Effect of pressure on ion transport in amorphous and semi-crystalline polymer electrolytes

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Abstract

Ionic conductivities of polyethylene oxide (PEO) complexes with LiClO4 have been measured at pressures up to 200 MPa over the temperature range 303-353 K. Two systems differing in phase morphology are compared by reference to their temperature-dependent activation energies and volumes. For an amorphous complex of composition PEO : LiClO4 (6 : 1), Vogel-Tammann-Fulcher (VTF) behaviour is found, enabling activation energies to be calculated as a function of temperature from the best fit equation, while activation volumes are obtained directly from the isothermal pressure dependence of the conductivity. While the behaviour of the amorphous complex is adequately described by the free volume model, the corresponding data for a polycrystalline material of overall 20 : 1 stoichiometry suggests the prevalence of surface conduction at lower temperatures. Such variable-pressure, variable-temperature (VPVT) data may in future provide new insights into the behaviour of more complex polymer electrolyte systems.

Original languageEnglish
Pages (from-to)395-399
Number of pages4
JournalPhysical Chemistry Chemical Physics
Volume5
Issue number5
DOIs
Publication statusPublished - 2003

Keywords

  • ELECTRICAL-CONDUCTIVITY
  • GLASS-TRANSITION
  • FREE-VOLUME
  • TEMPERATURE

Cite this

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title = "Effect of pressure on ion transport in amorphous and semi-crystalline polymer electrolytes",
abstract = "Ionic conductivities of polyethylene oxide (PEO) complexes with LiClO4 have been measured at pressures up to 200 MPa over the temperature range 303-353 K. Two systems differing in phase morphology are compared by reference to their temperature-dependent activation energies and volumes. For an amorphous complex of composition PEO : LiClO4 (6 : 1), Vogel-Tammann-Fulcher (VTF) behaviour is found, enabling activation energies to be calculated as a function of temperature from the best fit equation, while activation volumes are obtained directly from the isothermal pressure dependence of the conductivity. While the behaviour of the amorphous complex is adequately described by the free volume model, the corresponding data for a polycrystalline material of overall 20 : 1 stoichiometry suggests the prevalence of surface conduction at lower temperatures. Such variable-pressure, variable-temperature (VPVT) data may in future provide new insights into the behaviour of more complex polymer electrolyte systems.",
keywords = "ELECTRICAL-CONDUCTIVITY, GLASS-TRANSITION, FREE-VOLUME, TEMPERATURE",
author = "Z. Stoeva and Imrie, {Corrie Thomas} and Ingram, {Malcolm David}",
year = "2003",
doi = "10.1039/b208552f",
language = "English",
volume = "5",
pages = "395--399",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "ROYAL SOC CHEMISTRY",
number = "5",

}

TY - JOUR

T1 - Effect of pressure on ion transport in amorphous and semi-crystalline polymer electrolytes

AU - Stoeva, Z.

AU - Imrie, Corrie Thomas

AU - Ingram, Malcolm David

PY - 2003

Y1 - 2003

N2 - Ionic conductivities of polyethylene oxide (PEO) complexes with LiClO4 have been measured at pressures up to 200 MPa over the temperature range 303-353 K. Two systems differing in phase morphology are compared by reference to their temperature-dependent activation energies and volumes. For an amorphous complex of composition PEO : LiClO4 (6 : 1), Vogel-Tammann-Fulcher (VTF) behaviour is found, enabling activation energies to be calculated as a function of temperature from the best fit equation, while activation volumes are obtained directly from the isothermal pressure dependence of the conductivity. While the behaviour of the amorphous complex is adequately described by the free volume model, the corresponding data for a polycrystalline material of overall 20 : 1 stoichiometry suggests the prevalence of surface conduction at lower temperatures. Such variable-pressure, variable-temperature (VPVT) data may in future provide new insights into the behaviour of more complex polymer electrolyte systems.

AB - Ionic conductivities of polyethylene oxide (PEO) complexes with LiClO4 have been measured at pressures up to 200 MPa over the temperature range 303-353 K. Two systems differing in phase morphology are compared by reference to their temperature-dependent activation energies and volumes. For an amorphous complex of composition PEO : LiClO4 (6 : 1), Vogel-Tammann-Fulcher (VTF) behaviour is found, enabling activation energies to be calculated as a function of temperature from the best fit equation, while activation volumes are obtained directly from the isothermal pressure dependence of the conductivity. While the behaviour of the amorphous complex is adequately described by the free volume model, the corresponding data for a polycrystalline material of overall 20 : 1 stoichiometry suggests the prevalence of surface conduction at lower temperatures. Such variable-pressure, variable-temperature (VPVT) data may in future provide new insights into the behaviour of more complex polymer electrolyte systems.

KW - ELECTRICAL-CONDUCTIVITY

KW - GLASS-TRANSITION

KW - FREE-VOLUME

KW - TEMPERATURE

U2 - 10.1039/b208552f

DO - 10.1039/b208552f

M3 - Article

VL - 5

SP - 395

EP - 399

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 5

ER -