High ion content siloxane phosphonium ionomers with very low T g

Siwei Liang; Michael V. Oreilly; U. Hyeok Choi; Huai Suen Shiau; Joshua Bartels; Quan Chen; James Runt; Karen I. Winey; Ralph H. Colby

doi:10.1021/ma5001546

High ion content siloxane phosphonium ionomers with very low T _g

Siwei Liang, Michael V. Oreilly, U. Hyeok Choi, Huai Suen Shiau, Joshua Bartels, Quan Chen, James Runt, Karen I. Winey, Ralph H. Colby

Research output: Contribution to journal › Article › peer-review

52 Scopus citations

Abstract

Polysiloxane phosphonium single-ion conductors grafted with oligomeric PEO and with ion contents ranging from 5 to 22 mol % were synthesized via hydrosilylation reaction. The parent Br^- anion was exchanged to F^- or bis(trifluoromethanesulfonyl)imide (TFSI^-). X-ray scattering data suggest ion aggregation is absent in these phosphonium ionomers, which contributes to low glass transition temperatures (below -70 °C) with only a weak dependence on both ion content and counteranion type. Conductivities weakly increase with ion content but exhibit a strong dependence on anion type. The highest conductivity at 30 °C is 20 μS/cm for dry neat ionomer, with the TFSI^- anion, consistent with its relatively delocalized negative charge and large size that weaken interactions between TFSI^- and the phosphonium cation.

Original language	English
Pages (from-to)	4428-4437
Number of pages	10
Journal	Macromolecules
Volume	47
Issue number	13
DOIs	https://doi.org/10.1021/ma5001546
State	Published - 8 Jul 2014
Externally published	Yes

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title = "High ion content siloxane phosphonium ionomers with very low T g",

abstract = "Polysiloxane phosphonium single-ion conductors grafted with oligomeric PEO and with ion contents ranging from 5 to 22 mol % were synthesized via hydrosilylation reaction. The parent Br- anion was exchanged to F- or bis(trifluoromethanesulfonyl)imide (TFSI-). X-ray scattering data suggest ion aggregation is absent in these phosphonium ionomers, which contributes to low glass transition temperatures (below -70 °C) with only a weak dependence on both ion content and counteranion type. Conductivities weakly increase with ion content but exhibit a strong dependence on anion type. The highest conductivity at 30 °C is 20 μS/cm for dry neat ionomer, with the TFSI- anion, consistent with its relatively delocalized negative charge and large size that weaken interactions between TFSI- and the phosphonium cation.",

author = "Siwei Liang and Oreilly, {Michael V.} and Choi, {U. Hyeok} and Shiau, {Huai Suen} and Joshua Bartels and Quan Chen and James Runt and Winey, {Karen I.} and Colby, {Ralph H.}",

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doi = "10.1021/ma5001546",

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TY - JOUR

T1 - High ion content siloxane phosphonium ionomers with very low T g

AU - Liang, Siwei

AU - Oreilly, Michael V.

AU - Choi, U. Hyeok

AU - Shiau, Huai Suen

AU - Bartels, Joshua

AU - Chen, Quan

AU - Runt, James

AU - Winey, Karen I.

AU - Colby, Ralph H.

PY - 2014/7/8

Y1 - 2014/7/8

N2 - Polysiloxane phosphonium single-ion conductors grafted with oligomeric PEO and with ion contents ranging from 5 to 22 mol % were synthesized via hydrosilylation reaction. The parent Br- anion was exchanged to F- or bis(trifluoromethanesulfonyl)imide (TFSI-). X-ray scattering data suggest ion aggregation is absent in these phosphonium ionomers, which contributes to low glass transition temperatures (below -70 °C) with only a weak dependence on both ion content and counteranion type. Conductivities weakly increase with ion content but exhibit a strong dependence on anion type. The highest conductivity at 30 °C is 20 μS/cm for dry neat ionomer, with the TFSI- anion, consistent with its relatively delocalized negative charge and large size that weaken interactions between TFSI- and the phosphonium cation.

AB - Polysiloxane phosphonium single-ion conductors grafted with oligomeric PEO and with ion contents ranging from 5 to 22 mol % were synthesized via hydrosilylation reaction. The parent Br- anion was exchanged to F- or bis(trifluoromethanesulfonyl)imide (TFSI-). X-ray scattering data suggest ion aggregation is absent in these phosphonium ionomers, which contributes to low glass transition temperatures (below -70 °C) with only a weak dependence on both ion content and counteranion type. Conductivities weakly increase with ion content but exhibit a strong dependence on anion type. The highest conductivity at 30 °C is 20 μS/cm for dry neat ionomer, with the TFSI- anion, consistent with its relatively delocalized negative charge and large size that weaken interactions between TFSI- and the phosphonium cation.

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JO - Macromolecules

JF - Macromolecules

IS - 13

ER -

High ion content siloxane phosphonium ionomers with very low T _g

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