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Número de publicaciónCN100386367 C
Tipo de publicaciónConcesión
Número de solicitudCN 200610019386
Fecha de publicación7 May 2008
Fecha de presentación16 Jun 2006
Fecha de prioridad16 Jun 2006
También publicado comoCN1861668A
Número de publicación200610019386.6, CN 100386367 C, CN 100386367C, CN 200610019386, CN-C-100386367, CN100386367 C, CN100386367C, CN200610019386, CN200610019386.6
Inventores刘珊珊, 唐浩林, 牧 潘, 王晓恩, 袁润章
Solicitante武汉理工大学
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos:  SIPO, Espacenet
Preparation process of composite proton exchanging member based on hydrophilic porous poly tetrafluoro ethylene matrix
CN 100386367 C
Resumen  traducido del chino
本发明提供了一种基于亲水性多孔聚四氟乙烯基体的复合质子交换膜的制备方法,其特点是先对多孔聚四氟乙烯进行亲水处理,再向处理后的多孔聚四氟乙烯中填充质子传导树脂,然后热处理并质子化得到亲水性多孔聚四氟乙烯增强的复合质子交换膜。 The present invention provides a method for preparing a compound based on a hydrophilic porous polytetrafluoroethylene proton exchange membrane matrix, which is characterized by first hydrophilic treatment of porous polytetrafluoroethylene, porous polytetrafluoroethylene again after treatment proton conductive resin is filled, and then heat treated to obtain a hydrophilic protonated porous polytetrafluoroethylene reinforced composite proton exchange membrane. 亲水处理后多孔聚四氟乙烯基体与质子传导树脂能很好的结合,所制备的复合质子交换膜质子传导性好、机械强度高、气体渗透率,在质子交换膜燃料电池中具有很好的应用效果。 Hydrophilized porous PTFE matrix and proton conductive resin can be a good combination, prepared composite proton exchange membrane proton conductivity, high mechanical strength, gas permeability, proton exchange membrane fuel cells have good application effect.
Reclamaciones(8)  traducido del chino
1、一种基于亲水性多孔聚四氟乙烯基体的复合质子交换膜的制备方法,其特征是,按下述的步骤依次进行: 步骤1、对多孔聚四氟乙烯膜进行亲水处理,得亲水性多孔聚四氟乙烯膜,亲水处理方法是等离子处理或等离子体接枝聚合; 步骤2、取洁净的亲水性多孔聚四氟乙烯膜在含质子传导树脂的混合溶液中浸渍,浸渍时间为10分钟,混合溶液中质子传导树脂的含量为质量1%~20%,表面活性剂辛基酚聚乙氧基乙醇的含量为质量0~4%,溶剂为乙醇、丙醇和异丙醇中的任一种或者其混合物; 步骤3、将浸渍有质子传导树脂溶液的亲水性多孔聚四氟乙烯膜,采用双轮轮滚碾压去除表面多余的树脂溶液,碾压后的膜在真空干燥箱中热处理40~60秒钟; 步骤4、重复步骤2至步骤3的操作1~4次,直至膜变得透明; 步骤5、将步骤4得到的膜在乙醇或异丙醇中浸泡5~10分钟去除表面活性剂,然后,在沸腾的去离子水中浸泡10分钟,取出自然干燥后,在干燥箱中120~230℃热处理40~60秒钟,得到亲水性多孔聚四氟乙烯增强的复合质子交换膜。 1. A process for preparing a composite membrane based on hydrophilic porous polytetrafluoroethylene proton exchange matrix, wherein, according to the following steps sequentially: step 1, the porous polytetrafluoroethylene film to a hydrophilization treatment, have hydrophilic porous polytetrafluoroethylene film, the hydrophilic treatment is plasma treatment or plasma graft polymerization; impregnation step 2, take clean hydrophilic porous polytetrafluoroethylene film in a mixed solution containing a proton conductive resin immersion time of 10 minutes, a mixed solution of a proton conductive resin content is 1% to 20% by mass, the content of the surfactant of octyl phenol polyethoxy ethanol is from 0 to 4% by mass, the solvent is ethanol, iso-propanol, and propanol any one or a mixture thereof; step 3, impregnated with a hydrophilic proton conductive porous polytetrafluoroethylene film of the resin solution, using