrolytes
journal, June 2007

The morphology of symmetric diblock copolymers as revealed by neutron reflectivity
journal, May 1990

Salt Doping in PEO-Containing Block Copolymers: Counterion and Concentration Effects
journal, April 2009

Ion Transport Properties of Self-Assembled Polymer Electrolytes: The Role of Confinement and Interface
journal, June 2013

Enhanced Conductivity via Homopolymer-Rich Pathways in Block Polymer-Blended Electrolytes
journal, December 2019

Determination of Lithium-Ion Distributions in Nanostructured Block Polymer Electrolyte Thin Films by X-ray Photoelectron Spectroscopy Depth Profiling
journal, December 2014

Domain Spacing and Composition Profile Behavior in Salt-Doped Cyclic vs Linear Block Polymer Thin Films: A Joint Experimental and Simulation Study
journal, September 2017

Phase Behavior of Lithium Perchlorate-Doped Poly(styrene- b -isoprene- b -ethylene oxide) Triblock Copolymers
journal, April 2002

Effect of Interfaces on the Melting of PEO Confined in Triblock PS- b -PEO- b -PS Copolymers
journal, August 2013

On the Interfacial Width in Triblock versus Diblock Copolymers: A Neutron Reflectivity Investigation
journal, September 1998

Modeling of transport of small molecules in polymer blends: Application of effective medium theory
journal, February 1983

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

On the Composition of the Top Layer of Microphase Separated Thin PS-PEO Films
journal, July 2009

Charge Transport in Nanostructured PS–PEO–PS Triblock Copolymer Electrolytes
journal, April 2014

Rubbery Block Copolymer Electrolytes for Solid-State Rechargeable Lithium Batteries
journal, January 1999

Self-assembly of block copolymer thin films
journal, June 2010

Effect of Tapering on Morphology and Interfacial Behavior of Diblock Copolymers from Molecular Dynamics Simulations
journal, July 2015

Salt-doped block copolymers: ion distribution, domain spacing and effective χ parameter
journal, January 2012

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

Block copolymer electrolytes for rechargeable lithium batteries
journal, November 2013

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

Theory of block copolymer interfaces in the strong segregation limit
journal, November 1993

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

Interrogation of Electrochemical Properties of Polymer Electrolyte Thin Films with Interdigitated Electrodes
journal, January 2018

Hyperbolic tangent variational approximation for interfacial profiles of binary polymer blends
journal, September 1995

An Ambient Temperature Electrolyte with Superior Lithium Ion Conductivity based on a Self-Assembled Block Copolymer
journal, April 2018

Isolating the Effect of Molecular Weight on Ion Transport of Non-Ionic Diblock Copolymer/Ionic Liquid Mixtures
journal, March 2016

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

Surface Reconstruction Limited Conductivity in Block‐Copolymer Li Battery Electrolytes
journal, September 2019

Unifying Weak- and Strong-Segregation Block Copolymer Theories
journal, January 1996

Effect of Nanoscale Morphology on the Conductivity of Polymerized Ionic Liquid Block Copolymers
journal, July 2011

Monte Carlo Simulations of Asymmetric Diblock Copolymer Thin Films Confined between Two Homogeneous Surfaces
journal, May 2001

Quantifying Lithium Salt and Polymer Density Distributions in Nanostructured Ion-Conducting Block Polymers
journal, February 2018

Anisotropic Ionic Conductivity in Block Copolymer Membranes by Magnetic Field Alignment
journal, December 2010

Anisotropic Proton Conduction in Aligned Block Copolymer Electrolyte Membranes at Equilibrium with Humid Air
journal, January 2010

Theoretical and experimental determination of cell constants of planar-interdigitated electrolyte conductivity sensors
journal, March 1995

Ion Correlation Effects in Salt-Doped Block Copolymers
journal, March 2018

Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes
journal, July 2016

Ionic Liquids as Additives to Polystyrene- Block -Poly(Methyl Methacrylate) Enabling Directed Self-Assembly of Patterns with Sub-10 nm Features
journal, April 2018

Probing-models for interdigitated electrode systems with ferroelectric thin films
journal, April 2018

Effect of Molecular Weight and Salt Concentration on Ion Transport and the Transference Number in Polymer Electrolytes
journal, October 2015

Organizing thermodynamic data obtained from multicomponent polymer electrolytes: Salt‐containing polymer blends and block copolymers
journal, February 2019

Impedance study of (PEO)10LiClO4–Al2O3 composite polymer electrolyte with blocking electrodes
journal, March 2001

Ionic Conductivities of Block Copolymer Electrolytes with Various Conducting Pathways: Sample Preparation and Processing Considerations
journal, May 2012

Characterizing the Interface Scaling of High χ Block Copolymers near the Order–Disorder Transition
journal, December 2017

Arrhenius-type temperature dependence of the segmental relaxation below Tg
journal, June 1999

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

Designing Polymer Electrolytes for Safe and High Capacity Rechargeable Lithium Batteries
journal, March 2017

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

Leveraging Molecular Architecture To Design New, All-Polymer Solid Electrolytes with Simultaneous Enhancement in Modulus and Ionic Conductivity
journal, March 2018

Solid Polymer Electrolytes with Excellent High-Temperature Properties Based on Brush Block Copolymers Having Rigid Side Chains
journal, February 2017

Structure–Conductivity Relationships in Ordered and Disordered Salt-Doped Diblock Copolymer/Homopolymer Blends
journal, September 2016

Broadly Accessible Self-Consistent Field Theory for Block Polymer Materials Discovery
journal, June 2016

Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies
journal, January 2020

Interfacial Interaction Dependence of Microdomain Orientation in Diblock Copolymer Thin Films
journal, April 2005

Anisotropic Ion Diffusion and Electrochemically Driven Transport in Nanostructured Block Copolymer Electrolytes
journal, January 2018

Structure and Ionic Conductivity of Polystyrene- block -poly(ethylene oxide) Electrolytes in the High Salt Concentration Limit
journal, February 2016

Influence of molecular weight and degree of segregation on local segmental dynamics of ordered block copolymers
journal, January 2016

Gyroid and Other Ordered Morphologies in Single-Ion Conducting Polymers and Their Impact on Ion Conductivity
journal, December 2019

Thermodynamics of Block Copolymers with and without Salt
journal, December 2013

Role of Defects in Ion Transport in Block Copolymer Electrolytes
journal, June 2019