技术领域technical field
本发明涉及燃料电池质子交换膜技术领域，具体涉及一种磷酸硼包覆碳纳米管复合质子交换膜的制备方法。The invention relates to the technical field of fuel cell proton exchange membranes, in particular to a method for preparing a boron phosphate-coated carbon nanotube composite proton exchange membrane.
背景技术Background technique
质子交换膜(proton exchange membrane，PEM)是燃料电池(fuel cell，FC)的核心组件，目前广泛应用的仍是全氟磺酸膜，其代表产品是杜邦公司的系列膜，该膜具有化学稳定性好和质子传导率高等优点，但也存在着工艺复杂、成本高、使用温度低、在直接甲醇燃料电池(direct methanol fuel cell,DMFC)应用中阻醇性差等缺点，这些缺点加速了探寻新型非氟类聚合物材料的研发工作。目前研究比较多的非氟类聚合物PEM材料有聚酰亚胺、聚砜、聚苯并咪唑和磺化聚醚醚酮等芳香族聚合物。其中磺化聚醚醚酮(sulfonated polyether ether ketone,SPEEK)具有较高的电导率和较好的阻醇性以及良好的热稳定性和化学稳定性，因而被认为是最有希望代替全氟磺酸膜的非氟聚合物材料之一。The proton exchange membrane (proton exchange membrane, PEM) is the core component of the fuel cell (fuel cell, FC). At present, the perfluorosulfonic acid membrane is still widely used, and its representative product is DuPont's A series of membranes, which have the advantages of good chemical stability and high proton conductivity, but also have complex processes, high cost, low operating temperature, and poor alcohol resistance in direct methanol fuel cell (DMFC) applications, etc. These shortcomings have accelerated the research and development efforts to find new non-fluoropolymer materials. At present, the non-fluorine polymer PEM materials that have been studied more include aromatic polymers such as polyimide, polysulfone, polybenzimidazole and sulfonated polyether ether ketone. Among them, sulfonated polyether ether ketone (SPEEK) has high electrical conductivity, good alcohol resistance, good thermal stability and chemical stability, so it is considered to be the most promising alternative to perfluorosulfone. One of the non-fluoropolymer materials for acid membranes.
虽然SPEEK膜具有较好的应用前景，但仍存在着低磺化度的SPEEK膜电导率较低而高磺化度的尺寸稳定性和机械性能差等缺点，而采用交联虽然可增强膜的机械性能，但又常以降低电导率为代价。为了进一步提高SPEEK膜的电导率及其综合性能，制备无机-有机复合质子交换膜成为各国学者的研究热点。在SPEEK中掺杂无机物使其兼有SPEEK膜良好的柔韧性、成膜性和易加工性，及无机物的耐高温、耐腐蚀和高机械强度等特征。掺杂的物质主要包括两大类：一类是可增加膜吸水能力和机械性能的二氧化硅(SiO2)、碳纳米管(CNTs)等无机物；另一类是可提高膜电导率的杂多酸(HPA)、磷酸硼(BPO4)、磷酸锆等无机质子导体。Although SPEEK membranes have good application prospects, there are still disadvantages such as low electrical conductivity of SPEEK membranes with low sulfonation degrees and poor dimensional stability and poor mechanical properties of high sulfonation degrees. Mechanical properties, but often at the expense of reduced electrical conductivity. In order to further improve the conductivity and comprehensive performance of SPEEK membranes, the preparation of inorganic-organic composite proton exchange membranes has become a research hotspot of scholars from all over the world. The doping of inorganic substances in SPEEK makes it have the good flexibility, film-forming property and easy processability of SPEEK film, as well as the high temperature resistance, corrosion resistance and high mechanical strength of inorganic substances. Doping substances mainly include two categories: one is inorganic substances such as silicon dioxide (SiO2 ) and carbon nanotubes (CNTs) that can increase the water absorption capacity and mechanical properties of the membrane; the other is inorganic substances that can increase the membrane conductivity. Heteropoly acid (HPA), boron phosphate (BPO4 ), zirconium phosphate and other inorganic proton conductors.