two-wheeled roller rolling wheel to remove excess surface resin solution after the rolling film heat-treated in a vacuum oven of 40 to 60 seconds; Step 4 Repeat steps 2 through Step 3 of 1 to 4 times, until the film becomes transparent; Step 5, the film obtained in step 4 in ethanol or isopropanol soak for 5 to 10 minutes to remove the surfactant, and then, in boiling deionized water soak for 10 minutes, after removing the natural drying, heat treatment in the oven 120 ~ 230 ℃ 40 ~ 60 seconds to obtain a hydrophilic porous polytetrafluoroethylene vinyl fluoride reinforced composite proton exchange membrane.
2、 如权利要求1所述的方法,其特征是,所述的多孔聚四氟乙烯膜厚度为l〜 40微米,孔径0.05〜4微米,孔隙率70%〜95%。 2. A method as claimed in claim 1, characterized in that the thickness of the porous polytetrafluoroethylene membrane is l~ 40 microns, pore 0.05~4 microns, a porosity of 70% ~ 95%.
3、 如权利要求l所述的方法,其特征是,所述的等离子体处理是,使用Ar气对多孔聚四氟乙烯膜表面进行处理,Ar产生的自由基能与空气中的氧或水发生反应形成过氧化物使多孔聚四氟乙烯表面产生官能团基团,再采用功能单体丙烯酸与官能团化的多孔聚四氟乙烯膜进一歩反应交联聚合,取得亲水性表面。 3. A method as claimed in claim l, wherein said plasma treatment is an Ar gas porous polytetrafluoroethylene film surface treatment, Ar with the free radicals generated oxygen in the air or water peroxide react to form the porous PTFE surface functional groups groups, and then using functional monomer acrylic acid functional groups of the porous PTFE membrane into a ho reaction cross-linked polymer made hydrophilic surface.
4、 如权利要求l所述的方法,其特征是,所述的等离子体接枝聚合是,用Ar等离子体预处理多孔聚四氟乙烯膜,再用亲水性功能单体丙烯酸、苯乙烯磺酸钠盐、M V- 二甲基乙酰胺或甲基丙烯酸缩水甘油酯水溶液,在近紫外光的诱导下发生接枝共聚反应。 4. A method as claimed in claim l, wherein said plasma graft polymerization is to use Ar plasma pretreatment porous polytetrafluoroethylene film, then a hydrophilic functional acrylic monomers, styrene sodium salt, M V- dimethylacetamide or an aqueous solution of glycidyl methacrylate, graft copolymerization occurs in the near UV induced.
5、 如权利要求1所述的方法,其特征是,所述的质子传导树脂是全氟磺酸树脂、 磺化三氟苯乙烯树脂、聚甲基苯基磺酸硅氧烷树脂、磺化聚醚醚酮树脂、磺化聚苯乙烯-聚乙烯共聚物树脂和磺化聚苯乙烯一聚乙炜/丁烯一聚苯乙烯树脂中的任何一种。 5. The method according to claim 1, wherein said proton-conductive resin is a perfluorosulfonic acid resin, sulfonated trifluoromethyl styrene resin, polymethyl phenyl siloxane resin acids, sulfonated polyether ether ketone resin, sulfonated polystyrene - polyethylene copolymer resin and a polyethylene Wei sulfonated polystyrene / butene-polystyrene resin either.
6、 如权利要求l所述的方法,其特征是,所述的步骤2的混合溶液中质子传导树脂的含量为质量3%〜10%。 6. The method according to claim l, wherein said step of mixing a solution of 2 proton conductive resin content of 3% by mass of ~ 10%.
7、 如权利要求1所述的方法,其特征是,所述的多孔聚四氟乙烯膜厚度为8〜 20微米。 7. The method according to claim 1, wherein said porous polytetrafluoroethylene film thickness of 20 microns 8~.
8、 如权利要求l所述的方法,其特征是,所述的步骤3中浸渍有质子传导树脂的亲水性多孔聚四氟乙烯膜,碾压后的膜在真空干燥箱中于120〜2301C热处理40〜 60秒钟。 8. The method according to claim l, wherein said step 3 of porous polytetrafluoroethylene impregnated with a hydrophilic proton conducting resin film, the film after rolling in a vacuum oven at 120~ 2301C heat treatment 40~ 60 seconds.
Descripción  traducido del chino

