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 (US)
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 - Jul 8 2014

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/ma5001546

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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.\}",

year = "2014",

month = jul,

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doi = "10.1021/ma5001546",

language = "English (US)",

volume = "47",

pages = "4428--4437",

journal = "Macromolecules",

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publisher = "American Chemical Society",

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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.

UR - https://www.scopus.com/pages/publications/84903976055

UR - https://www.scopus.com/pages/publications/84903976055#tab=citedBy

U2 - 10.1021/ma5001546

DO - 10.1021/ma5001546

M3 - Article

AN - SCOPUS:84903976055

SN - 0024-9297

VL - 47

SP - 4428

EP - 4437

JO - Macromolecules

JF - Macromolecules

IS - 13

ER -

High ion content siloxane phosphonium ionomers with very low T _g

Abstract

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