Study of Ion-Polymer Interactions in Cationic and Anionic Ionomers From the Dependence of Conductivity on Temperature and Pressure

Duclot, M.; Alloin, Fannie; Brylev, Oleg; Sanchez, Jean‐Yves; Souquet, J.L.

doi:10.1142/9789812773104_0057

Cited by 4 publications

(9 citation statements)

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“…In that range it shows an unrealistic volume expansion because of the lack of attractive interactions, so that the density falls below reasonable melt densities. For pressures pտ0.1⑀/a 3 our results can be compared with measurements of the pressure-dependent conductivity in polymer electrolytes 42,4 which indeed reflect an exponential p dependence, in agreement with Eq. ͑10͒.…”

Section: Pressure-dependent Ionic Diffusionsupporting

confidence: 80%

“…On the other hand, the analysis of experimental data in Ref. 4 for temperatures close to T g amounts to setting Bϭ0.…”

Section: Pressure-dependent Ionic Diffusionmentioning

confidence: 99%

“…In order to optimize electrochemical, mechanical, and thermal properties, materials with increasing complexity are being developed. These include alkali ionomers, where anions are chemically grafted to the polymer, 4 composites, where nanosize inorganic particles are added to the polymer-salt system, 5,6 gel electroytes, 7 as well as mechanically stretched chain electrolytes where experiments suggest that orientation of chains facilities ionic transport. 8,9 At the same time, fundamental studies mostly on PEObased electrolytes are pursued with the aim to elucidate the mechanism of cation transport, controlled by the local structure and dynamics of the host network.…”

Section: Introductionmentioning

confidence: 99%

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Coupled ion and network dynamics in polymer electrolytes: Monte Carlo study of a lattice model

Dürr

Dieterich

Nitzan

2004

The Journal of Chemical Physics

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Monte Carlo simulations are used to study ion and polymer chain dynamic properties in a simplified lattice model with only one species of mobile ions. The ions interact attractively with specific beads in the host chains, while polymer beads repel each other. Cross linking of chains by the ions reduces chain mobilities which in turn suppresses ionic diffusion. Diffusion constants for ions and chains as a function of temperature follow the Vogel-Tammann-Fulcher (VTF) law with a common VTF temperature at low ion concentration, but both decouple at higher concentrations, in agreement with experimental observations. Our model allows us to introduce pressure as an independent variable through calculations of the equation of state using the quasichemical approximation, and to detect an exponential pressure dependence of the ionic diffusion.

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Section: Pressure-dependent Ionic Diffusionsupporting

confidence: 80%

“…On the other hand, the analysis of experimental data in Ref. 4 for temperatures close to T g amounts to setting Bϭ0.…”

Section: Pressure-dependent Ionic Diffusionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Coupled ion and network dynamics in polymer electrolytes: Monte Carlo study of a lattice model

Dürr

Dieterich

Nitzan

2004

The Journal of Chemical Physics

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“…[42][43][44] As in solid electrolytes with carbonate units there is no segmental motion like in electrolytes with PEG chains; the mobility of the ions only depends on the potential barrier, E hop , that the cation must overcome to move from one site to another. At higher concentrations the number of cationic charge carriers increases, but their mobility is hindered due to the formation of aggregates.…”

Section: Conductivity Measurementsmentioning

confidence: 99%

“…At higher concentrations the number of cationic charge carriers increases, but their mobility is hindered due to the formation of aggregates. [42][43][44] As in solid electrolytes with carbonate units there is no segmental motion like in electrolytes with PEG chains; the mobility of the ions only depends on the potential barrier, E hop , that the cation must overcome to move from one site to another. Increasing ion concentration leads to the formation of ion aggregates which increases this energy barrier.…”

Section: Conductivity Measurementsmentioning

confidence: 99%

Structure and ionic conductivity of liquid crystals having propylene carbonate units

et al. 2015

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Liquid-crystalline compounds with a perfluorinated aromatic ring as the mesogenic core and a propylene carbonate unit were prepared and mixed with lithium bis(trifluoro-methanesulfonyl)-imide (LiTFSI). The self-assembly was driven by the interaction of the polar propylene carbonate unit. Thus it is one of the few examples of liquid crystals with only one phenyl group that is able to self-assemble. Small-and Wide angle X-ray scattering (SAXS/WAXS) measurements indicate that the molecules spontaneously formed a smectic phase. Calculation of the Li-salt dissociation from the data obtained by a combination of impedance spectroscopy measurements and diffusion experiments by 7 Li and 19 F pulsed field gradient (PFG) NMR revealed good dissociation properties of the compounds. The complex of (2-Oxo-1,3dioxolan-4-yl)methyl 4-(decyloxy)-2,3,5,6-tetrafluorobenzoate (4b) with LiTFSI exhibited anisotropic conductivity. The conductivity parallel to the smectic orientation was 125 times higher than perpendicular and is one of the best reported for liquid crystals with propylene carbonate fragments. † Electronic supplementary information (ESI) available: DSC diagrams for the mixtures of 4a, 4b and 4c with various amounts of LiTFSI; WAXS/SAXS of 4a and 4b mixed with 10 mol% LiTFSI, ionic conductivity measurements for 4b, 6 and 8 with various amounts of LiTFSI; NMR spectra of all compounds discussed in this paper. See

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Synthesis and Lithium Ion Conduction of Polysiloxane Single-Ion Conductors Containing Novel Weak-Binding Borates

et al. 2012

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Three borate monomers: lithium triphenylstyryl borate (B1), a variant with three ethylene oxides between the vinyl and the borate (B2) and a third with perfluorinated phenyl rings (B3) were synthesized and used to prepare polysiloxane ionomers based on cyclic carbonates via hydrosilylation. B1 ion content variations show maximum 25 °C conductivity at 8 mol %, reflecting a trade-off between carrier density and glass transition temperature (T g ) increase. Ethylene oxide spacers (B2) lower T g , and increase the dielectric constant, both raising conductivity. Perfluorinating the four phenyl rings (B3) lowers the ion association energy, as anticipated by ab initio estimations. This increases conductivity, a direct result of 3 times higher measured carrier density. The ∼9 kJ/mol activation energy of simultaneously conducting ions is less than half that of ionomers with either sulfonate or bis(trifluoromethanesulfonyl) imide anions, suggesting that ionomers with weak-binding borate anions may provide a pathway to useful single-ion Li + conductors, if their T g can be lowered.

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Study of Ion-Polymer Interactions in Cationic and Anionic Ionomers From the Dependence of Conductivity on Temperature and Pressure

Cited by 4 publications

References 0 publications

Coupled ion and network dynamics in polymer electrolytes: Monte Carlo study of a lattice model

Coupled ion and network dynamics in polymer electrolytes: Monte Carlo study of a lattice model

Structure and ionic conductivity of liquid crystals having propylene carbonate units

Synthesis and Lithium Ion Conduction of Polysiloxane Single-Ion Conductors Containing Novel Weak-Binding Borates

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