CN100412116C - Proton conducting membrane and production - Google Patents

Proton conducting membrane and production Download PDF

Info

Publication number
CN100412116C
CN100412116C CN 200510007711 CN200510007711A CN100412116C CN 100412116 C CN100412116 C CN 100412116C CN 200510007711 CN200510007711 CN 200510007711 CN 200510007711 A CN200510007711 A CN 200510007711A CN 100412116 C CN100412116 C CN 100412116C
Authority
CN
Grant status
Grant
Patent type
Prior art keywords
membrane
group
proton
fluorine
polymer
Prior art date
Application number
CN 200510007711
Other languages
Chinese (zh)
Other versions
CN1817944A (en )
Inventor
施志哲
陈振銮
陈致源
Original Assignee
财团法人工业技术研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/56Manufacturing of fuel cells

Abstract

一种低甲醇穿透性的质子传导膜及其制法,是将含氟苯乙烯单体接枝(grafting)于高分子膜材上,再将该接枝有含氟苯乙烯的高分子膜材成膜后,即予酸化以令阳离子交换基取代于该含氟苯乙烯基的苯环上。 A low-permeability methanol proton conducting membrane preparation method, the polymer film is a fluorine-containing styrene monomer is graft (grafting) polymer in the membrane, then the fluorine-containing styrene graft after the deposition material, in order to make the verdict acidified cation exchange group on the phenyl ring substituted with a fluorine-containing styrene group. 该质子传导膜具有较现有者为低的甲醇穿透度,可应用在直接甲醇进料型燃料电池或传统氢-氧燃料电池,以降低燃料的穿透现象,提高电池效能。 The proton conducting membrane having a relatively low prior to penetration by methanol, can be used in a direct methanol type fuel cell or the feed conventional hydrogen - oxygen fuel cell, in order to reduce the phenomenon of the fuel penetration to improve battery performance.

