技术领域technical field
本发明属于燃料电池技术领域，具体涉及一种磷硅玻璃掺杂壳聚糖中温质子交换膜及其制备方法。The invention belongs to the technical field of fuel cells, and in particular relates to a chitosan medium-temperature proton exchange membrane doped with phosphosilicate glass and a preparation method thereof.
背景技术Background technique
质子交换膜燃料电池(PEMFC)是一类以质子交换膜作为电解质的燃料电池体系，而质子交换膜是燃料电池的核心部件，对电池性能与寿命起到决定性的作用。用于PEMFC的质子交换膜需要具有高的H+传导能力，还需要在高温低湿工作条件下具有良好的质子电导率和一定的机械强度。Proton exchange membrane fuel cell (PEMFC) is a kind of fuel cell system that uses proton exchange membrane as electrolyte, and proton exchange membrane is the core component of fuel cell, which plays a decisive role in battery performance and life. The proton exchange membrane used in PEMFC needs to have high H+ conductivity, and also needs to have good proton conductivity and certain mechanical strength under high temperature and low humidity working conditions.
目前常用的质子交换膜材料有全氟磺酸聚合物、聚芳醚酮、聚醚醚酮、壳聚糖和聚酰胺等聚合物。其中基于壳聚糖的质子交换膜的研究得到了越来越多的关注，这是因为壳聚糖广泛存在于蟹壳和虾壳中，为甲壳素脱乙酰基的产物，具有低毒、生物相容性、可降解性等优点，壳聚糖成膜工艺简单，成本低。另外，壳聚糖分子上的环状结构保证了壳聚糖膜的热化学稳定性，以及足够的力学性能。壳聚糖单体上存在羟基和氨基，表明壳聚糖膜具有制备成高性能质子膜的潜力。但是，研究表明未经交联和改性的壳聚糖干膜在室温下的质子传导率仅为10-9S·cm-1，相当于绝缘材料。因此需要对其进行改性处理，提高其质子电导率。At present, the commonly used proton exchange membrane materials include polymers such as perfluorosulfonic acid polymers, polyaryletherketones, polyetheretherketones, chitosan and polyamides. Among them, the research on chitosan-based proton exchange membranes has received more and more attention, because chitosan widely exists in crab shells and shrimp shells, and is a product of chitin deacetylation, which has low toxicity and biological properties. Compatibility, degradability and other advantages, chitosan film-forming process is simple, low cost. In addition, the ring structure on the chitosan molecule ensures the thermochemical stability and sufficient mechanical properties of the chitosan film. The presence of hydroxyl and amino groups on the chitosan monomer indicates that the chitosan membrane has the potential to be prepared as a high-performance proton membrane. However, studies have shown that the proton conductivity of uncrosslinked and modified chitosan dry film at room temperature is only 10-9 S·cm-1 , equivalent to insulating materials. Therefore, it needs to be modified to improve its proton conductivity.
发明内容Contents of the invention
为了解决现有技术的不足，本发明的目的之一是提供一种磷硅玻璃掺杂壳聚糖中温质子交换膜的制备方法，能够提高壳聚糖干膜的质子传导率。In order to solve the deficiencies of the prior art, one of the purposes of the present invention is to provide a method for preparing a chitosan medium-temperature proton exchange membrane doped with phosphosilicate glass, which can improve the proton conductivity of the chitosan dry membrane.
