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Title: Structure and Ionic Conductivity of Polystyrene-block-poly(ethylene oxide) Electrolytes in the High Salt Concentration Limit

Journal Article · · Macromolecules
 [1];  [2];  [3];  [2];  [4];  [5];  [6];  [7];  [8]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  3. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  4. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR)
  5. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division
  8. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering

We explore the relationship between the morphology and ionic conductivity of block copolymer electrolytes over a wide range of salt concentrations for the system polystyrene-block-poly(ethylene oxide) (PS-b-PEO, SEO) mixed with lithium bis-(trifluoromethanesulfonyl)imide salt (LiTFSI). Two SEO polymers were studied, SEO(16-16) and SEO(4.9-5.5), over the salt concentration range r = 0.03-0.55. The numbers x and y in SEO(x-y) are the molecular weights of the blocks in kg mol-1, and the r value is the molar ratio of salt to ethylene oxide moieties. Small-angle X-ray scattering was used to characterize morphology and grain size at 120 °C, differential scanning calorimetry was used to study the crystallinity and the glass transition temperature of the PEO-rich microphase, and ac impedance spectroscopy was used to measure ionic conductivity as a function of temperature. The most surprising observation of our study is that ionic conductivity in the concentration regime 0.11 ≤ r ≤ 0.21 increases in SEO electrolytes but decreases in PEO electrolytes. The maximum in ionic conductivity with salt concentration occurs at about twice the salt concentration in SEO (r = 0.21) as in PEO (r = 0.11). Here, we propose that these observations are due to the effect of salt concentration on the grain structure in SEO electrolytes.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1474926
Journal Information:
Macromolecules, Vol. 49, Issue 5; ISSN 0024-9297
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 105 works
Citation information provided by
Web of Science

References (75)