基于亲水性多孔聚四氟乙烯基体的复合质子交换膜的镧备方法 La preparation method based on composite proton exchange membrane hydrophilic porous PTFE matrix

技术领域 Technical Field

本发明涉及在质子交换膜燃料电池中,为电解MH^無离,道,同时又作为隔膜隔离两极 The present invention relates to a proton exchange membrane fuel cells, electrolytic MH ^ no off, road, while isolating the poles as the separator

反应气体的质子交换膜的制备方法。 Preparing membrane proton exchange reaction gas. 具体涉及一种基于亲水性多孔聚四氣乙烯基体的复合质子交换膜的制备方法。 Specifically it relates to a composite based proton hydrophilic porous poly vinyl form four gas exchange membrane preparation.

质子交换膜(Proton exchange membrane, PEM)是质子交换膜燃料电池(Proton exchange Proton exchange membrane (Proton exchange membrane, PEM) is a proton exchange membrane fuel cell (Proton exchange

membrane fiiel cell, PEMFC)的关键材料,其性能特征与燃料电池的输出性能密切相关。 membrane fiiel cell, PEMFC) the key material, which is closely related to the performance characteristics of the fuel cell output performance. 理想 Ideal

的质子交换膜不仅要具有较好的质子传导能力和化学稳定性,还需要有低的气体渗透率,足够的机械强度和较好的尺寸稳定性[Fuel Cells and Their Applications, 1996, Chapter 4〗。 The proton exchange membrane not only has good proton conductivity and chemical stability, but also needs to have low gas permeability, sufficient mechanical strength and good dimensional stability [Fuel Cells and Their Applications, 1996, Chapter 4〗 .

目前质子交换膜燃料电池主要采用的是全氟磺酸型质子交换膜,例如美国杜邦公司的Nafion系列膜,这类膜具有良好的质子传导能力和化学稳定性,但是其加工工艺较为复杂、 Currently proton exchange membrane fuel cell is mainly used in Nafion proton exchange membrane, such as DuPont's Nafion series of films, such films have good proton conductivity and chemical stability, but the process is more complicated,

价格昂贵。 Expensive. 更为重要的是其固有强度不是很高,纯粹的全氣磺酸型质子交换膜必须要具有--定的厚度,其强度才能满足燃料电池的实际霈要(一般认为干态厚度应为50um以上);由于电池运行中欧姆压降与膜的厚度几乎线性相关,即膜较厚导致欧姆压降较大[Journal of Membrane Science 237,2004, 1—7、 US Patent 5,547,551]。 More importantly, its inherent strength is not very high, pure sulfonic acid type full air proton exchange membrane must have - given thickness, the strength to meet the actual fuel cell to Pei (generally considered to be a dry thickness of 50um above); the thickness of the ohmic drop in battery operation and the film is almost linearly related, i.e. a thicker film resulting in large ohmic voltage drop [Journal of Membrane Science 237,2004, 1-7, US Patent 5,547,551].

为了解决质子交换膜强度与欧姆压降之间的矛盾,研究者对质子交换膜进行了纤维增强[Key Engineering Materials, 249, 2003, 385-3卯]或者多孔聚四觝乙烯[Handbook of Fuel Cells, Volume 3, Part 3, pp 566~575〕增强处理,并获得比较理想的结果。 In order to solve the contradiction of proton exchange membrane strength and the ohmic drop between researchers proton exchange membrane fiber reinforced [Key Engineering Materials, 249, 2003, 385-3 d] or porous polytetrafluoroethylene butt ethylene [Handbook of Fuel Cells , Volume 3, Part 3, pp 566 ~ 575] enhancement processing, and obtain more satisfactory results. 其中最有代表性的是戈尔(Gore)公司生产的多孔聚四氟乙烯增强全氟磺酸膜,他们采用EW值为1100的树脂制备的膜机械强度为纯全氟磺酸膜的2~3倍,因此其满足燃料电池需要的厚度可以减到20um,此时质子交换膜的纵向电导率为Nafionl12 (干态厚度51um)的1.5倍左右,电池性能相应有很大的提高,由于减少了昂贵的全氣磺酸树脂的使用量,其成本也有所降低。 One of the most representative is Gore (Gore) produced porous PTFE reinforced perfluorinated sulfonic acid membrane, they used resin prepared EW value of 1100, the mechanical strength of the film is pure Nafion membrane 2 ~ 3 times, so it meets the needs of the thickness of the fuel cell can be reduced to 20um, this time longitudinal proton exchange membrane conductivity of about Nafionl12 (dry thickness 51um) of 1.5 times the corresponding cell performance is greatly improved due to reduced use the full amount of expensive gas sulfonic acid resin, the cost has also been reduced.