为了实现上述目的，本发明的技术方案为：In order to achieve the above object, the technical solution of the present invention is:
一种磷硅玻璃掺杂壳聚糖中温质子交换膜的制备方法，将正硅酸乙酯、盐酸和磷酸水溶液混合均匀得到磷硅玻璃溶液，将磷硅玻璃溶液与壳聚糖溶液进行混合后放入冰水浴中搅拌获得溶胶，将获得的溶胶放入模具中进行热处理、干燥获得膜材料，再采用碱性溶液洗涤膜材料获得耐水膜材料即为磷硅玻璃掺杂壳聚糖中温质子交换膜。A preparation method of phosphosilicate glass doped chitosan medium-temperature proton exchange membrane, uniformly mixing ethyl orthosilicate, hydrochloric acid and phosphoric acid aqueous solution to obtain phosphosilicate glass solution, after mixing the phosphosilicate glass solution and chitosan solution Stir in an ice-water bath to obtain a sol, put the obtained sol into a mold for heat treatment, and dry to obtain a membrane material, and then wash the membrane material with an alkaline solution to obtain a water-resistant membrane material, which is phosphosilicate glass-doped chitosan medium-temperature proton exchange membrane.
本发明的目的之二是提供另一种磷硅玻璃掺杂壳聚糖中温质子交换膜的制备方法，将正硅酸乙酯、盐酸和磷酸水溶液混合均匀得到的磷硅玻璃溶液放入冰水浴静置，再进行干燥、粉碎获得磷硅玻璃粉末，然后将磷硅玻璃粉末加入至质子酸改性的壳聚糖溶液中获得胶体溶液，将获得的溶胶放入模具干燥获得膜材料，再采用碱性溶液洗涤膜材料获得耐水膜材料即为磷硅玻璃掺杂壳聚糖中温质子交换膜。The second object of the present invention is to provide another preparation method of phosphosilicate glass-doped chitosan medium-temperature proton exchange membrane. The phosphosilicate glass solution obtained by uniformly mixing tetraethyl orthosilicate, hydrochloric acid and phosphoric acid aqueous solution is placed in an ice water bath Stand still, then dry and pulverize to obtain phosphosilicate glass powder, then add the phosphosilicate glass powder to the protonic acid modified chitosan solution to obtain a colloidal solution, put the obtained sol into a mold to dry to obtain a membrane material, and then use The water-resistant membrane material obtained by washing the membrane material with alkaline solution is the intermediate temperature proton exchange membrane doped with chitosan in phosphosilicate glass.
本发明的目的之三是提供一种上述制备方法制备的磷硅玻璃掺杂壳聚糖中温质子交换膜。The third object of the present invention is to provide a medium-temperature proton exchange membrane doped with phosphosilicate glass and chitosan prepared by the above preparation method.
本发明的目的之四是提供一种质子交换膜燃料电池，采用上述磷硅玻璃掺杂壳聚糖中温质子交换膜。The fourth object of the present invention is to provide a proton exchange membrane fuel cell, which uses the above-mentioned phosphosilicate glass doped chitosan medium temperature proton exchange membrane.
本发明的有益效果：Beneficial effects of the present invention:
1.本发明采用磷硅玻璃掺杂壳聚糖制备出了中温质子交换膜，反应条件温和，制备工艺简单。1. The present invention uses phosphosilicate glass doped with chitosan to prepare a medium-temperature proton exchange membrane, with mild reaction conditions and simple preparation process.
2.本发明采用磷硅玻璃掺杂壳聚糖制备的中温质子交换膜在中温低湿度甚至无水条件下仍具有较高的质子电导率。2. The medium-temperature proton exchange membrane prepared by using phosphosilicate glass doped with chitosan in the present invention still has relatively high proton conductivity under medium-temperature, low-humidity or even anhydrous conditions.
附图说明Description of drawings
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。The accompanying drawings constituting a part of the present application are used to provide further understanding of the present application, and the schematic embodiments and descriptions of the present application are used to explain the present application, and do not constitute improper limitations to the present application.
图1为实施例1制备的磷硅玻璃掺杂壳聚糖中温质子交换膜的扫描电子显微镜(SEM)的照片；Fig. 1 is the photo of the scanning electron microscope (SEM) of the phosphosilicate glass doped chitosan intermediate temperature proton exchange membrane prepared by embodiment 1;
图2为实施例3制备的磷硅玻璃掺杂壳聚糖中温质子交换膜的扫描电子显微镜(SEM)的照片。2 is a scanning electron microscope (SEM) photo of the phosphosilicate glass-doped chitosan medium-temperature proton exchange membrane prepared in Example 3.