Description

质子传导膜及其制法财舰本发明是关于一种质子传导膜及其制法,特别是关于一种以含氟阳离子交换基为质子传导基的高分子质子传导膜及其制法。 Choi ship proton conductive membrane preparation method of the present invention relates to a proton conducting membrane fabrication method thereof, particularly to a fluorine-containing cation-exchange groups are proton conductive polymer proton-conducting membrane based method thereof. 背景技术直接甲醇进料型燃料电池(Direct Methanol Fuel Cell, DMFC)是使用甲醇-水溶液作为电池的燃料(foel),经由阳极触媒反应产生电子和质子,电子进入外电路,质子则经由质子传导膜(proton exchange membrane, PEM)传送到阴极,与氧气及来自外电路的电子结合,再经由触媒反应生成水。 BACKGROUND OF THE INVENTION Direct methanol feed fuel cells (Direct Methanol Fuel Cell, DMFC) using methanol - aqueous solution as a fuel cell (Foel), electrons and protons via the anode catalyst reaction, electrons enter the external circuit, the protons through the proton conductive membrane (proton exchange membrane, PEM) is transmitted to the cathode, combine with oxygen and electrons from the external circuit, and then through the catalyst reaction product water. 目前,存在于直接甲醇进料型燃料电池的质子传导膜的最大问题是,甲醇是与水高度兼容且易与质子形成错合物。 Currently, the biggest problem in the feed direct methanol fuel cell is a proton-conducting membrane, is highly compatible with water, methanol and readily form complexes with a proton. 氢离子(proton)是不含电的裸质子,由于其缺乏屏蔽原子核的电荷,质子会与其周围环境产生强烈交互作用形成共价键。 Hydrogen ions (Proton) is a proton-free electrically bare, due to its lack of charge screening nuclei, protons will strongly interact with the surrounding environment to form a covalent bond. 因此,DMFC使用的甲醇燃料容易在电池阳极与质子结合,经传导穿过PEM,造成阳极燃料的流失,通过PEM的甲醇燃料会在阴极消耗触媒与氧气,毒化阴极触媒,进而降低电极活性,该现象一般是称为甲醇穿透(Methanol Crossover),这是造成DMFC的效能不理想的重要原因之一。 Thus, DMFC methanol fuel cell anode used easily in conjunction with a proton, by conduction through the PEM, resulting in the loss of the anode of the fuel will be consumed at the cathode catalyst with oxygen, the cathode catalyst poisoning, thus reducing the active electrode through the PEM fuel methanol, the phenomenon is generally referred to as methanol crossover (methanol Crossover), which is one of the important causes of DMFC performance is not ideal. 一般而言,PEM若需要具备高质子传导性,其化学结构会形成强烈的亲水性(Hydrophilic)环境,亲水性环境也是甲醇很容易与水发生反应的环境,使甲醇穿透现象会越发地明显。 Generally, if the PEM requires high proton conductivity, which will form a strong chemical structure of hydrophilic (Hydrophilic) environment, the environment is hydrophilic and water environment methanol reactions easily occur, so that the methanol crossover phenomenon will become more It will be obvious. 因此,解决方法之一是降低结构的亲水性,或减少PEM离子基高亲水团簇(cluster)的体积。 Accordingly, one solution is to reduce the hydrophilicity of the structure, reduce the volume or PEM high ionic hydrophilic group clusters (Cluster) a. 然而,现有文献显示,当PEM结构的亲水性降低时,会伴随质子的导电度下降。 However, the existing literature shows, when the hydrophilic PEM structure decreases, accompanied by decrease of proton conductivity. 因此, 一个理想的质子传导膜必须同时具备高效率的质子传导能力,且对小分子甲醇具有高选择性。 Thus, a desirable proton conducting membrane must also have a proton conductivity of the high efficiency, and small molecules with high methanol selectivity. 但就化学结构而言,降低甲醇穿透现象与提高质子导电度是相互矛盾的,现有的单一材料无法满足适用于直接甲醇进料型燃料电池的质子传导膜的要求。 But in terms of chemical structure required to reduce methanol crossover phenomenon and improve the proton conductivity are mutually contradictory, not meet a conventional single material is suitable for direct feed methanol fuel cell proton conducting membrane. 目前市售商品中以杜邦(Du Pont)公司开发的Nafion(r)(全氟磺酸聚合物),是目前较具实用性的质子交换材料。 In currently commercially available DuPont (Du Pont) developed Nafion (r) (a perfluorosulfonic acid polymer), the more practical is the proton exchange material. 它是借由高分子亲/疏水相分离结构形成的纳米微相空间,该空间中的磺酸根集结形成的团簇结构借由吸收水分形成水通路,由所包括的水分子带动质子进行传导。 It is separated by means of affinity polymer / nanoparticles hydrophobic phase space structure formed cluster structure sulfonate build the space formed by the absorption of water by water passage is formed by water molecules comprising driven proton conduction. 这一高分子结构虽为燃料电池电解质研究带来突破性的发展,但在直接甲醇进料型燃料电池的应用上却发现有燃料大量渗透流失(Methanol Crossover)。 The polymer structure although bring a breakthrough in the development of electrolyte fuel cell research, but in the application of direct methanol fuel cell feed was found to have a large number of fuel penetration loss (Methanol Crossover). 而且Nafion(r)的价格昂贵(S800-1000/m2),使甲醇进料型燃料电池即使大量生产也无法有效降低制造成本。 And Nafion (r) are expensive (S800-1000 / m2), feed methanol fuel cell can not be mass-produced even reduce the manufacturing cost. 因此,极需要开发适用于直接甲醇进料型电池系统,同时具备低甲醇穿透性与高质子传导能力,且能以低成本大量制造的质子传导膜。 Thus, a need to develop extremely suitable for direct methanol type battery feed system, along with low methanol permeability and high proton conductivity, and can be mass-produced at low cost proton conducting membrane. 除了以上所述,针对DMFC中PEM的改进,目前尚有多种不同的方案提出。 In addition to the above, in the PEM for DMFC improvements, currently there are proposed a variety of different schemes. 其中之一是着眼于PEM中离子基浓度的降低。 One of these is focused on the concentration of ionic groups is reduced PEM. PEM中离子基的浓度(Ion Exchange Capacity)是决定PEM质子导电度的重要因素。 PEM concentration of ionic groups (Ion Exchange Capacity) is an important factor in determining the degree of proton conductivity of PEM. 