磷酸硼(BPO4)作为近年来一种新型的无机非金属磷酸盐是由P、B和O原子形成的正四面体晶体，PO4和BO4通过共享氧原子交替出现在三维空间网状结构中，这种特殊的结构赋予了BPO4在高温下优异的质子传导性能。Cho(EunKyung Cho.J.Membr.Sci.2008,318(1-2):355-362.)以(C3H7O)3B和H3PO4为前躯体，通过溶胶-凝胶法在SPEEK中原位生成BPO4制得复合质子交换膜SPEEK/BPO4-X(X＝10～40wt％)，结果使得复合质子交换膜的质子传导率大大增加。然而这种直接掺杂法使得有机相和无机相的相容性变差，这导致膜的均一性和理化性能均有所降低。而碳纳米管/聚合物复合材料因碳纳米管具有优异的力学性能以及耐化学性能，另外还具有尺寸小、长径比大、电导率高、密度小等优点，是复合材料理想的增强体。本发明人的课题组在中国专利CN 103296297A中公开了一种燃料电池用有机-无机复合质子交换膜的制备方法，该方法首先将碳纳米管经氧化处理，然后通过溶胶-凝胶法制备二氧化硅包覆的碳纳米管，再将二氧化硅包覆的碳纳米管分散液与磺化聚合物的分散液共混，进行溶液浇铸成膜。所制得的复合质子交换膜具有高吸水、高阻醇性能。专利CN104779400A则公开了一种用于质子交换膜的改性碳纳米管的制备方法，该方法将碳纳米管表面包裹一层磺酸化多巴胺，提高了碳纳米管与质子交换膜基质间的界面结合力，磺酸化的碳纳米管形成的质子传导通道提高了膜的质子电导率，同时纳米粒子在基体中的良好分散性使膜的甲醇渗透性能得到改善。Boron phosphate (BPO4 ), as a new type of inorganic non-metallic phosphate in recent years, is a regular tetrahedral crystal formed by P, B and O atoms. PO4 and BO4 appear alternately in a three-dimensional network structure by sharing oxygen atoms. Among them, this special structure endows BPO with excellent proton conductivity at high temperature. Cho (EunKyung Cho.J.Membr.Sci.2008,318(1-2):355-362.) using (C3 H7 O)3 B and H3 PO4 as precursors, by sol-gel method The composite proton exchange membrane SPEEK/BPO4 -X (X=10-40wt%) is produced by in-situ generation of BPO4 in SPEEK, and the proton conductivity of the composite proton exchange membrane is greatly increased as a result. However, this direct doping method makes the compatibility of the organic phase and the inorganic phase worse, which leads to a decrease in the uniformity and physical and chemical properties of the film. The carbon nanotube/polymer composite material has excellent mechanical properties and chemical resistance due to carbon nanotubes, and also has the advantages of small size, large aspect ratio, high electrical conductivity, and low density. It is an ideal reinforcement for composite materials. . The inventor's research group disclosed a method for preparing an organic-inorganic composite proton exchange membrane for fuel cells in Chinese patent CN 103296297A. In this method, carbon nanotubes are first oxidized, and then prepared by a sol-gel method. The silicon oxide-coated carbon nanotubes, and then the silicon dioxide-coated carbon nanotube dispersion and the sulfonated polymer dispersion are blended to form a film by solution casting. The prepared composite proton exchange membrane has the properties of high water absorption and high resistance to alcohol. Patent CN104779400A discloses a method for preparing modified carbon nanotubes used in proton exchange membranes. In this method, the surface of carbon nanotubes is coated with a layer of sulfonated dopamine, which improves the interfacial bonding between carbon nanotubes and proton exchange membrane matrix. The proton conduction channel formed by sulfonated carbon nanotubes improves the proton conductivity of the membrane, and the good dispersion of nanoparticles in the matrix improves the methanol permeability of the membrane.
本申请发明人基于对以上理论的理解和分析，结合磷酸硼和碳纳米管各自优点对磺化聚醚醚酮膜进行掺杂改性，一方面通过碳纳米管的骨架增强实现膜机械性能的提升；另一方面磷酸硼包覆在碳纳米管上在膜内形成通道，促进质子快速传递。Based on the understanding and analysis of the above theories, the inventors of the present application combined the respective advantages of boron phosphate and carbon nanotubes to modify the sulfonated polyether ether ketone membrane by doping and modifying it. On the other hand, boron phosphate is coated on carbon nanotubes to form channels in the membrane to promote the rapid transfer of protons.
发明内容Contents of the invention
针对现有技术中存在的不足，本发明的目的在于提供了一种磷酸硼包覆碳纳米管复合质子交换膜的制备方法。Aiming at the deficiencies in the prior art, the object of the present invention is to provide a method for preparing a boron phosphate-coated carbon nanotube composite proton exchange membrane.
为了实现上述发明目的，本发明采取了如下技术措施：In order to realize the foregoing invention object, the present invention has taken following technical measures:
一种磷酸硼包覆碳纳米管复合质子交换膜的制备方法，其步骤如下：A preparation method of boron phosphate coated carbon nanotube composite proton exchange membrane, the steps are as follows:
1)磺化聚醚醚酮的制备：1) Preparation of sulfonated polyether ether ketone:
将聚醚醚酮粉末(Mw＝38000)置于98wt％浓硫酸中，加热搅拌，反应2～4h，然后将反应液倒入冰水混合物中搅拌1h，静置过滤，所得固体用去离子水洗涤至洗出液的pH＝6.5-7.0，最后将分离出的固体在60℃下干燥24h得到磺化聚醚醚酮；Put polyether ether ketone powder (Mw=38000) in 98wt% concentrated sulfuric acid, heat and stir, react for 2-4 hours, then pour the reaction solution into ice-water mixture and stir for 1 hour, stand and filter, and use deionized water to obtain the solid Wash until the pH of the eluate = 6.5-7.0, and finally dry the separated solid at 60°C for 24 hours to obtain sulfonated polyether ether ketone;
所述聚醚醚酮粉末与98wt％浓硫酸固液比为1g:20～30mL；所述加热搅拌温度为50℃；The solid-to-liquid ratio of the polyetheretherketone powder to 98wt% concentrated sulfuric acid is 1g:20-30mL; the heating and stirring temperature is 50°C;