具体实施方式Detailed ways
应该指出，以下详细说明都是示例性的，旨在对本申请提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。It should be pointed out that the following detailed description is exemplary and is intended to provide further explanation to the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It should be noted that the terminology used here is only for describing specific implementations, and is not intended to limit the exemplary implementations according to the present application. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural, and it should also be understood that when the terms "comprising" and/or "comprising" are used in this specification, they mean There are features, steps, operations, means, components and/or combinations thereof.
本申请所述的碱性溶液是指pH大于7的溶液。The alkaline solution described in this application refers to a solution with a pH greater than 7.
正如背景技术所介绍的，现有技术中存在壳聚糖干膜或改性壳聚糖干膜质子导电率较低的不足，为了解决如上的技术问题，本申请提出了一种磷硅玻璃掺杂壳聚糖中温质子交换膜及其制备方法。As introduced in the background technology, in the prior art there is the deficiency that the proton conductivity of chitosan dry film or modified chitosan dry film is low. In order to solve the above technical problems, this application proposes a phosphosilicate glass Heterochitosan medium temperature proton exchange membrane and its preparation method.
本申请的一种典型实施方式，提供了一种磷硅玻璃掺杂壳聚糖中温质子交换膜的制备方法，将正硅酸乙酯、盐酸和磷酸水溶液混合均匀得到磷硅玻璃溶液，将磷硅玻璃溶液与壳聚糖溶液进行混合后放入冰水浴中搅拌获得溶胶，将获得的溶胶放入模具中进行热处理后，冷却干燥获得膜材料，再采用碱性溶液洗涤膜材料获得耐水膜材料即为磷硅玻璃掺杂壳聚糖中温质子交换膜。A typical implementation of the present application provides a method for preparing a phosphosilicate glass-doped chitosan medium-temperature proton exchange membrane, in which ethyl orthosilicate, hydrochloric acid and phosphoric acid aqueous solution are uniformly mixed to obtain a phosphosilicate glass solution, and phosphorus Silica glass solution and chitosan solution are mixed and put into an ice-water bath to stir to obtain a sol, the obtained sol is put into a mold for heat treatment, cooled and dried to obtain a membrane material, and then the membrane material is washed with an alkaline solution to obtain a water-resistant membrane material That is, phosphosilicate glass doped chitosan medium temperature proton exchange membrane.
为了增加壳聚糖在水中的溶解度，优选的，将壳聚糖加入至乙酸水溶液中。进一步优选的，乙酸水溶液中乙酸的质量分数为2％。In order to increase the solubility of chitosan in water, preferably, chitosan is added to the aqueous acetic acid solution. Further preferably, the mass fraction of acetic acid in the aqueous acetic acid solution is 2%.
为了增加磷硅玻璃掺杂壳聚糖中温质子交换膜的电导率，优选的，向壳聚糖溶液添加质子酸对壳聚糖进行改性。壳聚糖中的-NH2与质子酸发生酸碱反应，生成了-NH3+有利于质子的传导，因此质子改性后的隔膜的电导率会增大In order to increase the conductivity of the phosphosilicate glass-doped chitosan medium-temperature proton exchange membrane, preferably, a protonic acid is added to the chitosan solution to modify the chitosan. -NH2 in chitosan undergoes an acid-base reaction with proton acid to generate -NH3+ which is conducive to the conduction of protons, so the conductivity of the membrane after proton modification will increase
进一步优选的，所述质子酸为磷酸、亚磷酸、焦磷酸或硫酸。Further preferably, the protonic acid is phosphoric acid, phosphorous acid, pyrophosphoric acid or sulfuric acid.