然而,高离子基浓度的PEM也容易在其结构中形成亲水团簇(hydrophilic cluster),造成甲醇穿透PEM的现象。 However, high ionic group concentration can be easily formed PEM clusters hydrophilic (hydrophilic cluster) in its structure, resulting in the phenomenon of penetration of the PEM methanol. 因此有利用不同离子基浓度的PEM做成积层结构,或利用含苯环的高分子加以磺酸化,控制系统中离子基的浓度降低甲醇穿透PEM的技术提出。 Therefore with different concentrations of ionic groups PEM made of a laminated structure, or the use of polymer to be sulfonated benzene ring-containing, ionic group concentration control system is reduced methanol crossover PEM technology proposed. 例如,美国专利第5525436号、第5716727号、第6025085号、第6099988号、第6124060号及第5599639号等揭示的利用咪唑化合物的杂环提供质子传导性.,第6444343号美国专利等揭示的以聚磺酸苯乙烯(Polystyrene Sulfonic Acid, PSSA)与聚二氟乙烯(polyvinylidene fluoride; PVDF)交联反应形成薄膜;又美国专利第6365294号等揭示的以聚磷腈(polyphosphazene)为基材的PEM。 For example, an imidazole compound disclosed heterocyclic U.S. Patent No. 5,525,436, No. 5,716,727, No. 6,025,085, No. 6,099,988, No. 6,124,060 No. 5,599,639 to provide second proton conductivity., Disclosed in U.S. Patent No. 6,444,343, etc. poly styrene sulfonic acid (Polystyrene sulfonic acid, PSSA) and polyvinylidene fluoride (polyvinylidene fluoride; PVDF) cross-linking reaction to form a film; and U.S. Patent No. 6,365,294 discloses the like to polyphosphazene (polyphosphazene) as a base material PEM. 上述美国专利的技术虽以降低PEM 材料的离子基浓度或选用其它PEM替代材料,使形成的PEM的甲醇穿透率降低,但上述技术的实施大多需要在高温或无水的环境下操作才会有较佳的质子导电度,且其质子导电度会随着甲醇穿透率的降低而降低。 Although the above U.S. patent technology to reduce the concentration of ionic groups PEM PEM material, or alternatively use other materials, so that the methanol crossover PEM formation is reduced, but the implementation of the techniques described above mostly will need to operate at a high temperature environment or anhydrous there preferred proton conductivity, and its proton conductivity improves as the reduced methanol crossover decreases. 部分针对PEM材料改质的专利,是着眼于提高PEM在高温使用的饱水性,或降低氢氧气的穿透现象。 Portion of PEM material for the modified patent is focused on improving the high-temperature saturated aqueous PEM use, or to reduce the phenomenon of penetration of hydrogen gas. 研究利用简单的合成反应将无机金属氧化物填充在PEM材料的团簇(cluster)中,或直接与PEM材料掺混,期望借此增强PEM在高温环境中质子的导电稳定性或降低燃料的穿透率。 Utilization simple synthetic reaction of the inorganic metal oxide material filled in PEM cluster (Cluster) or directly blended with PEM material, thereby enhancing the desired stability of the PEM proton conductivity in a high temperature environment, or reduce the wear of the fuel penetration rate. 例如,美国专利第5849428号等揭示出在聚四氟乙烯(Polyterafluoroethylene; PTFE)与氧化锆磷(ZrOP)的多孔膜中加入无机氧化物的技术;美国专利第5849428号等揭示的在PEM中沉积ZrOP 的方法;美国专利第5919583号等揭示的在PEM中加入无机质子导体的方法;美国专利第6059943号、第6387230号等揭示的以溶胶-凝胶方法使PEM在高温下与ZiOP结合,提高其导电度;美国专利第5795496号等揭示的以聚醚醚酮(poly(ether ether ketone); s-PEEK)、聚醚砜(poly(ethersulfone); s-PES)与沸石(H-zeolite),利用高性能工程塑料的磺酸化,使高分子薄膜具有质子导电度,并加入沸石降低甲醇穿透率。 For example, U.S. Pat. No. 5,849,428, etc. disclosed a polytetrafluoroethylene (Polyterafluoroethylene; PTFE) technology into inorganic oxide with zirconium oxide film porous phosphorus (ZROP) in; U.S. Patent No. 5,849,428 discloses the like is deposited on the PEM the method of adding an inorganic proton conductor PEM disclosed in U.S. Patent No. 5,919,583 and the like;; ZROP method of U.S. Patent No. 6,059,943, No. 6,387,230, etc. disclosed in the sol - gel process combined with the PEM on ZiOP at high temperatures, improved its conductivity; U.S. Pat. No. 5,795,496, etc. disclosed in PEEK (poly (ether ether ketone); s-PEEK), polyether sulfone (poly (ethersulfone); s-PES) and zeolite (H-zeolite) by high-performance engineering plastics sulfonated, the polymer film having proton conductivity, and the zeolite was added to reduce methanol crossover. 然而上述方法虽能縮减传统PEM材料的亲水团簇(cluster)的体积,部分降低PEM的甲醇穿透率,但通常并未能有效改善,且因为降低PEM材料中亲水团簇的体积,也会同时减少质子的传导路径,造成导电度的下降。 However, although the above-described method can reduce the volume of conventional PEM material hydrophilic clusters (Cluster), and reducing methanol crossover portion of the PEM, but generally not effectively improved, and because of the reduced volume of hydrophilic material PEM Clusters , will also reduce the proton conduction paths, resulting in a decline in conductivity. 另一改善方案在于改变质子传导的方式。 Another embodiment is to change to improve the proton conduction. 改变质子传导的方式, 是将质子从原来在PEM中以离子基形态进行传导的方式,改为利用无机物固态酸基的质子跳跃机制(Hopping Mechanism)进行传导。 Changing the proton-conducting manner, it is the proton conduction from the original mode in a PEM to form ionic groups, to a proton hopping mechanism (Hopping Mechanism) using an inorganic solid acid group conduction. 例如, 美国专利第4594297号等提出的以聚乙烯醇(PVA)与杂多酸(Heteropoly add)在气相中反应时,改变质子传递方式;美国专利第4380575号提示的以杂多酸固体电解质于气相使用;WO 9852243号专利等提示出完全以沸石作为电解质。 For example, U.S. Patent No. 4,594,297 and the like made of polyvinyl alcohol (PVA) and a heteropolyacid (Heteropoly add) in gas phase, changing the aprotic embodiment; U.S. Pat. No. 4,380,575 to prompt heteropolyacid solid electrolyte in use gas; WO Patent No. 9852243 and the like out entirely tips zeolite as the electrolyte. 然而,碍于有机材料较难具备此特性,而无机材料在成膜加工性上有其先天限制,同时,室温下具有高质于导电度的无机材料有限且多为溶于水,因此该方法应用在PEM的改善,目前并无突破性的进展。 