2)磷酸硼包覆碳纳米管的制备：2) Preparation of boron phosphate-coated carbon nanotubes:
(1)配制浓度为50mmol/L的Tris(三羟甲基氨基甲烷)溶液，加入0.1mol/L的盐酸调节溶液pH值为8，得100ml Tris-HCl缓冲液，备用；将50mg多巴胺和50mg碳纳米管置于预先配置好的100ml Tris-HCl缓冲液中，超声分散1小时后，继续室温搅拌16小时，然后真空抽滤，先用无水乙醇洗涤3次，再用去离子水洗涤3次，至滤液无色，干燥后得到聚多巴胺修饰的碳纳米管；(1) preparation concentration is the Tris (trishydroxymethylaminomethane) solution of 50mmol/L, adds the hydrochloric acid adjustment solution pH value of 0.1mol/L to be 8, gets 100ml Tris-HCl buffer solution, for subsequent use; Mix 50mg dopamine and 50mg Place the carbon nanotubes in a pre-configured 100ml Tris-HCl buffer solution, ultrasonically disperse for 1 hour, continue to stir at room temperature for 16 hours, then vacuum filter, wash 3 times with absolute ethanol, and then wash 3 times with deionized water. times, until the filtrate is colorless, and after drying, polydopamine-modified carbon nanotubes are obtained;
所述多巴胺为左旋多巴；The dopamine is levodopa;
所述碳纳米管优选为多壁碳纳米管；The carbon nanotubes are preferably multi-walled carbon nanotubes;
(2)将40mg步骤2)中(1)所得聚多巴胺修饰的碳纳米管与20mg固体磷酸一起加入到100ml N,N-二甲基乙酰胺(DMAC)中，超声分散1小时后，在持续磁力搅拌下升温至80℃，然后缓慢滴加33mg硼酸三丙酯，滴加完后在110℃的条件下继续反应20小时，冷却至室温后经真空抽滤、溶剂DMAC洗涤、干燥后得磷酸硼包覆碳纳米管；(2) 40 mg of polydopamine-modified carbon nanotubes obtained in (1) in step 2) were added to 100 ml of N,N-dimethylacetamide (DMAC) together with 20 mg of solid phosphoric acid, and after ultrasonic dispersion for 1 hour, the Raise the temperature to 80°C under magnetic stirring, then slowly add 33 mg of tripropyl borate dropwise, continue to react at 110°C for 20 hours after the dropwise addition, cool to room temperature, vacuum filter, wash with solvent DMAC, and dry to obtain phosphoric acid Boron-coated carbon nanotubes;
3)复合质子交换膜的制备：3) Preparation of composite proton exchange membrane:
首先将步骤1)制得的磺化聚醚醚酮溶解在N,N-二甲基乙酰胺中形成质量分数为10％的溶液，然后加入步骤2)制得的磷酸硼包覆碳纳米管，充分混合后得到铸膜溶液，该铸膜溶液中磷酸硼包覆碳纳米管与磺化聚醚醚酮的质量比为0.5～5:100，将铸膜溶液倒入铸膜槽内，经分步干燥、冷却即可得到磷酸硼包覆碳纳米管复合质子交换膜；First, the sulfonated polyether ether ketone prepared in step 1) is dissolved in N,N-dimethylacetamide to form a solution with a mass fraction of 10%, and then the boron phosphate-coated carbon nanotubes prepared in step 2) are added , after fully mixing to obtain a film casting solution, the mass ratio of boron phosphate-coated carbon nanotubes to sulfonated polyetheretherketone in the film casting solution is 0.5 to 5:100, pour the film casting solution into the film casting tank, and Step-by-step drying and cooling can obtain boron phosphate-coated carbon nanotube composite proton exchange membrane;
所述铸膜槽选自聚四氟乙烯槽和玻璃槽中的一种；The cast film tank is selected from one of a polytetrafluoroethylene tank and a glass tank;
所述分步干燥分三步，具体为：先55℃～65℃干燥8～10h；然后95℃～105℃干燥8～10h；最后135℃～145℃干燥2～3h；The step-by-step drying is divided into three steps, specifically: firstly drying at 55°C-65°C for 8-10 hours; then drying at 95°C-105°C for 8-10 hours; finally drying at 135°C-145°C for 2-3 hours;
所述冷却具体为：冷却到20℃～35℃。The cooling specifically includes: cooling to 20°C to 35°C.
本发明技术方案与现有技术相比，具有如下优点和有益效果：Compared with the prior art, the technical solution of the present invention has the following advantages and beneficial effects:
1、与采用简单基团对碳纳米管的修饰相比，本发明采用左旋多巴(L-DOPA)在碱性缓冲液中发生氧化自聚合的特性对碳纳米管表面功能化修饰的方法简单、成本低，同时引入的聚多巴胺层，结果稳定、相容性好。1. Compared with the modification of carbon nanotubes by simple groups, the present invention uses levodopa (L-DOPA) to undergo oxidative self-polymerization in alkaline buffers, and the method for carbon nanotube surface functional modification is simple , low cost, and the polydopamine layer introduced at the same time, the result is stable and compatible.
2、与采用一系列复杂的化学接枝过程相比，本发明方法采用简单的溶胶-凝胶法将具有优异质子传导率的磷酸硼包覆在碳纳米管的表面，避免了复杂的化学处理过程，同时碳纳米管本身的结构得以完整保留。2. Compared with a series of complicated chemical grafting processes, the method of the present invention uses a simple sol-gel method to coat boron phosphate with excellent proton conductivity on the surface of carbon nanotubes, avoiding complicated chemical treatments process, while the structure of the carbon nanotube itself is preserved intact.
3、与纯SPEEK膜相比，磷酸硼包覆碳纳米管的加入不仅有效提高了复合质子交换膜的尺寸和氧化稳定性(见表1和图4)，同时也能显著提高复合质子交换膜的机械性能(见表1)；而且复合质子交换膜在高温下的质子传导性能也得到显著提高(见表2)。3. Compared with the pure SPEEK membrane, the addition of boron phosphate-coated carbon nanotubes not only effectively improves the size and oxidation stability of the composite proton exchange membrane (see Table 1 and Figure 4), but also significantly improves the composite proton exchange membrane. Mechanical properties (see Table 1); and the proton conductivity of the composite proton exchange membrane at high temperature has also been significantly improved (see Table 2).
附图说明Description of drawings
图1为实施例1至3及对比例1制备的质子交换膜的氧化稳定性数据图。FIG. 1 is a graph showing the oxidation stability data of the proton exchange membranes prepared in Examples 1 to 3 and Comparative Example 1.
