化工进展 ›› 2019, Vol. 38 ›› Issue (01): 529-537.DOI: 10.16085/j.issn.1000-6613.2018-0788

• 材料科学与技术 • 上一篇    下一篇

硫酸化SnO2/SPPESK复合质子交换膜的制备及燃料电池性能

甄栋兴(),唐帅,陈木森,万磊,吴雪梅,贺高红()   

  1. 大连理工大学精细化工国家重点实验室,膜科学与技术研究开发中心,辽宁 大连 116023
  • 收稿日期:2018-04-17 修回日期:2018-09-02 出版日期:2019-01-05 发布日期:2019-01-05
  • 通讯作者: 贺高红
  • 作者简介:甄栋兴(1987—),男,博士研究生,研究方向为质子交换膜燃料电池。E-mail:<email>zhendongxing@mail.dlut.edu.cn</email>。|贺高红,教授,博士生导师,主要研究方向为膜科学与技术、燃料电池。E-mail:<email>hgaohong@dlut.edu.cn</email>。
  • 基金资助:
    国家自然科学基金(21476044, 21406031);国家重点研究发展计划(2016YFB0101203);国家自然科学基金联合基金(U1663223);教育部长江学者奖励计划(T2012049);大连理工大学重大项目培育科研专题项目(DUT16TD19);国家自然科学基金(21476044, 21406031);国家重点研究发展计划(2016YFB0101203);国家自然科学基金联合基金(U1663223);教育部长江学者奖励计划(T2012049);大连理工大学重大项目培育科研专题项目(DUT16TD19)。

Preparation and fuel cell performance of sulfated SnO2/SPPESK composite proton exchange membranes

Dongxing ZHEN(),Shuai TANG,Musen CHEN,Lei WAN,Xuemei WU,Gaohong HE()   

  1. State Key Laboratory of Fine Chemicals,R&D Center of Membrane Science and Technology,Dalian University of Technology, Dalian 116023, Liaoning, China
  • Received:2018-04-17 Revised:2018-09-02 Online:2019-01-05 Published:2019-01-05
  • Contact: Gaohong HE

摘要:

非氟聚合物磺化聚芳醚砜酮(SPPESK)具有甲醇渗透率低、化学、热稳定性高等优点,但其高的电导率需通过提高磺化度获得,导致膜因过度溶胀而失去尺寸稳定性。添加无机纳米颗粒可以有效提高膜性能,但因其表面缺少功能化基团,导致颗粒有机相容性差,阻醇性能和质子传导率不易同时提高。硫酸化改性的纳米颗粒因其表面具有酸性位点和硫酸基团,能够有效克服这一问题。本文制备表面硫酸化改性的SnO2(SSnO2)纳米颗粒并引入SPPESK基质制备有机无机复合质子交换膜。当SSnO2含量不大于7.5%时,纳米颗粒具有良好的有机相容性,可均匀分散于聚合物基质。SSnO2含量为7.5%时,80℃下复合膜吸水率(19.6%)比SPPESK原膜提高19%,接近Nafion115。颗粒诱导膜内离子簇的聚集扩大,降低了质子的传导阻力,质子传导率分别比SPPESK原膜和Nafion115膜提高48%和30%。同时,纳米颗粒增大了甲醇传递空间位阻,甲醇渗透率较SPPESK原膜和Nafion115膜分别降低46%和71%。直接甲醇燃料电池0.5V处功率密度分别比SPPESK原膜和Nafion115膜高205%和50%。

关键词: 磺化聚芳醚砜酮, 硫酸化二氧化锡, 纳米粒子, 有机无机复合质子交换膜, 直接甲醇燃料电池

Abstract:

Sulfonated poly(phthalazinone ether sulfone ketone)(SPPESK), a novel non-fluorinated polymer, possesses the advantages of low methanol permeability, high chemical and thermal stability, but the obtained high conductivity needs high degree of sulfonation, resulting in the loss of membrane dimensional stability due to the excessive swelling. The introduction of inorganic nanoparticles can effectively improve the membrane performance. However, due to the lack of functional groups on the surface, the inorganic particles often show poor organic compatibility. Besides, the membrane’s anti-methanol permeability and proton conductivity cannot be easily improved simultaneously. The sulfated nanoparticles with acidic sites and sulfate groups on the surface can effectively overcome this problem. The SPPESK based composite proton exchange membranes were prepared by doping sulfated SnO2 (SSnO2) nanoparticles. The SSnO2 showed good organic compatibility when the content was not more than 7.5%. Compared with the pristine membrane, the composite membrane containing 7.5% SSnO2 showed higher water uptake (improved by 19%) at 80℃ in, and the swelling ratio (19.6%) was close to that of Nafion115. The nanoparticles induced the aggregation and expansion of the ion clusters in the membrane, which led to the low-resistance transfer of protons. Compared with pristine SPPESK and Nafion115, the composite membrane showed conductivity increases of 48% and 30% at 80℃, methanol permeability reductions of 46% and 71% and power density enhancements at 0.5V of direct methanol fuel cell of 205% and 50%, respectively.

Key words: sulfonated poly(phthalazinone ether sulfone ketone), sulfated tin dioxide, nanoparticles, organic-inorganic composite proton exchange membrane, direct methanol fuel cell

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