优选的，正硅酸乙酯与盐酸中HCl的摩尔比为1:0.0009～0.0011。Preferably, the molar ratio of ethyl orthosilicate to HCl in hydrochloric acid is 1:0.0009-0.0011.
优选的，所述磷酸水溶液中磷酸的质量分数为84～86％。Preferably, the mass fraction of phosphoric acid in the phosphoric acid aqueous solution is 84-86%.
优选的，壳聚糖溶液与磷硅玻璃溶液的体积比为1:2～10。玻璃掺杂过少会存在电导率提高效果不明显以及提高其耐温性，玻璃含量较高会使得复合膜的强度较差。Preferably, the volume ratio of the chitosan solution to the phosphosilicate glass solution is 1:2-10. If the glass doping is too small, the effect of improving the electrical conductivity will not be obvious and the temperature resistance will be improved, and if the glass content is too high, the strength of the composite film will be poor.
优选的，所述热处理条件为：温度为100±5℃，处理时间为8±0.5h。Preferably, the heat treatment conditions are: the temperature is 100±5°C, and the treatment time is 8±0.5h.
优选的，所述碱性溶液为氢氧化钠溶液、碳酸钠溶液或碳酸氢钠溶液。Preferably, the alkaline solution is sodium hydroxide solution, sodium carbonate solution or sodium bicarbonate solution.
优选的，所述洗涤次数为2～3次。Preferably, the number of times of washing is 2-3 times.
本申请的另一种典型实施方式，提供了另一种磷硅玻璃掺杂壳聚糖中温质子交换膜的制备方法，将正硅酸乙酯、盐酸和磷酸水溶液混合均匀得到的磷硅玻璃溶液放入冰水浴静置，再进行干燥、粉碎获得磷硅玻璃粉末，然后将磷硅玻璃粉末加入至质子酸改性的壳聚糖溶液中获得胶体溶液，将获得的溶胶放入模具干燥获得膜材料，再采用碱性溶液洗涤膜材料获得耐水膜材料即为磷硅玻璃掺杂壳聚糖中温质子交换膜。Another typical embodiment of the present application provides another method for preparing a phosphosilicate glass-doped chitosan medium-temperature proton exchange membrane. The phosphosilicate glass solution obtained by uniformly mixing tetraethyl orthosilicate, hydrochloric acid and phosphoric acid aqueous solution Put it in an ice-water bath and let it stand, then dry and pulverize it to obtain phosphosilicate glass powder, then add the phosphosilicate glass powder to the protonic acid-modified chitosan solution to obtain a colloidal solution, and put the obtained sol into a mold to dry to obtain a film material, and then wash the membrane material with alkaline solution to obtain a water-resistant membrane material, which is a medium-temperature proton exchange membrane doped with chitosan on phosphosilicate glass.
为了增加壳聚糖在水中的溶解度，优选的，将壳聚糖加入至乙酸水溶液中。进一步优选的，乙酸水溶液中乙酸的质量分数为2％。In order to increase the solubility of chitosan in water, preferably, chitosan is added to the aqueous acetic acid solution. Further preferably, the mass fraction of acetic acid in the aqueous acetic acid solution is 2%.
优选的，所述质子酸为磷酸、亚磷酸、焦磷酸或硫酸。Preferably, the protic acid is phosphoric acid, phosphorous acid, pyrophosphoric acid or sulfuric acid.
优选的，正硅酸乙酯与盐酸中HCl的摩尔比为1:0.0009～0.0011。Preferably, the molar ratio of ethyl orthosilicate to HCl in hydrochloric acid is 1:0.0009-0.0011.
为了获得均匀单一的磷硅玻璃粉末，优选的，将冰水浴静置、干燥后得到的磷硅玻璃片进行球磨。进一步优选的，球磨条件为：转速为600±10r/min，球磨时间为2～3h。In order to obtain uniform and single phosphosilicate glass powder, preferably, the phosphosilicate glass sheet obtained after standing in an ice-water bath and drying is subjected to ball milling. Further preferably, the ball milling conditions are: the rotating speed is 600±10 r/min, and the ball milling time is 2-3 hours.