图2为质子传导率测试平台示意图，图中1是聚四氟乙烯板，2是螺钉(起固定作用)，3是中空凹槽，4是膜样品，5是黑金箔电极，6是铂丝导线。Figure 2 is a schematic diagram of the proton conductivity test platform, in which 1 is a polytetrafluoroethylene plate, 2 is a screw (for fixing), 3 is a hollow groove, 4 is a membrane sample, 5 is a black gold foil electrode, and 6 is a platinum wire wire.
结合表1、2和图1可知，本发明的磷酸硼包覆碳纳米管复合质子交换膜由于掺杂体表层具有质子传导能力，将其掺杂到质子交换膜中，能够很好地改善质子交换膜的电导率，使其提高40％至60％；同时，掺杂体在基体中分散均匀，增强了质子交换膜的尺寸、氧化稳定性及机械性能。Combining Tables 1, 2 and Fig. 1, it can be seen that the boron phosphate-coated carbon nanotube composite proton exchange membrane of the present invention has proton conductivity due to the surface layer of the dopant, so doping it into the proton exchange membrane can well improve the proton exchange membrane. The conductivity of the exchange membrane is increased by 40% to 60%. At the same time, the dopant is uniformly dispersed in the matrix, which enhances the size, oxidation stability and mechanical properties of the proton exchange membrane.
图3和图4分别为实施例1所制备的磷酸硼包覆碳纳米管的扫描电镜图和透射电镜图。3 and 4 are scanning electron micrographs and transmission electron micrographs of boron phosphate-coated carbon nanotubes prepared in Example 1, respectively.
图5为不同质子交换膜的形貌：a和b分别为纯SPEEK膜的表面和截面形貌；c和d分别为实施例1和2制备的复合质子交换膜的截面形貌。Figure 5 shows the morphology of different proton exchange membranes: a and b are the surface and cross-sectional morphology of the pure SPEEK membrane, respectively; c and d are the cross-sectional morphology of the composite proton exchange membrane prepared in Examples 1 and 2, respectively.
具体实施方式detailed description
下面结合具体实施例对本发明做进一步说明。The present invention will be further described below in conjunction with specific embodiments.
以下实施例中，所用多巴胺均为左旋多巴(分析纯，含量≧99％)，磷酸为固体磷酸(分析纯，含量≧99％)，硼酸三丙酯为液体(分析纯，含量≧99％)，碳纳米管为多壁碳纳米管，管径为10-30nm，长度为5-15μm，购于深圳市纳米港有限公司，聚醚醚酮粉末购自英国Victrex公司，Mw＝38000；In the following examples, the dopamine used is levodopa (analytical pure, content >=99%), phosphoric acid is solid phosphoric acid (analytical pure, content >=99%), and tripropyl borate is liquid (analytical pure, content >=99%) ), carbon nanotubes are multi-walled carbon nanotubes with a diameter of 10-30nm and a length of 5-15 μm, purchased from Shenzhen Nanometer Harbor Co., Ltd., polyether ether ketone powder purchased from Victrex, UK, Mw=38000;
其他试剂均为常规市售商品。All other reagents are commercially available.
实施例1Example 1
一种磷酸硼包覆碳纳米管复合质子交换膜的制备方法，步骤如下：A preparation method of boron phosphate coated carbon nanotube composite proton exchange membrane, the steps are as follows:
1)磺化聚醚醚酮的制备：1) Preparation of sulfonated polyether ether ketone:
将聚醚醚酮粉末置于98wt％浓硫酸中(固液比为1g：20mL)，反应温度为50℃，充分搅拌反应3h，然后将反应液倒入大量的冰水混合物中搅拌1h，静置过滤，所得固体再用去离子水多次洗涤，直到洗出液pH＝6.5～7.0时过滤出沉降的聚合物，最后在60℃下干燥24h得到磺化聚醚醚酮；Put the polyetheretherketone powder in 98wt% concentrated sulfuric acid (solid-to-liquid ratio: 1g:20mL), the reaction temperature is 50°C, fully stir the reaction for 3h, and then pour the reaction solution into a large amount of ice-water mixture and stir for 1h, statically The resulting solid was washed with deionized water several times until the pH of the eluate was 6.5-7.0, and the precipitated polymer was filtered out, and finally dried at 60°C for 24 hours to obtain sulfonated polyether ether ketone;
2)磷酸硼包覆碳纳米管的制备：2) Preparation of boron phosphate-coated carbon nanotubes:
(1)配制浓度为50mmol/L的Tris(三羟甲基氨基甲烷)溶液，加入0.1mol/L的盐酸调节溶液pH值为8，得100ml Tris-HCl缓冲液；将50mg多巴胺和50mg碳纳米管置于预先配置好的100ml Tris-HCl缓冲液中，超声分散1小时后，继续室温搅拌16小时，然后真空抽滤，先用无水乙醇洗涤3次，再用去离子水洗涤3次，至滤液无色，干燥，得到聚多巴胺修饰的碳纳米管；(1) preparation concentration is the Tris (trishydroxymethylaminomethane) solution of 50mmol/L, adds the hydrochloric acid adjustment solution pH value of 0.1mol/L to be 8, obtains 100ml Tris-HCl buffer solution; Mix 50mg dopamine and 50mg carbon nano Place the tube in a pre-configured 100ml Tris-HCl buffer solution, ultrasonically disperse for 1 hour, continue to stir at room temperature for 16 hours, then vacuum filter, wash with absolute ethanol for 3 times, and then wash with deionized water for 3 times. Until the filtrate is colorless, dry to obtain polydopamine-modified carbon nanotubes;
