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<p>The sulfonated poly(<i>α</i>-methyl styrene-<i>b</i>-isobutylene-<i>b</i>-<i>α</i>-methyl styrene) copolymers (S-ASIBS) with the average molar percentage of sulfonic acid (-SO<sub>3</sub>H) groups (SP) ranging from 3.6 mol% to 14.3 mol% could be synthesized by sulfonation of ASIBS with acetyl sulfate. The hydrophilic ionic channels were generated for proton exchange membranes (PEMs) by ion aggregation of -SO<sub>3</sub>H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(<i>α</i>-methyl styrene) segments in S-ASIBS. The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS. The appropriate SP of ~12.7 mol% in S-ASIBS provides the available PEMs with high proton transport ability, low methanol permeability and good oxidative stability. The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals. The residual rates of weight (RW) and proton conductivity (R<i>σ</i>) of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3% and 88.1% respectively, near to those of commercial Nafion 117 (RW = 87.9%, R<i>σ</i> = 90.3%). The membrane electrode assembly (MEA) could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell. The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage (OCV) of 548 mV and peak power density (<i>P</i><sub>max</sub>) of 36.1 mW·cm<sup>-2</sup>, which is similar to those of Nafion 117 (OCV = 506 mV, P<sub>max</sub> = 35.6 mW·cm<sup>-2</sup>). To the best of our knowledge, this is the first example of advanced S-ASIBS membrane with high proton conductivity, excellent fuel barrier property and remarkable oxidative stability for promising PEMs.</p>

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Sulfonated Poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene) Copolymers for Advanced Proton Exchange Membranes

  • 期刊论文

  • 发表日期：

    2025年6月6日

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  • Ying-Ying Zhang,
  • Zhi-Chao Zhang,
  • Hao-Ran Zhao,
  • Xin Yang,
  • You-Guang Jin,
  • Yi-Xian Wu

摘要

The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene) copolymers (S-ASIBS) with the average molar percentage of sulfonic acid (-SO3H) groups (SP) ranging from 3.6 mol% to 14.3 mol% could be synthesized by sulfonation of ASIBS with acetyl sulfate. The hydrophilic ionic channels were generated for proton exchange membranes (PEMs) by ion aggregation of -SO3H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(α-methyl styrene) segments in S-ASIBS. The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS. The appropriate SP of ~12.7 mol% in S-ASIBS provides the available PEMs with high proton transport ability, low methanol permeability and good oxidative stability. The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals. The residual rates of weight (RW) and proton conductivity (Rσ) of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3% and 88.1% respectively, near to those of commercial Nafion 117 (RW = 87.9%, Rσ = 90.3%). The membrane electrode assembly (MEA) could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell. The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage (OCV) of 548 mV and peak power density (Pmax) of 36.1 mW·cm-2, which is similar to those of Nafion 117 (OCV = 506 mV, Pmax = 35.6 mW·cm-2). To the best of our knowledge, this is the first example of advanced S-ASIBS membrane with high proton conductivity, excellent fuel barrier property and remarkable oxidative stability for promising PEMs.