多孔聚四氟乙烯增强全氣磺酸膜的制备方法一般是直接将多孔聚四氣乙烯放置在质子传导树脂中浸渍[US Patent 5,547,551、 US5,599,614、 US5,635,041、 US 6,613,203]、或者在多孔聚四氟乙烯两边放置电极,然后采用电泳的方法让全氟磺酸树脂穿过多孔聚四氟乙烯[WO Patent 00/78850Al]、或者将高沸点有机溶剂溶解的全氣磺酸树脂溶液滴加到多孔聚四氟乙烯上挥发溶剂[中国专利CN1416186、 Journal of Membrane Science 212,2003, 213-223]制备而成。 The porous PTFE enhanced full gas acid membrane preparation method is generally porous polytetrafluoroethylene directly placed in the proton-conducting gas ethylene resin impregnated [US Patent 5,547,551, US5,599,614, US5,635,041, US 6,613,203], or The method of placing the electrodes on both sides of the porous polytetrafluoroethylene, then using electrophoresis allows perfluorinated sulfonic acid resin through the porous polytetrafluoroethylene [WO Patent 00 / 78850Al], or high-boiling organic solvent to dissolve the entire gas sulfonic acid resin solution dropped onto the porous polytetrafluoroethylene volatile solvent [Chinese patent CN1416186, Journal of Membrane Science 212,2003, 213-223] prepared by. 然而由于多孔聚四氟乙烯强烈的惽水性而且孔径只有在1微米左右,而全氟磺酸树脂实际上是一种强亲水材料,即使全氟磺酸树脂溶液中加入了表面活性剂,然而全氟磺酸树脂溶液进入多孔聚四氣乙烯中也是很困难的[ElectrochimicaActa50,2004, 571-575]。 However, due to the strong 惽 porous polytetrafluoroethylene aqueous and only about 1 micron pore size, and perfluorinated sulfonic acid resin it is actually a strongly hydrophilic material, even if the perfluorinated sulfonic acid resin was added surfactant, but perfluorinated sulfonic acid resin solution into the porous polytetrafluoroethylene ethylene gas is also very difficult [ElectrochimicaActa50,2004, 571-575].

发明内容 DISCLOSURE

本发明的目的是提供一种基于亲水性多孔聚四氟乙烯基体的复合质子交换膜的制备方法,其特点是对多孔聚四氟乙烯膜进行亲水处理,所制备的复合质子交,具有树脂填充度高、 质子传导性能好、机械强度髙、气体渗透率低、成本低的特点,特别适用于质子交换膜燃料电池。 The purpose of the present invention is to provide a method for preparing a composite based proton hydrophilic porous PTFE substrate exchange membrane, which is characterized by porous PTFE membrane hydrophilic treatment, composite proton prepared to pay, having resin-filled high proton conductivity good performance, mechanical strength Gao, gas permeability is low, low cost, especially for proton exchange membrane fuel cell.

本发明提供的基于亲水性多孔聚四氟乙烯基体的复合质子交换膜的制备方法,按下述的步骤依舰行: Preparation based composite proton exchange membrane hydrophilic porous PTFE substrate of the present invention provides, according to the following steps according to ship lines:

步骤1、对多孔聚四氟乙烯Hift行亲水处理,得亲水性多孔聚四氟乙烯膜; Step 1, the hydrophilic porous polytetrafluoroethylene Hift row, to give a hydrophilic porous polytetrafluoroethylene membrane;