为了使磷硅玻璃粉末与质子酸改性的壳聚糖溶液混合均匀，优选的，采用超声搅拌。In order to mix the phosphosilicate glass powder and the protonic acid-modified chitosan solution uniformly, preferably, ultrasonic stirring is used.
优选的，所述碱性溶液为氢氧化钠溶液、碳酸钠溶液或碳酸氢钠溶液。Preferably, the alkaline solution is sodium hydroxide solution, sodium carbonate solution or sodium bicarbonate solution.
优选的，所述洗涤次数为2～3次。Preferably, the number of times of washing is 2-3 times.
本申请的第三种实施方式，提供了一种上述制备方法制备的磷硅玻璃掺杂壳聚糖中温质子交换膜。The third embodiment of the present application provides a phosphosilicate glass-doped chitosan intermediate temperature proton exchange membrane prepared by the above preparation method.
本申请的第四种实施方式，提供了一种质子交换膜燃料电池，采用上述磷硅玻璃掺杂壳聚糖中温质子交换膜。The fourth embodiment of the present application provides a proton exchange membrane fuel cell, using the above-mentioned phosphosilicate glass doped chitosan medium temperature proton exchange membrane.
为了使得本领域技术人员能够更加清楚地了解本申请的技术方案，以下将结合具体的实施例与对比例详细说明本申请的技术方案。In order to enable those skilled in the art to understand the technical solution of the present application more clearly, the technical solution of the present application will be described in detail below in combination with specific examples and comparative examples.
实施例中壳聚糖的CAS号为9012-76-4。The CAS number of chitosan in the embodiment is 9012-76-4.
实施例1Example 1
称取4g脱乙酰度>85％的壳聚糖粉末，溶解于200mL质量分数为2％的乙酸溶液中，搅拌均匀制备壳聚糖溶液。取正硅酸乙酯溶液5g放入30mL的蒸馏水中，加入浓盐酸溶液，磁力搅拌1h，加入磷酸溶液搅拌2h。将50mL的壳聚糖溶液和10mL的磷硅玻璃溶液混合置于放入冰水混合浴中，持续搅拌4h得到溶胶，溶胶倒入聚四氟乙烯模盘中，随后依次在100℃条件下热处理8h，冷却干燥后将其从聚四氟乙烯模盘上剥离即得到磷硅玻璃掺杂壳聚糖高温质子交换膜。磷硅玻璃掺杂壳聚糖高温质子交换膜在NaOH溶液中清洗2-3次,真空热压干燥后即可得到耐水性质子交换膜，即为磷硅玻璃掺杂壳聚糖中温质子交换膜。膜的平均厚度60μm左右(扫描电镜图见图1)。Weigh 4g of chitosan powder with a degree of deacetylation>85%, dissolve it in 200mL of acetic acid solution with a mass fraction of 2%, and stir evenly to prepare a chitosan solution. Take 5 g of tetraethyl orthosilicate solution and put it into 30 mL of distilled water, add concentrated hydrochloric acid solution, magnetically stir for 1 h, add phosphoric acid solution and stir for 2 h. Mix 50mL of chitosan solution and 10mL of phosphosilicate glass solution, place them in an ice-water mixing bath, and keep stirring for 4 hours to obtain a sol, which is poured into a polytetrafluoroethylene mold, and then heat-treated at 100°C in turn After cooling and drying for 8 hours, it was peeled off from the polytetrafluoroethylene mold to obtain a high-temperature proton exchange membrane doped with phosphosilicate glass and chitosan. Phosphosilicate glass-doped chitosan high-temperature proton exchange membrane is washed in NaOH solution for 2-3 times, and after vacuum hot-pressing drying, a water-resistant proton exchange membrane can be obtained, that is, phosphosilicate glass-doped chitosan medium-temperature proton exchange membrane . The average thickness of the film is about 60 μm (see Figure 1 for the scanning electron microscope image).