However, because of the organic material is more difficult to have this characteristic, the inorganic material has its inherent limitations on the film formation process, while having a limited quality of the inorganic conductive material and are mostly soluble in water at room temperature, the process application in improving the PEM, currently there is no breakthrough. 发明内容为克服上述现有技术的缺点,本发明的主要目的在于提供适用于直接甲醇进料燃料电池的低甲醇穿透性的质子传导膜及其制法。 SUMMARY OF THE INVENTION To overcome the above disadvantages of the prior art, the main object of the present invention to provide a suitable protic low methanol permeability in direct methanol feed fuel cell conductive film fabrication method thereof. 为达成上述及其它目的,本发明提供的质子传导膜的制法是先将含氟苯乙烯单体接枝在高分子膜材,再将己接枝有含氟苯乙烯基的高分子膜材成膜,然后以含阳离子交换基的酸液酸化该膜,将该阳离子交换基取代于该含氟苯乙烯的苯环上。 To achieve the above and other objects, the present invention provides a proton-conducting membrane is first production method the fluorine-containing styrene monomer grafted onto a polymer membrane, and then been grafted with styrene-based polymer membrane fluorine deposition, then acidified with acid group-containing cation exchange membrane that, the cation exchange group of the fluorine-containing substituents on the phenyl ring of styrene. 本发明并提供-种用上述制法制成的质子传导膜。 The present invention is to provide - SYSTEM Species proton conducting membrane made as described above. 具体而言,本发明的质子传导膜的制法是用不同接枝位置的含氟苯乙烯单体接枝在如聚二氟乙烯树脂(PVDF)的偏氟系高分子膜材上,再经酸化后,使阳离子交换基取代于含氟苯乙烯基的苯环上制得本发明的质子传导膜。 Specifically, the present invention is the proton conducting membrane production method using a fluorine-containing styrene monomer is grafted on different locations, such as grafted polyvinylidene fluoride resin (PVDF) membrane of polyvinylidene fluoride-based polymer, and then after acidification, the cation exchange protons present invention is to obtain a fluorine-substituted styryl phenyl ring conductive film. 在较佳具体例中,本发明是以含氟磺酸化聚苯乙烯接枝到聚二氟乙烯树脂(PVDF-g-PS-F)为质子传导膜的主成份。 In particular preferred embodiment, the present invention is grafted to a fluorine-containing sulfonic acid polystyrene resin, polyvinylidene difluoride (PVDF-g-PS-F) for the proton conducting membrane of main component. 本发明将含氟苯乙烯单体接枝在如聚二氟乙烯树脂的偏氟系高分子膜材的制造,只要不影响反应的进行,可采用任何一种现有的物理或化学方法。 The present invention is a fluorine-containing styrene monomer is grafted polyvinylidene difluoride as in the manufacture of vinylidene fluoride, vinyl-based polymer membranes, which do not affect the reaction, may be employed any conventional physical or chemical method. 最好是以下述两种方法进行:其一是先用X-ray、电子束、 Y射线或电浆等照射如聚二氟乙烯树脂的高分子膜材,接着将含氟苯乙烯(fluoro-styrene)单体接枝到经活化的烯系高分子膜材上制得氟苯乙烯基接枝的聚二氟乙烯树脂;另一种方法是用自由基聚合法将含氟苯乙烯单体直接接枝到如聚二氟乙烯树脂的高分子膜材匕制得含氟苯乙烯基接枝的高分子膜材。 Preferably in the following two methods: One is to use irradiation X-ray, electron beam, Y-rays, or the like, such as plasma membranes polyvinylidene difluoride polymer resin, then the fluorine-containing styrene (fluoro- styrene) monomers are grafted onto polyvinyl difluoride resin was activated on membranes prepared olefinic polymer grafted with a vinyl-fluorophenyl; another method is to use a fluorine-containing radical polymerization of styrene monomer directly grafted onto a polymer such as polyvinylidene difluoride membrane dagger vinyl resin obtained fluorine-containing styrene-based graft polymer membrane. 在上述照射法中,控制照射剂量与单体的使用量可改变接枝度, 适当的接枝度可使树脂保留原有的机械性能,并有适合的溶剂溶解性, 这种溶解性有利于膜的制造或是后续改质过程的进行。 In the irradiation method, the irradiation dose and the control amount of the monomers may be varied degree of grafting, the grafting degree of the resin can suitably retain their mechanical properties, and solubility with a suitable solvent, such solubility beneficial produced films or subsequent reformulation. 在自由基聚合法中则可以起始剂的种类、添加量、单体的使用量及这项技术领域中熟知的聚合条件等来控制接枝度。 In the radical polymerization initiator may be the kind, the addition amount, and the amount of the monomer art polymerization conditions well known to control the degree of grafting. 无论用何种方法制备接枝有含氟苯乙烯基的偏氟系高分子膜材, 含氟苯乙烯基的接枝度以10至100wt。 Regardless of what kind of fluorine-containing styrene-based method for preparing the graft vinylidene fluoride-based polymer membrane, fluorine-containing styrene-based degree of grafting of from 10 to 100wt. /。 /. ((接枝后总重-原始高分子膜材重量)/原始高分子膜材重量)为宜,在这种接枝度下得到的接枝产物及酸化后的离子聚合物有较佳的机械性质。 ((The total weight of the grafted - Polymer membranes original weight) / weight of original polymer film material) is appropriate, and grafted products after acidification ionic polymer in which the degree of grafting obtained has better mechanical nature. 本发明的含氟苯乙烯单体上的氟原子可接枝在苯环上的任意位置,其中以接枝于对位(para)或间位(meta)为佳。 Fluorine atom fluorinated styrene monomer graft of the present invention may be any position on the benzene ring, wherein the grafted para (para) or meta (Meta) preferably. 举例而言,本发明的以含氟苯乙烯单体接枝的如聚二氟乙烯树脂的偏氟系高分子膜材较佳实例是对位-氟-聚苯乙烯基接枝的聚二氟乙烯树脂(PVDF-g-PS-pF或PVDF-g-PS-4-F)或间位-氟-聚苯乙烯接枝的聚二氟乙烯树脂(PVDF-g-PS-mF或PVDF-g-PS-3-F)。 For example, vinylidene fluoride-based polymer such as polyvinylidene fluoride resin membrane of the preferred examples of the fluorine-containing styrenic monomer grafted to the present invention is para - fluoro - polystyrene-based grafted polyvinylidene difluoride vinyl resin (PVDF-g-PS-pF or PVDF-g-PS-4-F) or meta - fluoro - polystyrene grafted polyvinylidene fluoride resin (PVDF-g-PS-mF or PVDF-g -PS-3-F). 