歩骤2、取洁净的亲水性多孔聚四氟乙烯I^E质子传导树J3雜液中浸渍,浸渍时间为0.5〜4 分钟,混合液中质子传导树脂的含量为质量1%〜20%,优选3%〜10%,表面活性剂Trinton-100(辛基酚聚乙氧基乙酌的含量为质量0〜4%,溶剂釆用乙醇、丙醉和异丙醇中的任一种或者其混^tl; Ho step 2, take clean hydrophilic porous polytetrafluoroethylene I ^ E proton conductive hybrid tree was immersed J3, 0.5~4 minutes immersion time, the content of the resin mixture, the proton conductivity is ~ 20% of 1% by mass , preferably 3% ~ 10%, surfactant Trinton-100 (octylphenol polyethoxylate acetate content of discretionary mass 0~4%, solvent preclude the use of ethanol, propanol and isopropyl alcohol drunk in any one or mixtures ^ tl;

步骤3、将浸渍有质子传导树脂溶液的亲水性多孔聚四氣乙稀膜,采用双轮轮滚碾压去除表面多余的树月雜液,碾压后的膜在真空:f^箱中热处理40〜60秒钟; Step 3, impregnated with a proton conductive resin solution of a hydrophilic porous polytetrafluoroethylene membrane ethylene gas, the use of two-wheeled round roll having to remove excess surface tree months miscellaneous liquid film after rolling in a vacuum: f ^ box heat treatment 40~60 seconds;

歩骤4、重复步骤2至步骤3的操作1〜4次,直至膜变得透明; Ho step 4. Repeat steps 2 through step 3 ~ 4 times, until the film becomes transparent;

步骤5、将歩骤4得到的膜在乙醇或异丙醇中浸泡5〜10分钟去除表面活性剂,然后在沸腾的去离子水中浸泡10分钟,取出经自然干燥后,在干燥箱中120〜23(TC热处理40〜60秒钟,得到亲水性多孔聚四氟乙烯增强的复合质子交换膜。 Step 5, ho step 4 was soaked in 5 to 10 minutes to remove the membrane surface active agent in ethanol or isopropanol, and then soaked in boiling deionized water for 10 minutes, remove by natural drying, oven 120~ 23 (TC heat treatment 40~60 seconds, to obtain a hydrophilic porous polytetrafluoroethylene reinforced composite proton exchange membrane.

本发明所述的多孔聚四氟乙烯膜厚度为1〜4C ^8〜20^*;孔径0.05〜4^, 孔隙率70%~95%。 The porous PTFE membrane of the present invention has a thickness of 1~4C ^ 8~20 ^ *; aperture 0.05~4 ^ porosity of 70% to 95%.

本发明所述的对多?L聚四氟乙烯,行亲水&a方法是等离子处理、等离子体接枝聚合、辐 Many of the present invention? L polytetrafluoroethylene, & a method of hydrophilizing plasma treatment, plasma graft polymerization, radiation

射接枝和化学改性其中的任何一种。 Any shot graft and chemical modification of them.

等离子体处理法是:利用等离子体产生的活性粒子如离子、电子、自由基、激发态原子及分子对材料表面进行处理。 Plasma treatment is: active particles generated by plasma such as ions, electrons, free radicals, excited atoms and molecules to the surface for processing. 使用非聚合性气体Ar,产生的自由基能与空气中的氧或水发生反应形成过氧化物,进一步与功能单体丙烯酸发生交联聚合,获得亲水性表面;或者使用聚合性气体,自由基能在气相或膜表面相互撞击,结合形成薄膜聚合物。 Use of non-polymerizable gas Ar, a radical generated can react with oxygen in the air or water to form a peroxide, and a further crosslinking functional monomer polymerized acrylic acid to obtain a hydrophilic surface; or by using a polymerizable gas, free group can collide with each other in the gas phase or membrane surface, to form a polymer film.

本发明所述的对多孔聚四氟乙烯皿行所述的等离子体处理是,使用Ar气对多孔聚四氟乙烯膜表面进行处理,Ar产生的自由基能与空气中的氧或水发生反应形成过氧化物使多孔聚四氟乙烯表面产生官能团基团,再采用功能单体丙烯酸与官能团化的多孔聚四氟乙烯膜进一步反应交联聚合,取得亲水性表面。 Of porous polytetrafluoroethylene according to pan-line plasma treatment of the present invention is the use of Ar gas porous PTFE membrane surface treatment, Ar radicals generated can react with oxygen in the air or water peroxide formation of the porous PTFE surface functional groups groups, and then using functional monomer acrylic acid and functionalized porous polytetrafluoroethylene membrane crosslinked polymer is further reacted to obtain a hydrophilic surface.

