多磺化聚芳醚质子交换膜材料的制备及性能研究
摘要
磺化聚芳醚作为燃料电池用质子交换膜材料被广泛研究,当前传统的磺化聚芳醚膜材料表现出质子传导率和水溶胀率难以平衡的问题。为了获得高传导率低水溶胀率的聚芳醚材料,研究人员把目光投向对聚合物的微结构的改良方面。
本文通过设计聚合物分子结构的方法,在不改变磺化聚芳醚芳香型碳氢结构的基础上,通过调整聚合物微结构的手段达到改善聚合物性能的目的。设计了聚合物亲水链段和疏水链段结构。首先,制备了四磺化的双氟单体,较之二磺化的磺化氟酮和磺化双氯,此单体的磺酸基团密度高,有利于聚合物内部的磺化链段聚集。同时在相同磺酸基团含量下,聚合物的疏水链段也相应的增加一倍,有利于提高聚合物的机械性能。为了进一步增加聚合物疏水链段的稳定性,将含氟的双酚(六氟双酚A)作为聚合物的双酚单体引入聚合物链段。
我们详尽的研究了聚合物的结构和性能。结构表征数据证明所制得的产物为预期的产物。性能数据显示所制备的多磺化聚芳醚材料具有较大的分子量、低的水溶胀行为、和高的质子传导率。实现了高传导率低溶胀率的性能指标。
综上,本文从聚合物结构设计出发设计、合成了一类新型聚芳醚质子交换膜材料。并对材料进行了详尽的性能评价,结果显示磺化聚芳醚材料的微相结构是影响材料性能的关键因素。本文的研究为优化聚芳醚质子交换膜材料提供了有利的借鉴。为磺化聚芳醚质子交换膜材料的广泛应用提供了研究基础。
Proton exchange membrane fuel cells (PEMFCs) have attracted particular interest due to their wide range of potential applications in areas such as portable and stationary power generation, personal electronic devices (e.g., mobile phones, laptop computers),and automobiles. As the key component in PEMFCs,the proton exchange membrane (PEM) must possess several characteristics including high proton conductivity, low electrical conductivity, low permeability to fuel and oxidant, oxidative and hydrolytic stability, balanced water transport, good mechanical properties, and the capability to be assembled into a membrane electrode assembly (MEA) at low cost. The ability of a PEM to mediate the transport of protons, typically via acid-bearing functionalities (e.g., sulfonic acid groups),is essential in order to achieve high levels of power generation.Under moderate operating conditions (temperature (T)<90℃, relative humidity (RH)≈100%), state-of-the-art membrane based on perfluorosulfonic acid (PFSA) ionomer(e.g., Nafion,117) as opposed to hydrocarbon ionomers (e.g.,sulfonated poly(ether ether ketone), SPEEK), and exhibit high levels of proton conductivity, water transport, and durability. However, under the more stringent operating conditions requested by industry (T>100℃, RH<50%), proton conductivity for PFSA membranes drops significantly, leading to a decrease in fuel cell performance. Thus, there is considerable interest in the development of new membranes with greatly improved levels of proton conduction for high T and low RH operation, but this requires a greater understanding of the factors that affect proton transport in these materials.
In this thesis, we attempt to used multi-sulfonated segment to improve the morphology for improved performance of sulfonated poly(arylene ether)s. The first, we design and synthesis of four sulfonated difluoro-monomer(TSFDK).the monomer structure was confirm by NMR and FT-IR instrument. The results prove that we got objective component. Then corresponding poly(arylene ether)(SPAE) was also prepared by copolymerization form above monomer and commercial monomers. The obtained sulfonated polymers have a high viscosity properties reveal in the polymers have molecular weight. The transparent and tough membrane was obtained by solution casting method, and thick about 100μm.
We also study on polymer properties in detail. Water uptake of sulfonated polymer is very closely related to conductivity and mechanical strength of polymer. Those sulfonated polymer exhibited moderate water uptake is below 30%and low swelling ratio at high temperature and high sulfoned degree. High sulfonated polymer exhibited high proton conductivity above 10-2 S/cm at room temperature, and low methanol permeability and excellent mechanical properties.