(2)将40mg步骤2)中(1)所得聚多巴胺修饰的碳纳米管与20mg固体磷酸一起加入到100ml N,N-二甲基乙酰胺(DMAC)中，超声分散1小时后，在持续磁力搅拌下升温至80℃，然后缓慢滴加33mg硼酸三丙酯，滴加完后在110℃的条件下继续反应20小时，冷却至室温后经真空抽滤、溶剂DMAC洗涤、干燥后得磷酸硼包覆碳纳米管；(2) 40 mg of polydopamine-modified carbon nanotubes obtained in (1) in step 2) were added to 100 ml of N,N-dimethylacetamide (DMAC) together with 20 mg of solid phosphoric acid, and after ultrasonic dispersion for 1 hour, the Raise the temperature to 80°C under magnetic stirring, then slowly add 33 mg of tripropyl borate dropwise, continue to react at 110°C for 20 hours after the dropwise addition, cool to room temperature, vacuum filter, wash with solvent DMAC, and dry to obtain phosphoric acid Boron-coated carbon nanotubes;
3)复合质子交换膜的制备：3) Preparation of composite proton exchange membrane:
首先将步骤1)制得的磺化聚醚醚酮溶解在N,N-二甲基乙酰胺中形成质量分数为10％的溶液，然后加入步骤2)制得的磷酸硼包覆碳纳米管，充分混合后得到铸膜溶液，该铸膜溶液中磷酸硼包覆碳纳米管与磺化聚醚醚酮的质量比为0.5:100，将铸膜溶液倒入聚四氟乙烯立方槽内，依次经60℃干燥8h、100℃干燥8h、140℃干燥2h后，25℃冷却即可得到磷酸硼包覆碳纳米管复合质子交换膜(通过滴定法，测得膜的离子交换容量(IEC)值为1.13mmol/g)。膜的各项性能测试结果详见表1、2和图1。First, the sulfonated polyether ether ketone prepared in step 1) is dissolved in N,N-dimethylacetamide to form a solution with a mass fraction of 10%, and then the boron phosphate-coated carbon nanotubes prepared in step 2) are added , after fully mixing to obtain a casting solution, the mass ratio of boron phosphate-coated carbon nanotubes to sulfonated polyether ether ketone in the casting solution is 0.5:100, pour the casting solution into a polytetrafluoroethylene cubic tank, After drying at 60°C for 8h, 100°C for 8h, and 140°C for 2h, then cooling at 25°C, a boron phosphate-coated carbon nanotube composite proton exchange membrane can be obtained (by titration, the ion exchange capacity (IEC) of the membrane was measured The value is 1.13 mmol/g). The performance test results of the membrane are shown in Table 1, 2 and Figure 1 in detail.
本实施例所制备的磷酸硼包覆碳纳米管的扫描电镜图和透射电镜图见图3和图4。从图3和图4中分别可以看出通过简单的溶胶-凝胶法，BPO4能够均匀包覆于碳纳米管的表面，且包覆层厚度约为10nm，同时碳纳米管自身的结构也保持较为完整。本实施例所制备的复合质子交换膜的截面形貌参见图5c，从图5c可以看出磷酸硼包覆的碳纳米管在磺化聚醚醚酮基体中分散十分均匀。The scanning electron micrographs and transmission electron micrographs of the boron phosphate-coated carbon nanotubes prepared in this example are shown in FIG. 3 and FIG. 4 . From Figure 3 and Figure 4, it can be seen that BPO4 can be uniformly coated on the surface of carbon nanotubes through a simple sol-gel method, and the thickness of the coating layer is about 10nm, and the structure of carbon nanotubes itself is also remain relatively complete. The cross-sectional morphology of the composite proton exchange membrane prepared in this example is shown in Fig. 5c. It can be seen from Fig. 5c that the boron phosphate-coated carbon nanotubes are dispersed very uniformly in the sulfonated polyether ether ketone matrix.
对比例1Comparative example 1
将醚醚酮粉末溶于98wt％浓硫酸(固液比为1g：25mL)中，反应温度50℃，搅拌下充分反应3h，然后将反应液倒入大量的冰水混合物中搅拌1h，静置过滤，所得固体再用去离子水多次洗涤，直到洗出液的pH＝6.5～7.0时过滤出沉降的聚合物，最后在60℃下干燥24h得到磺化产物磺化聚醚醚酮。通过滴定法，测得磺化度(DS)为45.4％，离子交换容量(IEC)值为1.36mmol/g。再将5g本对比例1制备的磺化聚醚醚酮溶解在N,N-二甲基乙酰胺中，形成10wt％的溶液，将溶液在洁净的立方玻璃槽内成膜，依次经55℃干燥8h、95℃干燥8h、135℃干燥2h，然后20℃冷却揭膜得纯磺化聚醚醚酮膜。膜的各项性能测试结果详见表1、2和图1。Dissolve ether ether ketone powder in 98wt% concentrated sulfuric acid (solid-to-liquid ratio: 1g:25mL) at a reaction temperature of 50°C, fully react for 3 hours under stirring, then pour the reaction solution into a large amount of ice-water mixture and stir for 1 hour, and let stand After filtering, the obtained solid was washed with deionized water several times until the pH of the eluate was 6.5-7.0, and the precipitated polymer was filtered out, and finally dried at 60° C. for 24 hours to obtain the sulfonated product, sulfonated polyetheretherketone. By titration method, the measured sulfonation degree (DS) was 45.4%, and the ion exchange capacity (IEC) value was 1.36 mmol/g. Then, 5 g of the sulfonated polyetheretherketone prepared in Comparative Example 1 was dissolved in N,N-dimethylacetamide to form a 10 wt% solution, and the solution was formed into a film in a clean cubic glass tank, and the Dry for 8 hours, 95°C for 8 hours, 135°C for 2 hours, and then cool at 20°C to peel off the film to obtain a pure sulfonated polyetheretherketone film. The performance test results of the membrane are shown in Table 1, 2 and Figure 1 in detail.