等离子体接枝聚合法是:等离子体引发接枝聚合改性,引入较长的亲水性髙分子链,对亲水性的改善程度更大,且表面性质的改善不随时间而衰减。 Plasma graft polymerization are: plasma-initiated graft polymerization modification, introduction of hydrophilic Gao longer molecular chain, the greater the degree of improvement of hydrophilic and improve the surface properties and does not decay over time.

本发明所述的对多孔聚四氟乙烯膜进行等离子体接枝聚合是:用Ar等离子体预处理多孔聚 The plasma membrane of porous polytetrafluoroethylene graft polymerization of the present invention is: Ar plasma pre-treatment of porous polyethylene

四氟乙烯膜,再用亲水性功能单体丙烯酸、苯乙烯磺酸钠盐、a; w-二甲基乙酰胺或甲基丙 Tetrafluoroethylene membrane, and then a hydrophilic functional monomer acrylic acid, styrene sulfonic acid sodium salt, a; w- dimethylacetamide or methacrylic

烯酸縮水甘油酯水溶液,在近紫外光的诱导下发生接枝共聚反应。 Glycidyl acid aqueous solution, the occurrence of graft copolymerization reaction induced by near-ultraviolet light.

本发明所述的对多孔聚四氟乙烯皿^H射接枝是:将多孔聚四氟乙稀膜置于苯乙烯、反丁烯二酸或甲基丙烯酸酯类可聚合的单体中,以,0辐射,单体在多孔聚四氟乙烯膜表面发生 Porous Teflon pan according to the invention ^ H is shot graft is: the porous PTFE membrane was placed styrene, fumaric acid or methacrylic acid esters of polymerizable monomers, to, 0 radiation, monomer porous PTFE membrane surface

化学接枝聚合,从而使多孔聚四氟乙烯膜表面形成一层易于粘接的接枝聚合物。 Chemical graft polymerization, so that the surface layer of a porous polytetrafluoroethylene film readily bonded graft polymer.

本发明所述的对多孔聚四氟乙烯膜进行化学改性是,将多孔聚四氟乙烯膜经过化学试剂处 The porous PTFE membrane is chemically modified according to the present invention, the porous PTFE membrane after chemical agents at

理以提髙其表面亲水性,所述的化学试剂是金属钠的氨溶液,萘钠四氨呋喃溶液,碱金属汞齐, 五碳基铁溶液中的任何一种。 Gao surface treated to provide hydrophilicity, the chemical agents are ammonia solution of sodium metal, sodium naphthalene tetracarboxylic furan ammonia solution, alkali metal amalgam, five-carbon iron solution either.

本发明所述的质子传导树脂是^IR欲酸树脂、磺ifcH氟苯乙烯树脂、聚甲基苯基磺酸硅氧烷树脂> 磺化聚继醚兩树脂、磺tt^苯乙梯-聚乙烯共聚物树脂,和磺化聚苯乙烯一聚乙烯/丁烯一聚苯乙烯树脂中的,一种。 Proton conductive resin of the present invention is ^ IR For acid resin, styrene sulfonic ifcH fluorine resin, silicone resin, poly methyl phenyl acid> sulfonated poly ether Following two resins, styrene sulfonic tt ^ ladder - Poly ethylene copolymer resin, a sulfonated polystyrene, and polyethylene / butylene a polystyrene resin, a method.

本发明将浸渍有质子传导树脂的亲水性多孔聚四氟乙烯膜,在120〜230t:热处理30〜60秒钟,挥发掉树脂的溶剂,选取的热处理亂度与选取的质子传导树脂有关,热处理温度介于质子传导树脂和亲水性多孔聚四氣乙烯膜的自化MS之间。 The present invention is impregnated with a hydrophilic porous polytetrafluoroethylene membrane proton conductive resin, in 120~230t: heat treatment 30~60 seconds to evaporate the solvent resin selected scrambling degree heat treatment and selection of a proton conductive resin related, The heat treatment temperature is between proton conductive resin and hydrophilic porous polyethylene between four gas from ethylene film of MS.

