Effect of Superacidic Side Chain Structures on High Conductivity Aromatic Polymer Fuel Cell Membranes

Ying Chang; Angela D. Mohanty; Sarah B. Smedley; Khaldoon Abu-Hakmeh; Young Hun Lee; Joel E. Morgan; Michael A. Hickner; Seung Soon Jang; Chang Y. Ryu; Chulsung Bae

doi:10.1021/acs.macromol.5b01739

Effect of Superacidic Side Chain Structures on High Conductivity Aromatic Polymer Fuel Cell Membranes

Ying Chang, Angela D. Mohanty, Sarah B. Smedley, Khaldoon Abu-Hakmeh, Young Hun Lee, Joel E. Morgan, Michael A. Hickner, Seung Soon Jang, Chang Y. Ryu, Chulsung Bae

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

61 Scopus citations

Abstract

Proton-conducting superacidic polymer membranes with different fluoroalkyl sulfonate pendants attached to aromatic polymer backbones were synthesized via C-H functionalization and Suzuki coupling reactions. Variation in the chemical structures of the pendant acidic sulfonate moieties and their effects on membrane properties including water uptake, ion exchange capacity, morphology, and proton conductivity were systemically investigated. Membranes containing the short -OCF₂SO₃H pendant (PSU-S₅) showed a smaller hydrophilic domain size and lower proton conductivity than those containing the longer pendants -OCF₂CF₂SO₃H (PSU-S₁) and -SCF₂CF₂SO₃H (PSU-S₄), likely due to the short chain's less favorable aggregation and lower acidity. Polymer electrolyte membranes with unique branched fluoroalkyl sulfonate pendants (PSU-S₆) gave larger ionic domain sizes, more uniform hydrophilic channels, and higher proton conductivity than samples with analogous linear pendant chains (PSU-S₁), indicating that branched sulfonate structures may be a key future direction in the field of fuel cell membrane.

Original language	English (US)
Pages (from-to)	7117-7126
Number of pages	10
Journal	Macromolecules
Volume	48
Issue number	19
DOIs	https://doi.org/10.1021/acs.macromol.5b01739
State	Published - Sep 29 2015

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/acs.macromol.5b01739

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title = "Effect of Superacidic Side Chain Structures on High Conductivity Aromatic Polymer Fuel Cell Membranes",

abstract = "Proton-conducting superacidic polymer membranes with different fluoroalkyl sulfonate pendants attached to aromatic polymer backbones were synthesized via C-H functionalization and Suzuki coupling reactions. Variation in the chemical structures of the pendant acidic sulfonate moieties and their effects on membrane properties including water uptake, ion exchange capacity, morphology, and proton conductivity were systemically investigated. Membranes containing the short -OCF2SO3H pendant (PSU-S5) showed a smaller hydrophilic domain size and lower proton conductivity than those containing the longer pendants -OCF2CF2SO3H (PSU-S1) and -SCF2CF2SO3H (PSU-S4), likely due to the short chain's less favorable aggregation and lower acidity. Polymer electrolyte membranes with unique branched fluoroalkyl sulfonate pendants (PSU-S6) gave larger ionic domain sizes, more uniform hydrophilic channels, and higher proton conductivity than samples with analogous linear pendant chains (PSU-S1), indicating that branched sulfonate structures may be a key future direction in the field of fuel cell membrane.",

author = "Ying Chang and Mohanty, {Angela D.} and Smedley, {Sarah B.} and Khaldoon Abu-Hakmeh and Lee, {Young Hun} and Morgan, {Joel E.} and Hickner, {Michael A.} and Jang, {Seung Soon} and Ryu, {Chang Y.} and Chulsung Bae",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2015",

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day = "29",

doi = "10.1021/acs.macromol.5b01739",

language = "English (US)",

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T1 - Effect of Superacidic Side Chain Structures on High Conductivity Aromatic Polymer Fuel Cell Membranes

AU - Chang, Ying

AU - Mohanty, Angela D.

AU - Smedley, Sarah B.

AU - Abu-Hakmeh, Khaldoon

AU - Lee, Young Hun

AU - Morgan, Joel E.

AU - Hickner, Michael A.

AU - Jang, Seung Soon

AU - Ryu, Chang Y.

AU - Bae, Chulsung

PY - 2015/9/29

Y1 - 2015/9/29

N2 - Proton-conducting superacidic polymer membranes with different fluoroalkyl sulfonate pendants attached to aromatic polymer backbones were synthesized via C-H functionalization and Suzuki coupling reactions. Variation in the chemical structures of the pendant acidic sulfonate moieties and their effects on membrane properties including water uptake, ion exchange capacity, morphology, and proton conductivity were systemically investigated. Membranes containing the short -OCF2SO3H pendant (PSU-S5) showed a smaller hydrophilic domain size and lower proton conductivity than those containing the longer pendants -OCF2CF2SO3H (PSU-S1) and -SCF2CF2SO3H (PSU-S4), likely due to the short chain's less favorable aggregation and lower acidity. Polymer electrolyte membranes with unique branched fluoroalkyl sulfonate pendants (PSU-S6) gave larger ionic domain sizes, more uniform hydrophilic channels, and higher proton conductivity than samples with analogous linear pendant chains (PSU-S1), indicating that branched sulfonate structures may be a key future direction in the field of fuel cell membrane.

AB - Proton-conducting superacidic polymer membranes with different fluoroalkyl sulfonate pendants attached to aromatic polymer backbones were synthesized via C-H functionalization and Suzuki coupling reactions. Variation in the chemical structures of the pendant acidic sulfonate moieties and their effects on membrane properties including water uptake, ion exchange capacity, morphology, and proton conductivity were systemically investigated. Membranes containing the short -OCF2SO3H pendant (PSU-S5) showed a smaller hydrophilic domain size and lower proton conductivity than those containing the longer pendants -OCF2CF2SO3H (PSU-S1) and -SCF2CF2SO3H (PSU-S4), likely due to the short chain's less favorable aggregation and lower acidity. Polymer electrolyte membranes with unique branched fluoroalkyl sulfonate pendants (PSU-S6) gave larger ionic domain sizes, more uniform hydrophilic channels, and higher proton conductivity than samples with analogous linear pendant chains (PSU-S1), indicating that branched sulfonate structures may be a key future direction in the field of fuel cell membrane.

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Effect of Superacidic Side Chain Structures on High Conductivity Aromatic Polymer Fuel Cell Membranes

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