Modifying a proton conductive membrane by embedding a "barrier".
Modifying a proton conductive membrane by embedding a "barrier".
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DOI：
10.1021/jp104514t
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发表时间：
2010-09
期刊：
影响因子：
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通讯作者：
Liang Wu;Chuanhui Huang;J. Woo;Dan Wu;Sung-Hyun Yun;Seok-Jun Seo;T. Xu;S. Moon
中科院分区：
文献类型：
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作者：
Liang Wu;Chuanhui Huang;J. Woo;Dan Wu;Sung-Hyun Yun;Seok-Jun Seo;T. Xu;S. Moon
在质子导电膜的开发中，平衡质子导电性和甲醇渗透性是一个难题；然而，本研究提出了一个简单的策略来解决这个问题，即在全氟磺化基质中嵌入一个质子导电“屏障”。通过将两性磺化聚（酞嗪酮醚砜酮）（SPPESK）包埋在半结晶全氟磺酸聚合物基体（FSP）中，验证了该策略。经过退火后，spesk的畴转变为势垒。两种酸碱相互作用分别构成质子转移和甲醇阻塞的屏障。一方面，通过退火，在磺酸基和酞嗪酮基之间形成亲水性较差的离子酸碱相互作用(- so(3)（-）…NH(+)-)，有利于甲醇的阻断。另一方面，更亲水的氢键酸碱相互作用(-SO(3)H…（H(2)O）(n)…N-, N≤3)也可以在水合条件下形成，并根据grotthuss型机制促进质子输运。因此，最终膜具有极低的甲醇渗透率（为Nafion-112的30%）和优异的燃料电池性能（与80°C的Nafion-112相比）。
For development of proton conductive membranes, it is a difficult dilemma to balance proton conductivity and methanol permeability; however, this research proposes a simple strategy to solve this problem, i.e., embedding a proton conductive "barrier" into the perflorosulfonated matrix. The strategy is exemplified by embedding the amphoteric sulfonated poly(phthalazinone ether sulfone kentone) (SPPESK) into a semicrystalline perflorosulfonic acid polymer matrix (FSP). After being annealed, the domain of SPPESK is converted to the barrier. Two acid-base interactions constitute the barrier for both the transfer of protons and the blockage of methanol, respectively. On one hand, poorly hydrophilic ionic acid-base interactions (-SO(3)(-)...NH(+)-) are formed between sulfonic acid group and phthalazinone group through annealing and are useful for methanol blocking. On the other hand, more hydrophilic hydrogen-bonded acid-base interaction (-SO(3)H...(H(2)O)(n)...N-, n ≤ 3) can also be formed under hydrated condition and facilitate proton transport according to the Grotthuss-type mechanism. As a result, the final membrane exhibits an extremely low methanol permeability (30% of that of Nafion-112) and an excellent fuel cell performance (as compared with Nafion-112 at 80 °C).