本对比例1所制备的纯磺化聚醚醚酮膜的表面和截面形貌参见图5a和5b，从图5a和5b可以看出所制备的膜非常的均相、致密，这说明SPEEK适合作为燃料电池用隔膜。See Figures 5a and 5b for the surface and cross-sectional morphology of the pure sulfonated polyetheretherketone membrane prepared in Comparative Example 1. From Figures 5a and 5b, it can be seen that the prepared membrane is very homogeneous and dense, which shows that SPEEK is suitable as Separators for fuel cells.
实施例2Example 2
一种磷酸硼包覆碳纳米管复合质子交换膜的制备方法，步骤如下：A preparation method of boron phosphate coated carbon nanotube composite proton exchange membrane, the steps are as follows:
1)磺化聚醚醚酮的制备：1) Preparation of sulfonated polyether ether ketone:
将聚醚醚酮粉末置于98wt％浓硫酸中(固液比为1g:20mL)，反应温度为50℃，充分反应3h，然后将反应液倒入大量的冰水混合物中搅拌1h，静置过滤，所得固体再用去离子水多次洗涤，直到洗出液的pH＝6.5～7.0时过滤出沉降的聚合物，最后在60℃下干燥24h得到磺化聚醚醚酮；Put the polyetheretherketone powder in 98wt% concentrated sulfuric acid (solid-to-liquid ratio: 1g:20mL) at a reaction temperature of 50°C and fully react for 3 hours, then pour the reaction solution into a large amount of ice-water mixture and stir for 1 hour, then let stand Filtrate, and wash the obtained solid with deionized water several times until the pH of the eluate is 6.5-7.0, filter out the precipitated polymer, and finally dry at 60°C for 24 hours to obtain sulfonated polyether ether ketone;
2)磷酸硼包覆碳纳米管的制备：2) Preparation of boron phosphate-coated carbon nanotubes:
(1)配制浓度为50mmol/L的Tris(三羟甲基氨基甲烷)溶液，加入0.1mol/L的盐酸调节溶液pH值为8，得100ml Tris-HCl缓冲液；将50mg多巴胺和50mg碳纳米管置于预先配置好的100ml Tris-HCl缓冲液中，超声分散1小时后，继续室温搅拌16小时，然后真空抽滤，先用无水乙醇洗涤3次，再用去离子水洗涤3次，至滤液无色，干燥，得到聚多巴胺修饰的碳纳米管；(1) preparation concentration is the Tris (trishydroxymethylaminomethane) solution of 50mmol/L, adds the hydrochloric acid adjustment solution pH value of 0.1mol/L to be 8, obtains 100ml Tris-HCl buffer solution; Mix 50mg dopamine and 50mg carbon nano Place the tube in a pre-configured 100ml Tris-HCl buffer solution, ultrasonically disperse for 1 hour, continue to stir at room temperature for 16 hours, then vacuum filter, wash with absolute ethanol for 3 times, and then wash with deionized water for 3 times. Until the filtrate is colorless, dry to obtain polydopamine-modified carbon nanotubes;
(2)将40mg步骤2)中(1)所得聚多巴胺修饰的碳纳米管与20mg固体磷酸一起加入到100ml N,N-二甲基乙酰胺(DMAC)中，超声分散1小时后，在持续磁力搅拌下升温至80℃，然后缓慢滴加33mg硼酸三丙酯，滴加完后在110℃的条件下继续反应20小时，冷却至室温后经真空抽滤、溶剂DMAC洗涤、干燥后得磷酸硼包覆碳纳米管；(2) 40 mg of polydopamine-modified carbon nanotubes obtained in (1) in step 2) were added to 100 ml of N,N-dimethylacetamide (DMAC) together with 20 mg of solid phosphoric acid, and after ultrasonic dispersion for 1 hour, the Raise the temperature to 80°C under magnetic stirring, then slowly add 33 mg of tripropyl borate dropwise, continue to react at 110°C for 20 hours after the dropwise addition, cool to room temperature, vacuum filter, wash with solvent DMAC, and dry to obtain phosphoric acid Boron-coated carbon nanotubes;
3)复合质子交换膜的制备：3) Preparation of composite proton exchange membrane:
首先将步骤1)制得的磺化聚醚醚酮溶解在N,N-二甲基乙酰胺中形成质量分数为10％的溶液，然后加入步骤2)制得的磷酸硼包覆碳纳米管，充分混合后得到铸膜溶液，该铸膜溶液中磷酸硼包覆碳纳米管与磺化聚醚醚酮的质量比为2:100，将铸膜溶液倒入聚四氟乙烯立方槽内，经60℃干燥9h、100℃干燥9h、140℃干燥2h后，30℃冷却即可得到磷酸硼包覆碳纳米管复合质子交换膜(通过滴定法，测得膜的离子交换容量(IEC)值为1.02mmol/g)。膜的各项性能测试结果详见表1、2和图1。First, the sulfonated polyether ether ketone prepared in step 1) is dissolved in N,N-dimethylacetamide to form a solution with a mass fraction of 10%, and then the boron phosphate-coated carbon nanotubes prepared in step 2) are added , after fully mixing, the casting solution is obtained. In the casting solution, the mass ratio of boron phosphate-coated carbon nanotubes to sulfonated polyetheretherketone is 2:100, and the casting solution is poured into a polytetrafluoroethylene cubic tank. After drying at 60°C for 9 hours, at 100°C for 9 hours, and at 140°C for 2 hours, then cooling at 30°C to obtain a boron phosphate-coated carbon nanotube composite proton exchange membrane (by titration, the ion exchange capacity (IEC) value of the membrane was measured is 1.02mmol/g). The performance test results of the membrane are shown in Table 1, 2 and Figure 1 in detail.