上述用含氟聚苯乙烯单体接枝的高分子膜材随后是用适当的阳离子化试剂或含阳离子交换基的酸液处理,制得具有阳离子交换基的含氟苯乙烯接枝的高分子膜材。 Acid treatment of the graft monomer with a fluorine-containing polystyrene polymer membrane followed by a suitable cationizing agent or containing a cation exchange group, to obtain a fluorine-containing styrene graft polymer having cation exchange groups membrane. 适用于本发明的阳离子基可以是磺酸基、 羧基、磷酸基、亚酰胺基、磺亚酰胺基或磺酰胺基等,其中以解离度及酸度较佳的磺酸酯基为佳(PVDF-g-SPS-4-F)。 Cationic groups suitable for the present invention may be a sulfonic acid group, a carboxyl group, a phosphoric acid group, imide group, sulfonamide group or a sulfonyl imide group, of which the degree of dissociation and its acidity preferred sulfonate groups preferably (PVDF -g-SPS-4-F). 该阳离子化试剂的选择,可依反应所需加以适当选择,以磺酸酯基化试剂为例,可使用的包括例如浓硫酸、氯磺酸、三氧化硫、发烟硫酸、乙酰磺酸盐等。 Select the cationic reagent, required to follow the reaction to be suitably selected, to a sulfonate group as an example of agents, including concentrated sulfuric acid may be used, for example, chlorosulfonic acid, sulfur trioxide, fuming sulfuric acid, acetyl sulfonate Wait. 而所形成的具有阳离子交换基的含氟苯乙烯接枝的偏氟系高分子膜材中,阳离子交换当量至少为0.1mmol/g,较佳是Ol至10mmol/g,尤以0.1至2.5mmol/g为更佳。 Vinylidene fluoride and a fluorine-containing styrene-based polymer membrane having cation exchange groups of the graft formed by the cation exchange equivalent weight of at least 0.1mmol / g, preferably Ol is to 10mmol / g, especially 0.1 to 2.5mmol / g for the better. 为了进一步提升膜的抗化性、耐热性与机械性质,本发明的质子传导膜内也可添加其它树脂成分或结合其它电子传导膜形成复合膜。 To further enhance chemical resistance, heat resistance and mechanical properties of the film, the proton conducting membrane of the present invention may be added with other ingredients or other resin film forming the electron-conducting composite membrane. 该其它树脂成分可以是含氟树脂或不含氟树脂。 The other resin components may be fluorine resin or fluorine resin. 含氟树脂可以是单聚物或共聚物,例如聚偏二氟乙烯、聚偏二氟乙烯/六氟丙烯共聚合物、 聚偏二氟乙烯/一氯三氟乙烯共聚合物、聚偏二氟乙烯/六氟丙烯/四氟乙烯三聚合物或聚一氯三氟乙烯等。 Fluorine-containing resin may be a homopolymer or a copolymer, such as polyvinylidene fluoride, polyvinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride / chlorotrifluoroethylene copolymer, polyvinylidene fluoride / hexafluoropropylene / tetrafluoroethylene terpolymer poly-chlorotrifluoroethylene or the like. 碳氢类树脂可例如是聚丙烯酸酯(polyacrylate)、聚酉旨(polyester)、聚醚醚酮(polyether ether ketone)、聚石黄酸酯(polysulfonate)、聚醚(polyether)、聚酰胺(polyamide)、聚苯醚(polyphenylene oxide)及聚环氧乙烷(polyethylene oxide)等传统熟知的碳氢树脂。 Of hydrocarbon resin may, for example, polyacrylate (polyacrylate), poly unitary purpose (polyester), PEEK (polyether ether ketone), poly stone xanthate (polysulfonate), polyether (polyether), polyamide (polyamide ), polyphenylene ether (polyphenylene oxide) and polyethylene oxide (polyethylene oxide) and the like well known in the traditional hydrocarbon resins. Ji述其它树脂成分的添加量以具阳离子交换基的含氟苯乙烯接枝的偏氟系高分子膜材的重量计算为0至50重量%间较佳(添加树脂的重量除以具阳离子交换基的含氟苯乙烯接枝的偏氟系高分子膜材与树脂的重量和)。 By weight of vinylidene fluoride, fluorine-containing styrene-based polymer membrane Ji said grafted amount of the other resin component is added to the calculated cation exchange groups having from 0 to 50 wt%, preferably between (divided by the added weight of the resin having a cation exchange by weight vinylidene fluoride based polymer membrane and a fluorine-containing resin and a styrene-based graft). 膜的制造中使用的溶剂可以是非质子溶剂,如二屮基甲酰胺(Dimethylformamide) 、 1 -甲基-2-吡咯烷酮(1 -肘6出^-2卞丫0"0旧0^)或二甲亚砜(Dimethylsulfoxide)等,也可添加少量的质子性溶剂,如醇类溶剂等。将含氟苯乙烯接枝的偏氟系高分子膜材及其它添加剂等成份的混合物溶解后,即能以刮刀涂布方式成膜。除溶剂法外,制膜的方式也可以任何传统熟知的方式,如热压法、滚绕薄膜法、旋转涂布法或挤压法等来制造。膜的成份内也可添加如表面活性剂、可塑剂、膜平整剂、抗氧化剂等成份来改善膜的加工性与其它性能。这种复合膜具有良好的耐热性、耐酸碱性、机械性与可挠曲性,该膜在pH值1至14范闱内长期储存时也无分解现象。根据本发明制得的质子传导膜,其质子导电度至少为1X1(^至1 X10"S/cm,且其甲醇穿透率为1Xl(r8至2X10-6cm2/sec。附图说明图l(a)是本发明 The solvent used in producing the film may be an aprotic solvent, such as dimethyl formamide Che (Dimethylformamide), 1-- methyl-2-pyrrolidone (l - ^ -2 Bian elbow 6 Ah 0 "0 0 ^ old) or di- after sulfoxide (Dimethylsulfoxide) and the like, may be added a small amount of a protic solvent, solvents such as alcohols and the like. the fluorine-containing styrene graft component mixture of vinylidene fluoride-based polymer membrane and dissolve other additives, that can in forming the blade coating method. in addition to the solvent method, the way the film may also be any conventional known manner, such as pressing, rolling around the film manufacturing method, a spin coating method or an extrusion method or the like. the film components the ingredients may be added such as surfactants, plasticizers, film leveling agents, antioxidants, and the like to improve the processability of the film. such a composite film has good heat resistance and other properties, acid resistance, and mechanical properties can be flexibility, of the film at 14 to a pH within the range of long-term storage Quarters 1 and no decomposition phenomena. the conductive film prepared by the invention proton, proton conductivity of at least 1X1 (^ to 1 X10 "S / cm, and which is a methanol crossover 1Xl (r8 to 2X10-6cm2 / sec. FIG. l (a) of the present invention are 施例1的质子传导膜(PVDF-g-SPS-pF)的化学结构图;图l(b)是本发明实施例1的质子传导膜(PVDF-g-SPS-pF)的IR分析结果图;图2是本发明实施例2的质子传导斷PVDF-g-SPS-pF)的化学结构图。