本文通过设计聚合物分子结构的方法,在不改变磺化聚芳醚芳香型碳氢结构的基础上,通过调整聚合物微结构的手段达到改善聚合物性能的目的。设计了聚合物亲水链段和疏水链段结构。首先,制备了四磺化的双氟单体,较之二磺化的磺化氟酮和磺化双氯,此单体的磺酸基团密度高,有利于聚合物内部的磺化链段聚集。同时在相同磺酸基团含量下,聚合物的疏水链段也相应的增加一倍,有利于提高聚合物的机械性能。为了进一步增加聚合物疏水链段的稳定性,将含氟的双酚(六氟双酚A)作为聚合物的双酚单体引入聚合物链段。
我们详尽的研究了聚合物的结构和性能。结构表征数据证明所制得的产物为预期的产物。性能数据显示所制备的多磺化聚芳醚材料具有较大的分子量、低的水溶胀行为、和高的质子传导率。实现了高传导率低溶胀率的性能指标。
综上,本文从聚合物结构设计出发设计、合成了一类新型聚芳醚质子交换膜材料。并对材料进行了详尽的性能评价,结果显示磺化聚芳醚材料的微相结构是影响材料性能的关键因素。本文的研究为优化聚芳醚质子交换膜材料提供了有利的借鉴。为磺化聚芳醚质子交换膜材料的广泛应用提供了研究基础。
Proton exchange membrane fuel cells (PEMFCs) have attracted particular interest due to their wide range of potential applications in areas such as portable and stationary power generation, personal electronic devices (e.g., mobile phones, laptop computers),and automobiles. As the key component in PEMFCs,the proton exchange membrane (PEM) must possess several characteristics including high proton conductivity, low electrical conductivity, low permeability to fuel and oxidant, oxidative and hydrolytic stability, balanced water transport, good mechanical properties, and the capability to be assembled into a membrane electrode assembly (MEA) at low cost. The ability of a PEM to mediate the transport of protons, typically via acid-bearing functionalities (e.g., sulfonic acid groups),is essential in order to achieve high levels of power generation.Under moderate operating conditions (temperature (T)<90℃, relative humidity (RH)≈100%), state-of-the-art membrane based on perfluorosulfonic acid (PFSA) ionomer(e.g., Nafion,117) as opposed to hydrocarbon ionomers (e.g.,sulfonated poly(ether ether ketone), SPEEK), and exhibit high levels of proton conductivity, water transport, and durability. However, under the more stringent operating conditions requested by industry (T>100℃, RH<50%), proton conductivity for PFSA membranes drops significantly, leading to a decrease in fuel cell performance. Thus, there is considerable interest in the development of new membranes with greatly improved levels of proton conduction for high T and low RH operation, but this requires a greater understanding of the factors that affect proton transport in these materials.
In this thesis, we attempt to used multi-sulfonated segment to improve the morphology for improved performance of sulfonated poly(arylene ether)s. The first, we design and synthesis of four sulfonated difluoro-monomer(TSFDK).the monomer structure was confirm by NMR and FT-IR instrument. The results prove that we got objective component. Then corresponding poly(arylene ether)(SPAE) was also prepared by copolymerization form above monomer and commercial monomers. The obtained sulfonated polymers have a high viscosity properties reveal in the polymers have molecular weight. The transparent and tough membrane was obtained by solution casting method, and thick about 100μm.
We also study on polymer properties in detail. Water uptake of sulfonated polymer is very closely related to conductivity and mechanical strength of polymer. Those sulfonated polymer exhibited moderate water uptake is below 30%and low swelling ratio at high temperature and high sulfoned degree. High sulfonated polymer exhibited high proton conductivity above 10-2 S/cm at room temperature, and low methanol permeability and excellent mechanical properties.
引文
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[2]Ralph T, Hards G A, Keating J E, et al.Low Cost Electrodes for Proton Exchange Membrane Fuel Cells[J] J.Electrochem.Soc.,1997,144,3845-3850.
[3]Dhar H P,On solid polymer fuel cells[J].J.Electroanal.Chem.1993,357,237-250.
[4]Shoesmith J P,Collins R D,Oakley M J,Stevensonet D K. Status of solid polymer fuel cell system development[J].J.Power Source,1994,49,129-142.
[5]Yoshida N,Ishisaki T,Watanabe A,et al.Characterization of Flemion membranes for PEFC.Electrochimica Acta,1998,43,3749-3754.
[6]Wakizoe M,Velev O A,Srinivasan S.Anaiysis of Proton exchange membrane fuel cell performance with alternate membranes.Electrochimica Aeta,1995,40,335-344.
[7]Yoshitake M,Tamura M,Yoshida N,etal.Studies of perfluorinated ion exchange membranes for polymerelecrtolyte fuel cells.Denki Kagaku,1996,64,727-736.
[8]Gierke T D,Munn G E,Wilson F C,The morphology in nafion perfluorinated membraneproducts,as determined by wide-and small-angle x-ray studies[J].Journal of Polymer Seience:Polymer Physics Edition 1981,19,1687-1704.
[9]Yang, C, P Costamagna, et al. Approaches and technical challenges to high temperature operation of proton exchange membrane fuel cells[J]. Journal of Power Sources 2001, 103(1):1-9.
[10]Hamnett, A.Mechanism and electrocatalysis in the direct methanol fuel cell[J]. Catalysis Today 1997,38(4):445-457.
[11]Robertson G P,Mikhailenko S D,Wang K P,et al.Casting solvent interactions with sulfonated poly(ether ether ketone)during proton exchange membrane fabrication[J] Journal of Membrane Science,2003,219,113-121.
[12]Daoust D,Devaux J,Godard P.Mechanism and kinetics of poly(ether ether ketone) (PEEK)sulfonation in concentrated sulfuric acid at room temperature Part 1.Qualita comparison between polymer and monomer model compound sulfonation[J].Polym Int.,2001,50,917-924.
[13]Daoust D,Devaux J,Godard P.Mechanism and kinetics of poly(ether ether ketone) (PEEK)sulfonation in concentrated sulfuric acid at room temperature Part 2. Quantitative interpretation of model compound sulfonation[J].Polym.Int.,2001,50,925-931
[14]Daoust D,Devaux J,Godard P.Mechanism and kinetics of poly(ether ether ketone) (PEEK)sulfonation in concentrated sulfuric acid at room temperature Part 3.Genera kinetic model of the sulfonation of PEEK fluoroarylketone chain-end repeat unit[J]. Polym.Int.,2001,50,932-936.
[15]Wang, F, M Hickner, et al. Direct polymerization of sulfonated poly (arylene ether sulfone) random (statistical) copolymers:candidates for new proton exchange membranes[J]. Journal of Membrane Science 2002,197(1-2):231-242.
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