实施例2Example 2
称取4g脱乙酰度>85％的壳聚糖粉末，溶解于200mL质量分数为2％的乙酸溶液中，搅拌均匀制备壳聚糖溶液。取正硅酸乙酯溶液5g放入30ml的蒸馏水中，加入浓盐酸溶液，磁力搅拌1h，加入磷酸溶液搅拌2h。取10ml的稀硫酸溶液加入50mL的壳聚糖溶液，制备成交联的壳聚糖溶液。将制备好的交联壳聚糖溶液和10mL的磷硅玻璃溶液混合置于放入冰水混合浴中，持续搅拌4h得到溶胶，溶胶倒入聚四氟乙烯模盘中，随后依次在100℃条件下热处理8h，冷却干燥后将其从聚四氟乙烯模盘上剥离即得到磷硅玻璃掺杂壳聚糖高温质子交换膜。磷硅玻璃掺杂壳聚糖高温质子交换膜在NaOH溶液中清洗2-3次,真空热压干燥后即可得到耐水性质子交换膜，即为磷硅玻璃掺杂壳聚糖中温质子交换膜。膜的平均厚度60μm左右。Weigh 4g of chitosan powder with a degree of deacetylation>85%, dissolve it in 200mL of acetic acid solution with a mass fraction of 2%, and stir evenly to prepare a chitosan solution. Take 5 g of tetraethyl orthosilicate solution and put it into 30 ml of distilled water, add concentrated hydrochloric acid solution, magnetically stir for 1 hour, add phosphoric acid solution and stir for 2 hours. Get 10ml of dilute sulfuric acid solution and add 50mL of chitosan solution to prepare a cross-linked chitosan solution. Mix the prepared cross-linked chitosan solution and 10 mL of phosphosilicate glass solution and place them in an ice-water mixing bath, and continue to stir for 4 hours to obtain a sol, which is poured into a polytetrafluoroethylene mold, and then sequentially heated at 100 Heat treatment for 8 hours under the same conditions, cooling and drying, and peeling off from the polytetrafluoroethylene mold to obtain a high-temperature proton exchange membrane doped with phosphosilicate glass and chitosan. Phosphosilicate glass-doped chitosan high-temperature proton exchange membrane is washed in NaOH solution for 2-3 times, and after vacuum hot-pressing drying, a water-resistant proton exchange membrane can be obtained, that is, phosphosilicate glass-doped chitosan medium-temperature proton exchange membrane . The average thickness of the film is about 60 μm.
实施例3Example 3
称取4g脱乙酰度>85％的壳聚糖粉末，溶解于200mL质量分数为2％的乙酸溶液中，搅拌均匀制备壳聚糖溶液。取正硅酸乙酯溶液5g放入30mL的蒸馏水中，加入浓盐酸溶液，磁力搅拌1h，加入磷酸溶液搅拌2h，将制备备好的玻璃干燥，然后在球磨机中以转数600r/min球磨2h成为粉末。取10mL的稀硫酸溶液加入50mL的壳聚糖溶液，制备成交联的壳聚糖溶液。将制备好的交联壳聚糖溶液和5g磷硅玻璃粉末超声混合均匀后，将溶胶倒入聚四氟乙烯模盘中，真空干燥后将其从聚四氟乙烯模盘上剥离即得到磷硅玻璃粉末掺杂壳聚糖高温质子交换膜。磷硅玻璃粉末掺杂壳聚糖高温质子交换膜在NaOH溶液中清洗2-3次,真空热压干燥后即可得到耐水性质子交换膜，即为磷硅玻璃掺杂壳聚糖中温质子交换膜。膜的平均厚度70μm左右(扫描电镜图见图2)。Weigh 4g of chitosan powder with a degree of deacetylation>85%, dissolve it in 200mL of acetic acid solution with a mass fraction of 2%, and stir evenly to prepare a chitosan solution. Take 5g of tetraethyl orthosilicate solution and put it into 30mL of distilled water, add concentrated hydrochloric acid solution, stir magnetically for 1h, add phosphoric acid solution and stir for 2h, dry the prepared glass, and then ball mill in a ball mill at 600r/min for 2h Become a powder. Get 10mL of