具体实施方式实施例1将20g对位-氟苯乙烯(p-fluoro-styrene)单体(纯度99.8%)力卩入40g 聚二氟乙烯树脂(PVDF)中,搅拌均匀后,以Co-60进行辐射照射进行接枝反应,照射剂量是控制在25gGy。所得的PVDF-g-PS-pF粗产物以乙酸乙酯进行索氏萃取(Soxhlet extraction),除去未反应的单体及苯乙烯均聚合物。产物在室温或加热干燥下得到白色的PVDF-g-PS产物, 接枝重量百分比为38.5重量%。将PVDF-g-PS-pF与10mg氟素表面活性剂FC-430 —起加入l-甲基-2-卩比咯垸酮20ml中(固体含量3至50wt%),接着以刮刀涂布法在加热下(120'C诚膜。之后,该膜以氯磺酸在25"C下进行磺酸化反应,反应时间为8小时。磺酸化后的膜先后用四氢呋喃 Proton Example 1 conducting chemical structure diagrams membrane (PVDF-g-SPS-pF); Figure l (b) is an IR analysis FIG proton Example 1 conducting membrane (PVDF-g-SPS-pF) of the embodiment of the present invention ; FIG. 2 is a proton Example 2 of the present invention, conducting off the PVDF-g-SPS-pF) chemical structure of Example 1 20g of FIG DETAILED DESCRIPTION embodiments of para - fluoro-styrene (p-fluoro-styrene) monomer (. purity 99.8%) into a force Jie 40g polyvinylidene fluoride resin (PVDF), stirred uniformly, to Co-60 radiation grafting reaction performed, the irradiation dose is controlled 25gGy. the resulting PVDF-g-PS-pF the crude product was subjected to Soxhlet extraction with ethyl acetate (Soxhlet extraction), to remove unreacted monomers, and styrene homopolymer. the product obtained PVDF-g-PS product as a white at room temperature or heat drying, the graft weight percent 38.5% by weight of the PVDF-g-PS-pF and 10mg fluorocarbon surfactant FC-430 -. l- methyl-2 was added from pyrrole embankment Jie-one in 20ml (solid content of 3 to 50wt%), followed by a doctor blade method after heating at (120'C Cheng film. the film chlorosulfonic acid sulfonation reaction at 25 "C, the reaction time was 8 hours. after sulfonation the membrane washed with tetrahydrofuran 水清洗,接着在80'C在真空条件下干燥6小时,即制得本发明的质子传导膜。制得的质子传导膜的化学结构见图l(a),其IR 分析结果见图l(b)。以AC交流阻抗方法测试该质子传导膜的质子导电度为1.3X l(T2S/cm。实施例2将20g间位-氟苯乙烯(m-fluoro-styrene)单体(纯度99.8%)加入40g 聚二氟乙烯树職PVDF沖,搅拌均匀后,以Co-60进行辐射照射以产生接枝反应,照射剂量是控制在25gGy。 Washed with water, followed by drying under vacuum to 80'C for 6 hours according to the present invention, i.e., proton conducting membrane was obtained. The resulting proton conductive membrane chemical structure shown in Figure l (A), which IR analysis shown in Figure l ( . B) to the AC impedance method of testing proton conducting membrane is proton conductivity of 1.3X l (T2S / cm Example 2 20g of meta embodiment - fluorostyrene (m-fluoro-styrene) monomer (99.8% purity ) was added 40g polyvinyl difluoride PVDF tree level red, stir to Co-60 radiation to produce for the grafting reaction, the irradiation dose is controlled 25gGy. 所得的PVDF-g-PS-mF粗产物以乙酸乙酯进行索氏萃取(Soxhlet extraction),除去未反应的单体及苯乙烯均聚合物。 The resulting PVDF-g-PS-mF The crude product was subjected to Soxhlet extraction with ethyl acetate (Soxhlet extraction), to remove unreacted monomers, and styrene homopolymer. 产物在室温或加热干燥下得到白色的PVDF-g-PS产物,接枝重量百分比为32.5重量%。 The product was obtained as a white PVDF-g-PS product was dried at room temperature or under heating, a graft percentage of 32.5 wt% by weight. 将PVDF-g-PS-3-F与lOmg氟素表面活性剂FC-430 —起加入l-甲基-2-吡咯烷酮20ml中(固体含量3至50wt%),接着以刮刀涂布法在加热下(130'C)成膜。 The PVDF-g-PS-3-F and lOmg fluorine surfactant FC-430 - since added 20ml of methyl-l- (solid content of 3 to 50wt%), followed by heating in a doctor blade coating method lower (130'C) film. 之后,此膜以氯磺酸在25'C下进行磺酸化反应,反应时间为8小时。 Thereafter, this film chlorosulfonic acid sulfonation reaction at 25'C, the reaction time is 8 hours. 磺酸化后的膜先后用四氢呋喃及水清洗,接着在80'C真空条件下干燥6小时,即制得本发明的质子传导膜。 Film after sulfonation washed successively with tetrahydrofuran and water, and then dried under vacuum at 80'C for 6 hours according to the present invention, i.e., proton conducting membrane was obtained. 制得的质子传导膜的化学结构见图2。 The resulting proton conductive membrane chemical structure shown in Figure 2. 以AC交流阻抗方法测试该质子传导膜的质子导电度为3.5X 10'3S/cm。 The method of testing an AC impedance of the proton conducting membrane is proton conductivity of 3.5X 10'3S / cm. 吸水率分析将干燥的具有磺酸基的聚苯乙烯接枝的聚二氟乙烯树脂制成的质子传导膜在沸水(或甲醇)中煮30分钟后,将其取出并用拭镜纸将膜表面的水滴擦干,随即将擦干的质子传导膜秤重,将膜所吸收水的重量除以具有磺酸基的聚苯乙烯接枝的聚二氟乙烯树脂制成干膜的重量, 即得到膜的吸水率。 After water absorption analysis protons produced are dried polystyrene having sulfonic acid groups grafted polyvinylidene fluoride resin conductive film in boiling water (or methanol) for 30 minutes, remove it with lens paper and the film surface droplets dry, then dry the proton conductive membrane of the weighing, the weight of water absorbed by the membrane divided by the dry film has a weight made of polystyrene sulfonic acid groups grafted polyvinylidene fluoride resin, i.e., to give the water absorption of the film. 比较试验以市售的Nafionll7与本发明实施例1制得的质子传导膜进行导电度、甲醇穿透(methanolcrossover),吸水率及甲醇吸收率的比较试验, 其结果见表1。 Comparative tests of commercially available conductivity Nafionll7 conductive film of the present invention prepared in Example 1 proton embodiment, methanol crossover (methanolcrossover), water absorption rate and absorption methanol comparative test results shown in Table 1. 表1<table>table see original document page 11</column></row> <table> Table 1 <table> table see original document page 11 </ column> </ row> <table>