Issues and challenges facing rechargeable lithium batteries journal November 2001
Challenges for Rechargeable Li Batteries journal February 2010
Dendrite Growth in Lithium/Polymer Systems journal January 2003
Lithium bis(fluorosulfonyl)imide/poly(ethylene oxide) polymer electrolyte journal July 2014
Safer Electrolytes for Lithium-Ion Batteries: State of the Art and Perspectives journal June 2015
Electrolytes for Li-ion transport – Review journal August 2015
Block copolymer electrolytes for rechargeable lithium batteries journal November 2013
Melt-Formable Block Copolymer Electrolytes for Lithium Rechargeable Batteries journal January 2001
Ionic Conductivities of Block Copolymer Electrolytes with Various Conducting Pathways: Sample Preparation and Processing Considerations journal May 2012
High Toughness, High Conductivity Ion Gels by Sequential Triblock Copolymer Self-Assembly and Chemical Cross-Linking journal June 2013
Evolution of Morphology, Modulus, and Conductivity in Polymer Electrolytes Prepared via Polymerization-Induced Phase Separation journal February 2015
Charge Transport in Nanostructured PS–PEO–PS Triblock Copolymer Electrolytes journal April 2014
Effect of Ion Distribution on Conductivity of Block Copolymer Electrolytes journal March 2009
Effect of Molecular Weight on the Mechanical and Electrical Properties of Block Copolymer Electrolytes journal June 2007
Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes journal July 2009
Anisotropic Ionic Conductivity in Block Copolymer Membranes by Magnetic Field Alignment journal December 2010
Effect of Grain Size on the Ionic Conductivity of a Block Copolymer Electrolyte journal July 2014
Thermodynamic and Structural Changes in Ion-Containing Symmetric Diblock Copolymers: A Small-Angle X-ray Scattering Study journal December 2011
Ionic Conductivity, Self-Assembly, and Viscoelasticity in Poly(styrene- b -ethylene oxide) Electrolytes Doped with LiTf journal September 2015
Lithium-Salt-Containing High-Molecular-Weight Polystyrene- block -Polyethylene Oxide Block Copolymer Films journal August 2015
Simple Route for Tuning the Morphology and Conductivity of Polymer Electrolytes: One End Functional Group is Enough journal October 2013
Mechanisms Underlying Ion Transport in Lamellar Block Copolymer Membranes journal March 2012
How Does Nanoscale Crystalline Structure Affect Ion Transport in Solid Polymer Electrolytes? journal June 2014
The Measurement of a Complete Set of Transport Properties for a Concentrated Solid Polymer Electrolyte Solution journal January 1995
Ion-pairing in polyether solid electrolytes and its influence on ion transport journal October 1981
Phase Diagrams and Conductivity Characterization of Some PEO-LiX Electrolytes journal January 1986
Mechanism of Ion Transport in Amorphous Poly(ethylene oxide)/LiTFSI from Molecular Dynamics Simulations journal February 2006
Physical properties of solid polymer electrolyte PEO(LiTFSI) complexes journal August 1995
Comparative study of poly(ethylene oxide) electrolytes made with LiN(CF3SO2)2, LiCF3SO3 and LiClO4: Thermal properties and conductivity behaviour journal January 1992
Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes journal December 1994
Slow recrystallization in the polymer electrolyte system poly(ethylene oxide) n –LiN(CF 3 SO 2 ) 2 journal September 2000
Mechanism of ion transport in PEO/LiTFSI complexes: Effect of temperature, molecular weight and end groups journal October 2012
Infrared and Raman study of the PEO-LiTFSI polymer electrolyte journal April 1998
The influence of phase segregation on properties of semicrystalline PEO:LiTFSI electrolytes journal September 2008
Salt Doping in PEO-Containing Block Copolymers: Counterion and Concentration Effects journal April 2009
ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties journal July 2015
Butyllithium-Initiated Anionic Synthesis of Well-Defined Poly(styrene-block-ethylene oxide) Block Copolymers with Potassium Salt Additives journal January 1996
Anionic polymerization: High vacuum techniques journal January 2000
Ionic Conductivity of Low Molecular Weight Block Copolymer Electrolytes journal January 2013
The effect of molecular weight on cation mobility in polymer electrolytes journal March 1993
Effect of molecular weight on conductivity of polymer electrolytes journal November 2011
A SAXS/WAXS/GISAXS Beamline with Multilayer Monochromator journal October 2010
Deciphering the three-dimensional morphology of free-standing block copolymer thin films by transmission electron microscopy journal January 2013
Thermodynamics of Block Copolymers with and without Salt journal December 2013
Unifying Weak- and Strong-Segregation Block Copolymer Theories journal January 1996
Block Copolymer Thermodynamics: Theory and Experiment journal October 1990
Theory of Microphase Separation in Block Copolymers journal November 1980
Fluctuation effects in the theory of microphase separation in block copolymers journal July 1987
Anisotropy of lamellar block copolymer grains journal November 2002
Nucleation and growth of anisotropic grain in block copolymers near order-disorder transition journal November 1996
Effect of quench depth on grain structure in quiescently ordered block copolymers journal June 2001
Random isotropic structures and possible glass transitions in diblock copolymer melts journal March 2006
Grain Growth and Defect Annihilation in Block Copolymers journal October 1996
Role of Grain Boundary Defects During Grain Coarsening of Lamellar Block Copolymers journal December 2012
Measuring Relative Grain-Boundary Energies in Block-Copolymer Microstructures journal March 2012
Lamellar Diblock Copolymer Grain Boundary Morphology. 4. Tilt Boundaries journal October 1994
Lamellar diblock copolymer grain boundary morphology. 1. Twist boundary characterization journal August 1993
Three-Dimensional Observations of Grain Boundary Morphologies in a Cylinder-Forming Block Copolymer journal December 2006
Kink grain boundaries in a block copolymer lamellar phase journal November 1997
Reordering transitions during annealing of block copolymer cylinder phases journal January 2016
Time-Resolved Analysis of Domain Growth and Alignment of Cylinder-Forming Block Copolymers Confined within Nanopatterned Substrates journal August 2013
Structural evolution of cylindrical-phase diblock copolymer thin films journal January 2004
Diffusion of a symmetric block copolymer in a periodic potential journal November 1991
Mechanisms of Chain Diffusion in Lamellar Block Copolymers journal July 1995
Anisotropy of Diffusion in a Lamellar Styrene−Isoprene Block Copolymer journal November 1998
Thermodynamic Properties of Block Copolymer Electrolytes Containing Imidazolium and Lithium Salts journal October 2010
Ion-Complexation-Induced Changes in the Interaction Parameter and the Chain Conformation of PS- b -PMMA Copolymers journal July 2008
Effects of Ion Solvation on the Miscibility of Binary Polymer Blends journal December 2008
Polymer Crystallization Confined in One, Two, or Three Dimensions journal December 2001
Crystallization of tethered polyethylene in confined geometries journal August 1999
Crystallization Temperature-Dependent Crystal Orientations within Nanoscale Confined Lamellae of a Self-Assembled Crystalline−Amorphous Diblock Copolymer journal June 2000
Phase structures and morphologies determined by self-organization, vitrification, and crystallization: confined crystallization in an ordered lamellar phase of PEO-b-PS diblock copolymer journal June 2001
Crystal Orientation Changes in Two-Dimensionally Confined Nanocylinders in a Poly(ethylene oxide)- b -polystyrene/Polystyrene Blend journal September 2001
Modeling of transport of small molecules in polymer blends: Application of effective medium theory journal February 1983
Percolating Transport and the Conductive Scaling Relationship in Lamellar Block Copolymers under Confinement journal February 2015

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