dilute sulfuric acid solution and add 50mL of chitosan solution to prepare a cross-linked chitosan solution. After the prepared cross-linked chitosan solution and 5g of phosphosilicate glass powder are ultrasonically mixed, the sol is poured into the polytetrafluoroethylene mold, and after vacuum drying, it is peeled off from the polytetrafluoroethylene mold to obtain phosphorus Silica glass powder doped chitosan high temperature proton exchange membrane. Phosphosilicate glass powder-doped chitosan high-temperature proton exchange membrane is washed in NaOH solution for 2-3 times, and after vacuum hot-pressing drying, a water-resistant proton exchange membrane can be obtained, which is phosphosilicate glass-doped chitosan medium-temperature proton exchange membrane. membrane. The average thickness of the film is about 70 μm (see Figure 2 for the scanning electron micrograph).
对实施例1～3制备的磷硅玻璃掺杂壳聚糖中温质子交换膜进行物理性能表征，其结果如表1。The physical properties of the phosphosilicate glass-doped chitosan medium-temperature proton exchange membranes prepared in Examples 1-3 were characterized, and the results are shown in Table 1.
表1实施例1～3制备的磷硅玻璃掺杂壳聚糖中温质子交换膜进行物理性能Table 1 The physical properties of the phosphosilicate glass doped chitosan medium temperature proton exchange membrane prepared in Examples 1 to 3
表中膜的拉伸强度测试是通过万能材料试验机，测试过程如下：将隔膜裁成长度为8cm，宽度为1cm的长条然后进行测试，样品实际拉伸的长度为6cm，两边各留1cm作为夹端，按照10mm/min的速度进行测试。The tensile strength test of the film in the table is through a universal material testing machine. The test process is as follows: Cut the diaphragm into a strip with a length of 8cm and a width of 1cm and then test it. The actual stretched length of the sample is 6cm, leaving 1cm on each side As a clamp end, the test is carried out at a speed of 10 mm/min.
表中膜的无水电导率是在温度为110℃，湿度为30％的条件下，采用三电极交流阻抗法(A.C.Impedance)测试。电导率测试的夹具是自制的，隔膜按照夹具的大小进行裁剪。裁剪后的隔膜置于蒸馏水中浸泡30s后开始测试，其中测试的频率为0.1Hz-1MHz。电导率的计算公式如下：其中σ为电导率，R为测试得到的膜的电阻值，L为膜的厚度，A为夹具与膜的接触面积。The anhydrous conductivity of the films in the table was tested by the three-electrode AC impedance method (A.C. Impedance) under the conditions of a temperature of 110° C. and a humidity of 30%. The jig for conductivity test is self-made, and the diaphragm is cut according to the size of the jig. The cut diaphragm was soaked in distilled water for 30s before testing, and the testing frequency was 0.1Hz-1MHz. The formula for calculating the conductivity is as follows: where σ is the conductivity, R is the resistance value of the film obtained from the test, L is the thickness of the film, and A is the contact area between the fixture and the film.