本实施例所制备的磷酸硼包覆碳纳米管复合质子交换膜的截面形貌参见图5d，从图5d可以看出随着磷酸硼包覆碳纳米管掺入量增加，其在基体SPEEK中的分散依然十分均匀。See Figure 5d for the cross-sectional morphology of the boron phosphate-coated carbon nanotube composite proton exchange membrane prepared in this example. The dispersion is still very uniform.
实施例3Example 3
一种磷酸硼包覆碳纳米管复合质子交换膜的制备方法，步骤如下：A preparation method of boron phosphate coated carbon nanotube composite proton exchange membrane, the steps are as follows:
1)磺化聚醚醚酮的制备：1) Preparation of sulfonated polyether ether ketone:
将聚醚醚酮粉末置于98wt％浓硫酸中(固液比为1g:30mL)，反应温度为50℃，充分反应3h，然后将反应液倒入大量的冰水混合物中搅拌1h，静置过滤，所得固体再用去离子水多次洗涤，直到洗出液的pH＝6.5～7.0时过滤出沉降的聚合物，最后在60℃下干燥24h得到磺化聚醚醚酮；Put polyetheretherketone powder in 98wt% concentrated sulfuric acid (solid-to-liquid ratio: 1g:30mL) at a reaction temperature of 50°C for a full reaction of 3 hours, then pour the reaction solution into a large amount of ice-water mixture and stir for 1 hour, then let stand Filtrate, and wash the obtained solid with deionized water several times until the pH of the eluate is 6.5-7.0, filter out the precipitated polymer, and finally dry at 60°C for 24 hours to obtain sulfonated polyether ether ketone;
2)磷酸硼包覆碳纳米管的制备：2) Preparation of boron phosphate-coated carbon nanotubes:
(1)配制浓度为50mmol/L的Tris(三羟甲基氨基甲烷)溶液，加入0.1mol/L的盐酸调节溶液pH值为8，得100ml Tris-HCl缓冲液；将50mg多巴胺和50mg碳纳米管置于预先配置好的100ml Tris-HCl缓冲液中，超声分散1小时后，继续室温搅拌16小时，然后真空抽滤，先用无水乙醇洗涤3次，再用去离子水洗涤3次，至滤液无色，干燥，得到聚多巴胺修饰的碳纳米管；(1) preparation concentration is the Tris (trishydroxymethylaminomethane) solution of 50mmol/L, adds the hydrochloric acid adjustment solution pH value of 0.1mol/L to be 8, obtains 100ml Tris-HCl buffer solution; Mix 50mg dopamine and 50mg carbon nano Place the tube in a pre-configured 100ml Tris-HCl buffer solution, ultrasonically disperse for 1 hour, continue to stir at room temperature for 16 hours, then vacuum filter, wash with absolute ethanol for 3 times, and then wash with deionized water for 3 times. Until the filtrate is colorless, dry to obtain polydopamine-modified carbon nanotubes;
(2)将40mg步骤2)中(1)所得聚多巴胺修饰的碳纳米管与20mg固体磷酸一起加入到100ml N,N-二甲基乙酰胺(DMAC)中，超声分散1小时后，在持续磁力搅拌下升温至80℃，然后缓慢滴加33mg硼酸三丙酯，滴加完后在110℃的条件下继续反应20小时，冷却至室温后经真空抽滤、溶剂DMAC洗涤、干燥后得磷酸硼包覆碳纳米管；(2) 40 mg of polydopamine-modified carbon nanotubes obtained in (1) in step 2) were added to 100 ml of N,N-dimethylacetamide (DMAC) together with 20 mg of solid phosphoric acid, and after ultrasonic dispersion for 1 hour, the Raise the temperature to 80°C under magnetic stirring, then slowly add 33 mg of tripropyl borate dropwise, continue to react at 110°C for 20 hours after the dropwise addition, cool to room temperature, vacuum filter, wash with solvent DMAC, and dry to obtain phosphoric acid Boron-coated carbon nanotubes;
3)复合质子交换膜的制备：3) Preparation of composite proton exchange membrane:
首先将步骤1)制得的磺化聚醚醚酮溶解在N,N-二甲基乙酰胺中形成质量分数为10％的溶液，然后加入步骤2)制得的磷酸硼包覆碳纳米管，充分混合后得到铸膜溶液，该铸膜溶液中磷酸硼包覆碳纳米管与磺化聚醚醚酮的质量比为5:100，将铸膜溶液倒入聚四氟乙烯立方槽内，经65℃干燥10h、105℃干燥10h、145℃干燥3h后，35℃冷却即可得到磷酸硼包覆碳纳米管复合质子交换膜(通过滴定法，测得膜的离子交换容量(IEC)值为0.86mmol/g)。膜的各项性能测试结果详见表1、2和图1。First, the sulfonated polyether ether ketone prepared in step 1) is dissolved in N,N-dimethylacetamide to form a solution with a mass fraction of 10%, and then the boron phosphate-coated carbon nanotubes prepared in step 2) are added , after fully mixing to obtain a casting solution, the mass ratio of boron phosphate-coated carbon nanotubes to sulfonated polyether ether ketone in the casting solution is 5:100, pour the casting solution into a polytetrafluoroethylene cubic tank, After drying at 65°C for 10h, at 105°C for 10h, and at 145°C for 3h, then cooling at 35°C to obtain a boron phosphate-coated carbon nanotube composite proton exchange membrane (by titration, the ion exchange capacity (IEC) value of the membrane was measured is 0.86mmol/g). The performance test results of the membrane are shown in Table 1, 2 and Figure 1 in detail.