本发明与背景技术相比,所制备的基于亲水性多孔聚四氟乙烯基体的的复合质子交换膜具有良好的树脂填充度,质子传导能力强、气体渗透能力小、机械性能高、在电池中可以长时间稳定工作。 Compared with the background, based on hydrophilic porous PTFE matrix composite proton exchange membrane prepared with good resin filling degree, proton conduction ability, small gas permeability, high mechanical performance, battery It can be a long time stability. 附图说明 Brief Description

附图1为实施例1中亲水性多孔聚四氟乙烯增强的全豕碘麟子交鄉的截面照片; 附图2为实施例1中作为对比的,未亲水处理多孔聚四氟乙烯增强的全氟磺酸质子交换膜的截面照片; Figure 1 is a cross-sectional picture 1 implementation of the hydrophilic porous PTFE-enhanced whole hog example iodine-lin Township Transactions; Fig. 2 in Example 1. As a comparison, and not treating the porous hydrophilic polytetrafluoroethylene Enhanced Nafion proton exchange membranes sectional photograph;

附图3为实施例2中亲水性多?Ug四氟乙烯增强的敝聚鹏酮质子交换膜的截面照片: 附图4为为实施例2中作为对比的,未亲水^多孔聚四氟乙烯增强的磺化聚醚醚酮质子交皿的截面照片。 Example 2 Figure 3 is hydrophilic Ug more spacious reinforced poly tetrafluoroethylene Peng sectional photograph one proton exchange membrane:? 4 of the accompanying drawings in Example 2. As a comparison, the non-porous hydrophilic polytetramethylene ^ fluoride enhanced speek proton cross sectional dish photo.

具体实施力式 DETAILED DESCRIPTION force formula

下面aa实施例对本发明作进一步说明。 Aa following examples further illustrate the present invention. 实施例i Example i

取1鄉米厚、孔御.05〜2微米、孔隙率85%的多孔聚四氣乙烯(PTFE)膜,使用Ar气对PTFE 表面进行处理,Ar气产生的自由基能与空气中的氧或水发生反应形成过氣化物,进一步与功能单体一丙烯酸发生交联聚合,获得亲水性表面。 Take a township meter thick, hole Royal .05~2 microns, a porosity of 85% ethylene gas porous polytetrafluoroethylene (PTFE) membrane, using Ar gas on the PTFE surface treatment, Ar gas can generate oxygen radicals in the air or over-react to form water vapor, further functional monomer and a crosslinking polymerization of acrylic acid to obtain a hydrophilic surface. 将亲水处理后的多孔聚四氟乙烯膜放置在5% (质量) 的全tUII子传导树脂(Nafion, EW值1100)的异丙,液中浸渍IO分钟,然后取出采用双轮轮滚碾压一遍,碾压后的膜lfc^真空flS箱,调节M至160"C,热处理60秒钟,重复上述浸渍处理过程4遍,得到透明的复合膜;将,在异丙醉中浸泡5,去掉有机杂质,然后在沸腾的去离子水浸泡10分钟,取出经自然干燥后,在fli箱中14(TC热处理40秒钟,得到亲水性多孔聚四氟乙烯增强的质子交«' The treated hydrophilic porous polytetrafluoroethylene membrane was placed in a 5% (by mass) of the whole tUII proton conductivity resin (Nafion, EW value 1100) isopropyl, was immersed IO minutes and then removed using the two-wheeled roller grinding wheel pressure again, after rolling membrane lfc flS ^ vacuum box, adjusted to M 160 "C, the heat treatment for 60 seconds, repeating the above process 4 times the impregnation, to obtain a transparent composite film; will, soaked in isopropyl drunk 5, remove organic impurities, then boiling deionized water soak for 10 minutes, remove by natural drying, fli box 14 (TC heat treatment for 40 seconds to obtain a hydrophilic porous PTFE reinforced proton cross «'