Claims (23)

  1. 1. 一种质子传导膜,是由含氟苯乙烯单体接枝在高分子膜材形成的,其特征在于,该接枝在高分子膜材上的含氟苯乙烯基的苯环上取代有阳离子交换基,且该含氟苯乙烯基的氟取代苯环的对位或间位。 A proton conducting membrane is a fluorinated styrene monomer in graft polymer membrane formed, wherein the substituents on the phenyl ring grafted on a polymer membrane of a fluorine-containing styrene-based cation exchange group, and the fluorine-containing fluoro-substituted styryl phenyl ring in the para or meta position.
  2. 2. 如权利要求1所述的质子传导膜,其特征在于,该质子传导膜的导电度是1X10—3至1X10—'S/cm。 2. The proton-conducting membrane of claim 1, wherein the conductivity of the proton conductive membrane is 1X10-3 to 1X10-'S / cm.
  3. 3. 如权利要求1所述的质子传导膜,其特征在于,该质子传导膜的甲醇穿透率为1 X 10—8至2X 10—6cm2/sec。 3. The proton-conducting membrane of claim 1, wherein the proton conducting membrane of methanol crossover is 1 X 10-8 to 2X 10-6cm2 / sec.
  4. 4. 如权利要求1所述的质子传导膜,其特征在于,该阳离子交换基是选自由磺酸基、羧基、磷酸基、亚酰胺基、磺亚酰胺基与磺酰胺基所成群组中的其中之一。 4. The proton-conducting membrane of claim 1, wherein the cation exchange group is selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphoric acid group, imide group, sulfo group and imide group into the sulfonamide group It is one of them.
  5. 5. 如权利要求1所述的质子传导膜,其特征在于,该阳离子交换基的当量至少为0.1 mmol/g。 5. The proton-conducting membrane of claim 1, wherein the cation-exchange group equivalent weight of at least 0.1 mmol / g.
  6. 6. 如权利要求5所述的质子传导膜,其特征在于,该阳离子交换基的当量为0.1至10mmol/g。 5 protons as claimed in claim conducting membrane, wherein the cation exchange group equivalent of from 0.1 to 10mmol / g.
  7. 7. 如权利要求6所述的质子传导膜,其特征在于,该阳离子交换基的当量为0J至2.5mmol/g。 7. The proton-conducting membrane of claim 6, wherein the cation-exchange group equivalent weight of 0J to 2.5mmol / g.
  8. 8. 如权利要求1所述的质子传导膜,其特征在于,还包括由界面活性剂、可塑剂、膜平整剂及抗氧化剂所成群组中的其中之一。 8. The proton-conducting membrane of claim 1, characterized by further comprising one made of surfactants, plasticizers, leveling agents and film antioxidant group.
  9. 9. 如权利要求1所述的质子传导膜,其特征在于,该含氟苯乙酰单体与高分子膜材的接枝度为10至100重量%,其中,接枝度根据下式计算-(接枝后总重-原始高分子膜材重量)/原始高分子膜材重量。 - a proton as claimed in claim 1 wherein the degree of grafting is calculated according to the formula in claim conductive film, wherein the degree of grafting monomer and a polymer containing difluorophenacetyl membrane is from 10 to 100 wt%, (total weight of grafted - polymer membranes original weight) / weight of original polymer membrane.
  10. 10. —种质子传导膜的制法,其特征在于,该制法包括下列歩骤: 将含氟苯乙烯单体接枝在高分子膜材上,该含氟苯乙烯基的氟取代苯环的对位或间位;将接枝有含氟苯乙烯的高分子膜材成膜;以及以具有阳离子交换基的酸液酸化该接枝有含氟苯乙烯的高分子膜材所成的膜,使阳离子交换基取代该含氟苯乙烯基的苯环。 10. - Method protonic conductive film, characterized in that the ho step process which comprises the following: fluorine-containing styrene monomer is grafted to the polymer membrane, the fluorine-containing styrene-fluoro-substituted phenyl group the para or meta position to; grafted with a polymer membrane forming the fluorine-containing styrene; and acidified to acid having a cation exchange group of the fluorine-containing styrene graft polymer membrane formed by a film , the cation exchange group of the fluorine-containing styrene substituted phenyl ring.
  11. 11. 如权利要求10所述的制法,其特征在于,该质子传导膜的导电度为1 X l(T3至1 X 10" S/cm。 11. Method according to claim 10, wherein the proton conductive membrane conductivity was 1 X l (T3 to 1 X 10 "S / cm.
  12. 12. 如权利要求10所述的制法,其特征在于,该质子传导膜的甲醇穿透率为1 X l(T8至2X IO-6 cm2/sec。 12. Method according to claim 10, wherein the proton conductive membrane is methanol crossover 1 X l (T8 to 2X IO-6 cm2 / sec.
  13. 13. 如权利要求IO所述的制法,其特征在于,该阳离子交换基是选自由磺酸基、羧基、磷酸基、亚酰胺基、磺亚酰胺基与磺酰胺基所成群组中的其中之一。 13. Method according to claim IO wherein the cation exchange group is selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphoric acid group, imide group, sulfo group and imide group into a sulfonamido group in the one of them.
  14. 14. 如权利要求IO所述的制法,其特征在于,该阳离子交换基的当量至少为0.1 mmol/g。 IO 14. Method according to claim, wherein the cation-exchange group equivalent weight of at least 0.1 mmol / g.
  15. 15. 如权利要求14所述的制法,其特征在于,该阳离子交换基的当量为0.1至10mmol/g。 15. Method according to claim 14, wherein the cation exchange group equivalent of from 0.1 to 10mmol / g.
  16. 16. 如权利要求15所述的制法,其特征在于,该阳离子交换基的当量为0.1至2.5mmol/g。 16. Method according to claim 15, wherein the cation exchange group equivalent of from 0.1 to 2.5mmol / g.
  17. 17. 如权利要求IO所述的制法,其特征在于,该高分子膜材是选自由聚二氟乙烯树脂、聚二氟乙烯/六氟丙烯共聚物、聚二氟乙烯/一氯三氟乙烯共聚物、聚二氟乙烯/六氯丙烯/四氟乙烯三聚物及聚一氯三氟乙烯所成群组中的其屮之一。 17. Method according to claim IO, wherein the polymer membrane is selected from the group consisting of polyvinylidene fluoride resins, polyvinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride / chlorotrifluoroethylene ethylene copolymer, polyvinylidene fluoride / hexafluoropropylene / tetrafluoroethylene terpolymers of ethylene, and poly (chlorotrifluoroethylene) formed by one of Che group.
  18. 18. 如权利要求10所述的制法,其特征在于,使该含氟苯乙烯单体接枝于高分子膜材的方式是通过X-ray、电子束、Y射线或电浆的任一者照射由该高分子膜材与含氟苯乙烯单体混合而成的混合物实施的。 18. Method according to claim 10, wherein the styrenic monomer grafted to the fluorinated polymer membrane is by X-ray, electron beam, Y-rays, or any of a plasma irradiation of the polymer film material by mixing the fluorine-containing styrene monomer mixture obtained by the embodiment.
  19. 19. 如权利要求IO所述的制法,其特征在于,适用于将该接枝有含氟苯乙烯基的高分子膜材成膜的方法是选自由热压法、滚绕薄膜法、旋转涂布法或挤压法所成组群中的其中之一。 19. Method according to claim IO, characterized in that for the grafted fluorine-containing styrene-based polymer membrane forming method is selected from the group consisting of pressing, rolling around the film, spin one group of the extrusion coating method or a percent.
  20. 20. 如权利要求IO所述的制法,其特征在于,该含氟苯乙酰单体与高分子膜材的接枝度为10至100重量%,其中,接枝度根据下式计算:(接枝后总重-原始高分子膜材重量y原始高分子膜材重量。 20. Method as claimed in claim IO wherein the degree of grafting is calculated according to the formula in claim, wherein the degree of grafting monomer and a polymer containing difluorophenacetyl membrane is from 10 to 100 wt% :( graft total weight - the weight of the original polymer membrane original y molecular weight membrane.
  21. 21. —种复合膜,其特征在于,是以如权利要求10所述制法制备的质子传导膜,与其它质子传导膜积层或掺混形成的。 21. - species composite membrane, wherein the proton 10 is prepared made Method as claimed in claim conductive film, and other proton conductive membrane laminated or blended form.
  22. 22. 如权利要求21所述的复合膜,其特征在于,该其它质于传导膜为含离子传导官能基的全氟或半氟高分子膜材。 22. The composite membrane according to claim 21, wherein the other film is a conductive substance on the ion-conducting functional group-containing perfluoro polymer membrane or a semi-fluoro.
  23. 23. 如权利要求21所述的复合膜,其特征在于,该其它质子传导膜是Nafion及PVDF-接枝-磺酸化苯乙烯中的至少一个。 23. The composite membrane according to claim 21, characterized in that the proton-conducting membrane is Nafion other PVDF- and graft - styrene sulfonic acid at least one.
CN 200510007711 2005-02-07 2005-02-07 Proton conducting membrane and production CN100412116C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200510007711 CN100412116C (en) 2005-02-07 2005-02-07 Proton conducting membrane and production