上述各例制备的膜的性能测试条件：The performance test condition of the membrane that above-mentioned each example prepares:
(1)吸水率和溶胀率：膜的吸水率采用干湿重法测试，将膜于100℃真空干燥24h，称重得到Wdry，然后将膜在蒸馏水中室温浸泡24h，用滤纸拭去膜表面的水分，迅速称重得到Wwet，吸水率由下式进行计算：(1) Water absorption rate and swelling rate: The water absorption rate of the membrane is tested by dry-wet weight method. The membrane is vacuum-dried at 100°C for 24 hours, weighed to obtain Wdry , then soaked in distilled water at room temperature for 24 hours, and wiped off the membrane with filter paper The moisture on the surface, quickly weighed to get Wwet , water absorption It is calculated by the following formula:
溶胀性测试是分别测定干膜和在80℃去离子水中保持了24h的湿膜的长、宽和厚度尺寸，然后计算出相应的体积变化率，如：The swelling test is to measure the length, width and thickness of the dry film and the wet film kept in 80°C deionized water for 24 hours, and then calculate the corresponding volume change rate, such as:
式(2)中，为体积溶胀率，Vf为膜处于湿态时的体积，Vi为膜处于干态下的体积。In formula (2), is the volume swelling ratio, Vf is the volume of the membrane in the wet state, and Vi is the volume of the membrane in the dry state.
(2)质子传导率：膜的电阻采用交流阻抗法在频率响应分析仪上进行测试，频率扫描范围为0.1-106Hz，交流信号振幅为100mV。将裁剪好的膜(2cm×3cm)放在自制的测试平台上(如图2所示)，在测试之前，膜样品置于去离子水48h。膜的质子传导率σ(S/cm)通过下式(3)进行计算：(2) Proton conductivity: the resistance of the membrane was tested on a frequency response analyzer using the AC impedance method, the frequency scanning range was 0.1-106 Hz, and the AC signal amplitude was 100 mV. The cut membrane (2cm×3cm) was placed on a self-made test platform (as shown in Figure 2), and the membrane sample was placed in deionized water for 48h before testing. The proton conductivity σ (S/cm) of the membrane is calculated by the following formula (3):
式(3)中，a和A分别为两电极的间距和两电极间待测膜的有效横截面积，R是膜的电阻，通过交流阻抗测试所得的Nyquist图求取。In formula (3), a and A are the distance between the two electrodes and the effective cross-sectional area of the film to be tested between the two electrodes, respectively, and R is the resistance of the film, which is obtained from the Nyquist diagram obtained from the AC impedance test.
(3)拉伸强度和断裂伸长率：将膜样品裁成长×宽＝80×10mm的长方形样条，在室温条件下采用2mm/min的拉伸速率，在ShimadzuAG-IC万能拉伸机上进行拉伸测试，通过记录膜样品直至断裂为止所受的最大拉伸应力即为拉伸强度，断裂时薄膜样品长度增加的百分率即为断裂伸长率。(3) Tensile strength and elongation at break: Cut the film sample into a rectangular spline of length × width = 80 × 10mm, and adopt a tensile rate of 2mm/min at room temperature on a Shimadzu AG-IC universal stretching machine In the tensile test, the maximum tensile stress suffered by the film sample until it breaks is the tensile strength, and the percentage increase in the length of the film sample at break is the elongation at break.
(4)氧化稳定性：分别对不同质子交换膜进行了氧化稳定性测试，将膜放在80℃含有2mg·L-1FeSO4的3％wt H2O2溶液中(此种溶液称为Fenton溶液)，该溶液可以模拟燃料电池中的强氧化环境。通过记录膜在浸泡前后不同时间的质量保留量评估交换膜的氧化稳定性。(4) Oxidation stability: Oxidation stability tests were carried out on different proton exchange membranes. The membranes were placed in a 3% wt H2 O2 solution containing 2 mg·L-1 FeSO4 at 80°C (this solution is called Fenton's solution), which can simulate the strong oxidizing environment in fuel cells. The oxidation stability of the exchange membrane was evaluated by recording the mass retention of the membrane at different times before and after immersion.
表1实施例1至3及对比例1的基本性能比较The basic performance comparison of table 1 embodiment 1 to 3 and comparative example 1
表2实施例1至3及对比例1在不同温度下质子传导率比较Table 2 embodiment 1 to 3 and comparative example 1 proton conductivity comparison at different temperatures
| Application Number | Priority Date | Filing Date | Title |
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| CN201511005151.7ACN105390721B (en) | 2015-12-28 | 2015-12-28 | A kind of preparation method of boron phosphate enveloped carbon nanometer tube compound proton exchange membrane |
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| CN201511005151.7ACN105390721B (en) | 2015-12-28 | 2015-12-28 | A kind of preparation method of boron phosphate enveloped carbon nanometer tube compound proton exchange membrane |
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| CN105390721A CN105390721A (en) | 2016-03-09 |
| CN105390721Btrue CN105390721B (en) | 2017-11-03 |
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| CN201511005151.7AActiveCN105390721B (en) | 2015-12-28 | 2015-12-28 | A kind of preparation method of boron phosphate enveloped carbon nanometer tube compound proton exchange membrane |
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| CN (1) | CN105390721B (en) |
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