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Title: Highly Proton Conducting Polyelectrolyte Membranes with Unusual Water Swelling Behavior Based on Triptycene-containing Poly(arylene ether sulfone) Multiblock Copolymers

Abstract

Multiblock poly(arylene ether sulfone) copolymers are attractive for polyelectrolyte membrane fuel cell applications due to their reportedly improved proton conductivity under partially hydrated conditions and better mechanical/thermal stability compared to Nafion. However, the long hydrophilic sequences required to achieve high conductivity usually lead to excessive water uptake and swelling, which degrade membrane dimensional stability. Herein, we report a fundamentally new approach to address this grand challenge by introducing shape-persistent triptycene units into the hydrophobic sequences of multiblock copolymers, which induce strong supramolecular chain-threading and interlocking interactions that effectively suppress water swelling. Consequently, unlike previously reported multiblock copolymer systems, the water swelling of the triptycene-containing multiblock copolymers did not increase proportionally with water uptake. This combination of high water uptake and low swelling behavior of these copolymers resulted in excellent proton conductivity and membrane dimensional stability under fully hydrated conditions. In particular, the triptycene-containing multiblock copolymer film with the longest hydrophilic block length (i.e., BPSH100-TRP0-15k-15k) had a water uptake of 105%, an excellent proton conductivity of 0.150 S/cm, and a volume swelling ratio of just 29% (more than 42% reduction compared to Nafion 212).

Authors:
 [1]; ORCiD logo [2];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
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  1. Univ. of Notre Dame, IN (United States)
  2. Wayne State Univ., Detroit, MI (United States)
  3. Pennsylvania State Univ., University Park, PA (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Center of Sustainable Energy at Notre Dame (ND Energy)
OSTI Identifier:
1427852
Grant/Contract Number:  
SC0010330; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE; polyelectrolyte membranes; triptycene-containing poly(arylene ether sulfone); multiblock copolymers; supramolecular interaction; water swelling

Citation Formats

Aboki, Joseph, Jing, Benxin, Luo, Shuangjiang, Zhu, Yingxi, Zhu, Liang, and Guo, Ruilan. Highly Proton Conducting Polyelectrolyte Membranes with Unusual Water Swelling Behavior Based on Triptycene-containing Poly(arylene ether sulfone) Multiblock Copolymers. United States: N. p., 2017. Web. doi:10.1021/acsami.7b13542.
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Aboki, Joseph, Jing, Benxin, Luo, Shuangjiang, Zhu, Yingxi, Zhu, Liang, & Guo, Ruilan. Highly Proton Conducting Polyelectrolyte Membranes with Unusual Water Swelling Behavior Based on Triptycene-containing Poly(arylene ether sulfone) Multiblock Copolymers. United States. https://doi.org/10.1021/acsami.7b13542
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Aboki, Joseph, Jing, Benxin, Luo, Shuangjiang, Zhu, Yingxi, Zhu, Liang, and Guo, Ruilan. Tue . "Highly Proton Conducting Polyelectrolyte Membranes with Unusual Water Swelling Behavior Based on Triptycene-containing Poly(arylene ether sulfone) Multiblock Copolymers". United States. https://doi.org/10.1021/acsami.7b13542. https://www.osti.gov/servlets/purl/1427852.
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@article{osti_1427852,
title = {Highly Proton Conducting Polyelectrolyte Membranes with Unusual Water Swelling Behavior Based on Triptycene-containing Poly(arylene ether sulfone) Multiblock Copolymers},
author = {Aboki, Joseph and Jing, Benxin and Luo, Shuangjiang and Zhu, Yingxi and Zhu, Liang and Guo, Ruilan},
abstractNote = {Multiblock poly(arylene ether sulfone) copolymers are attractive for polyelectrolyte membrane fuel cell applications due to their reportedly improved proton conductivity under partially hydrated conditions and better mechanical/thermal stability compared to Nafion. However, the long hydrophilic sequences required to achieve high conductivity usually lead to excessive water uptake and swelling, which degrade membrane dimensional stability. Herein, we report a fundamentally new approach to address this grand challenge by introducing shape-persistent triptycene units into the hydrophobic sequences of multiblock copolymers, which induce strong supramolecular chain-threading and interlocking interactions that effectively suppress water swelling. Consequently, unlike previously reported multiblock copolymer systems, the water swelling of the triptycene-containing multiblock copolymers did not increase proportionally with water uptake. This combination of high water uptake and low swelling behavior of these copolymers resulted in excellent proton conductivity and membrane dimensional stability under fully hydrated conditions. In particular, the triptycene-containing multiblock copolymer film with the longest hydrophilic block length (i.e., BPSH100-TRP0-15k-15k) had a water uptake of 105%, an excellent proton conductivity of 0.150 S/cm, and a volume swelling ratio of just 29% (more than 42% reduction compared to Nafion 212).},
doi = {10.1021/acsami.7b13542},
journal = {ACS Applied Materials and Interfaces},
number = 1,
volume = 10,
place = {United States},
year = {Tue Dec 19 00:00:00 EST 2017},
month = {Tue Dec 19 00:00:00 EST 2017}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acsami.7b13542
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Cited by: 28 works
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Figures / Tables:

Scheme 1 Scheme 1: Synthesis of telechelic unsulfonated hydrophobic oligomers (TRP0) with terminal phenoxide groups and their end-capping with DFBP
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    Works referencing / citing this record:

    Synthesis and Properties of Novel Side‐Chain Sulfonated Poly(Arylene Ether Sulfone)s for Proton Exchange Membranes
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    The role of synthetic P (MMA-co-MAH) as compatibilizer in the preparation of chlorinated polyethylene/polysodium acrylate water-swelling rubber
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    Do acid–base interactions really improve the ion conduction in a proton exchange membrane? – a study on the effect of basic groups
    journal, January 2019

    • Sui, Yuqian; Du, Yexin; Hu, Huayuan
    • Journal of Materials Chemistry A, Vol. 7, Issue 34
    • DOI: 10.1039/c9ta06508c
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