本发明所制备的亲7jC性多孔聚四氟乙烯增强的全氟磺鹏子交换膜截面照片如附图l所示,由于质子传导树脂填充度的提高,^fj备的膜具有优异的性能,详细性能参数列于表l。 Pro 7jC porous polytetrafluoroethylene prepared by the invention of reinforced perfluorosulfonic Peng exchange membrane l sectional photograph as shown in the drawings, because the proton conductive resin filling degree increase, the film ^ fj equipment has excellent performance, detailed performance parameters are listed in Table l. 作为对比, 不对多孔聚四氟乙烯膜进行亲水处理,其它过程与本实施例相同的复合质子交,的截面照片如 In contrast, no porous polytetrafluoroethylene membrane hydrophilic treatment, for example, the same composite proton cross other processes of the present embodiment, the cross-sectional photograph as

附图2所示,这种复合膜不具有很好的填充度a Shown in Figure 2, the composite film does not have a good degree of filling

实施例2 Example 2

取丄2微米厚、孔径0.0S〜2絲、孔隙率85%的多孔聚四氟乙烯(PTFE)膜,用Ar等离子 Take Shang 2 microns thick, pore 0.0S~2 silk, 85% porosity porous polytetrafluoroethylene (PTFE) membrane, with Ar plasma

体预处理PTFE膜,再用亲水性功能单体丙烯酸、苯乙烯aHg钠盐、N, N-二甲基乙酰胺和甲基丙烯酸縮水甘油酯水溶液在近紫外光的诱导下发生接枝共聚反应。 PTFE membrane body pretreatment, and then a hydrophilic functional acrylic monomers, styrene aHg salt, N, N- dimethylacetamide and glycidyl methacrylate graft copolymerization in aqueous solution occurs near ultraviolet light induced reaction. 将亲水处理后的多孔聚四氟乙烯膜放置在5°/。 The porous PTFE membrane hydrophilized placed in 5 ° /. (质量〉的磺化聚醚醚酮树脂(s-PEEK, EW值900)与2% (质量)的Trinton-lOO 乙醇溶液中浸渍10分钟,然后取出采用双轮轮滚碾压一遍,碾压后的膜放入真空干燥箱,调节温度至230'C,热处理50秒钟,重复上述漫渍处理过程5遍,得到透明的复合膜;将该膜在异丙醇中浸泡5分钟去掉有机杂质,然后在沸腾的去离子水浸泡10,,取出经自然干燥后,在干燥箱中230'C热处理60秒钟,亲水性多孔聚四氟乙烯增强的磺化聚醚醚酮质子交换膜。其截面照片如附图3所示;作为对比,不对多孔聚四氟乙烯膜进行亲水处理,其它过程与本实施例相同的复合质子交换膜的截面照片如附图4所示,这种复合膜不具有很好的填充度。 表l.复合质子交皿的性能参数<formula>formula see original document page 6</formula> (Quality> sulfonated polyether ether ketone resin (s-PEEK, EW value of 900) and 2% (by mass) of Trinton-lOO immersed in ethanol for 10 minutes, then remove the use of two-wheeled roller wheel rolling again, rolling After the film was placed in a vacuum oven, adjust the temperature to 230'C, heat treatment for 50 seconds, repeat the above process stains diffuse 5 times, to obtain a transparent composite film; five minutes the membrane was immersed in isopropanol to remove organic impurities , then in boiling deionized water soak for 10 ,, after removal by natural drying, heat-treated in a dry box 230'C for 60 seconds, the hydrophilic porous polytetrafluoroethylene reinforced sulfonated polyetheretherketone proton exchange membrane. Its cross-section as shown in Figure 3 photograph; In contrast, not porous polytetrafluoroethylene membrane hydrophilic treatment, other processes are the same with the embodiment of the present composite proton exchange membrane as a cross-sectional photograph shown in the drawings, the composite 4 film does not have a good degree of filling Table l. Composite Proton cross dish performance parameters <formula> formula see original document page 6 </ formula>

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Referencia
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Clasificaciones
Clasificación internacionalH01M8/1041, H01M8/1069, H01M8/1018, C08J5/22, B29C71/00, C08L27/18
Clasificación cooperativaY02E60/50
Eventos legales
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15 Nov 2006C06Publication
10 Ene 2007C10Entry into substantive examination
7 May 2008C14Grant of patent or utility model
12 Ago 2015EXPYTermination of patent right or utility model