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200510007711 CN100412116C (en) 2005-02-07 2005-02-07 Proton conducting membrane and production

Publications (2)

Publication Number Publication Date
CN1817944A true CN1817944A (en) 2006-08-16
CN100412116C true CN100412116C (en) 2008-08-20

Family

ID=36918159

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200510007711 CN100412116C (en) 2005-02-07 2005-02-07 Proton conducting membrane and production

Country Status (1)

Country Link
CN (1) CN100412116C (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110045381A1 (en) * 2009-08-18 2011-02-24 Gm Global Technology Operations, Inc. Hydrocarbon PEM Membranes with Perfluorosulfonic Acid Groups for Automotive Fuel Cells
CN102324534B (en) * 2011-08-02 2014-01-08 东华大学 Polyamide membrane with proton conduction property, and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1385459A (en) 2002-05-09 2002-12-18 华南理工大学 Polystyrene sulfonate film for low-temp. direct methanol fuel cell and preparation process thereof
US6607856B2 (en) 1999-11-29 2003-08-19 Kabushiki Kaisha Toyota Chuo Kenkyusho Solid polymer electrolyte having high-durability
CN1479399A (en) 2002-08-29 2004-03-03 南通硬派电池有限公司 Manufacturing process electrolyte membrane special for solid lithium ion battery
JP2004107461A (en) 2002-09-18 2004-04-08 Univ Waseda Polyelectrolyte membrane
US6723758B2 (en) 1997-11-12 2004-04-20 Ballard Power Systems Inc. Graft polymeric membranes and ion-exchange membranes formed therefrom
EP1257348B1 (en) 2000-02-14 2004-10-06 Ballard Power Systems Inc. Graft polymeric membranes and ion-exchange membranes formed therefrom

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6723758B2 (en) 1997-11-12 2004-04-20 Ballard Power Systems Inc. Graft polymeric membranes and ion-exchange membranes formed therefrom
US6607856B2 (en) 1999-11-29 2003-08-19 Kabushiki Kaisha Toyota Chuo Kenkyusho Solid polymer electrolyte having high-durability
EP1257348B1 (en) 2000-02-14 2004-10-06 Ballard Power Systems Inc. Graft polymeric membranes and ion-exchange membranes formed therefrom
CN1385459A (en) 2002-05-09 2002-12-18 华南理工大学 Polystyrene sulfonate film for low-temp. direct methanol fuel cell and preparation process thereof
CN1479399A (en) 2002-08-29 2004-03-03 南通硬派电池有限公司 Manufacturing process electrolyte membrane special for solid lithium ion battery
JP2004107461A (en) 2002-09-18 2004-04-08 Univ Waseda Polyelectrolyte membrane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
用于聚合物电解质膜燃料电池中的质子导电膜. 吴洪等.高分子材料科学与工程,第17卷第4期. 2001
聚偏氟乙烯溶液法接枝苯乙烯磺酸膜的结构与形貌研究. 李文琼等.功能高分子学报,第17卷第3期. 2004

Also Published As

Publication number Publication date Type
CN1817944A (en) 2006-08-16 application

Similar Documents

Publication Publication Date Title
Slade et al. Investigations of conductivity in FEP-based radiation-grafted alkaline anion-exchange membranes
Chikh et al. (Semi-) Interpenetrating polymer networks as fuel cell membranes
Scott et al. Performance of the direct methanol fuel cell with radiation-grafted polymer membranes
Kraytsberg et al. Review of advanced materials for proton exchange membrane fuel cells
Yamaguchi et al. Pore-filling type polymer electrolyte membranes for a direct methanol fuel cell
Chen et al. Preparation and characterization of chemically stable polymer electrolyte membranes by radiation-induced graft copolymerization of four monomers into ETFE films
Li et al. Casting Nafion–sulfonated organosilica nano-composite membranes used in direct methanol fuel cells
Smitha et al. Solid polymer electrolyte membranes for fuel cell applications—a review
US20060083962A1 (en) Proton-conductive composite electrolyte membrane and producing method thereof
Savadogo Emerging membrane for electrochemical systems:(I) solid polymer electrolyte membranes for fuel cell systems
Bae et al. Sulfonated polystyrene grafted polypropylene composite electrolyte membranes for direct methanol fuel cells
US20060134493A1 (en) Highly durable polymer electrolytic membrane for a fuel cell having a cross-linked structure
US20040241518A1 (en) Solid polymer membrane for fuel cell prepared by in situ polymerization
US20050137351A1 (en) Polymer electrolyte membranes crosslinked by direct fluorination
US6277512B1 (en) Polymer electrolyte membranes from mixed dispersions
Song et al. Chemically-modified Nafion®/poly (vinylidene fluoride) blend ionomers for proton exchange membrane fuel cells
Zhang et al. Synthesis and characterization of poly (vinylidene fluoride)-g-sulfonated polystyrene graft copolymers for proton exchange membrane
US20070104994A1 (en) Electrolyte memberane for polymer electrolyte fuel cell, process for its production and membrane-electrode assembly for polymer electrolyte fuel cell
US20040126638A1 (en) Layered proton exchange membrane and method for preparing the same
Chen et al. Chemical and radiation crosslinked polymer electrolyte membranes prepared from radiation-grafted ETFE films for DMFC applications
Chen et al. Preparation of sulfonated crosslinked PTFE-graft-poly (alkyl vinyl ether) membranes for polymer electrolyte membrane fuel cells by radiation processing
US20070166590A1 (en) Electrolytic membrane, process for producing the same, membrane electrode assembly, fuel cell and method of operating the same
Lin et al. Semi-interpenetrating network based on cross-linked poly (vinyl alcohol) and poly (styrene sulfonic acid-co-maleic anhydride) as proton exchange fuel cell membranes
US6444343B1 (en) Polymer electrolyte membranes for use in fuel cells
JP2005154710A (en) Polymer solid electrolyte, method for producing the same, and solid polymer type fuel cell by using the same

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
C14 Grant of patent or utility model