表中膜的含水率的测试过程如下：将膜在真空干燥箱中60℃下干燥12h，除去膜中水分后，取出膜迅速称重得到膜的干重W1。然后，将膜放入一定温度的去离子水中浸泡24h，待膜的吸水过程充分平衡后，取出膜擦去表面残余液态水后称重得到膜的湿重W2。膜的含水率通过以下式子来定义：The test process of the water content of the film in the table is as follows: dry the film in a vacuum drying oven at 60°C for 12 hours, remove the water in the film, take out the film and weigh it quickly to obtain the dry weight W1 of the film. Then, soak the membrane in deionized water at a certain temperature for 24 hours. After the water absorption process of the membrane is fully balanced, take out the membrane and wipe off the residual liquid water on the surface, then weigh it to obtain the wet weight W2 of the membrane. The water content of the membrane is defined by the following formula:
以上所述仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。The above descriptions are only preferred embodiments of the present application, and are not intended to limit the present application. For those skilled in the art, there may be various modifications and changes in the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of this application shall be included within the protection scope of this application.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711435099.8ACN108155406B (en) | 2017-12-26 | 2017-12-26 | Phosphosilicate glass doped chitosan intermediate-temperature proton exchange membrane and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711435099.8ACN108155406B (en) | 2017-12-26 | 2017-12-26 | Phosphosilicate glass doped chitosan intermediate-temperature proton exchange membrane and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN108155406Atrue CN108155406A (en) | 2018-06-12 |
| CN108155406B CN108155406B (en) | 2021-04-06 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711435099.8AActiveCN108155406B (en) | 2017-12-26 | 2017-12-26 | Phosphosilicate glass doped chitosan intermediate-temperature proton exchange membrane and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN108155406B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775838A (en)* | 2005-12-15 | 2006-05-24 | 北京航空航天大学 | Preparation method of chitosan proton exchange membrane for fuel cell |
| CN101418080A (en)* | 2008-11-13 | 2009-04-29 | 北京科技大学 | Method for preparing chitosan proton exchange membrane for hydrogen sensor |
| CN101624449A (en)* | 2009-07-23 | 2010-01-13 | 天津大学 | Organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane as well as preparation and application |
| CN101671120A (en)* | 2009-10-21 | 2010-03-17 | 上海交通大学 | Preparation method of proton conducting material |
| CN101901917A (en)* | 2010-06-30 | 2010-12-01 | 上海交通大学 | Proton conductive composite glass film and preparation method thereof |
| CN102315463A (en)* | 2011-08-05 | 2012-01-11 | 上海交通大学 | Preparation method for flexible inorganic/organic composite proton exchange membrane |
| US20130323613A1 (en)* | 2011-04-01 | 2013-12-05 | The Hong Kong University Of Science And Technology | Graphene-based self-humidifying membrane and self-humidifying fuel cell |
| CN103849011A (en)* | 2014-03-13 | 2014-06-11 | 天津大学 | Chitosan/in-situ amphoteric silicon-titanium hybrid film as well as preparation method and application thereof |
| CN103897221A (en)* | 2014-03-13 | 2014-07-02 | 天津大学 | Chitosan/phosphorylated silicon dioxide particle hybrid film as well as preparation and application thereof |
| CN104163932A (en)* | 2013-05-16 | 2014-11-26 | 北京航空航天大学 | Meso-structural chitosan-phosphotungstic acid proton exchange membrane and preparation method thereof |
| CN104485470A (en)* | 2014-12-16 | 2015-04-01 | 武汉理工大学 | Polysiloxane- and polyphosphonic acid-doped chitosan high-temperature proton exchange film and preparation method thereof |
| CN104538657A (en)* | 2014-12-16 | 2015-04-22 | 武汉理工大学 | High-temperature crosslinked chitosan/nitrogenous phosphonic acid polysiloxane proton exchange membrane and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775838A (en)* | 2005-12-15 | 2006-05-24 | 北京航空航天大学 | Preparation method of chitosan proton exchange membrane for fuel cell |
| CN101418080A (en)* | 2008-11-13 | 2009-04-29 | 北京科技大学 | Method for preparing chitosan proton exchange membrane for hydrogen sensor |
| CN101624449A (en)* | 2009-07-23 | 2010-01-13 | 天津大学 | Organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane as well as preparation and application |
| CN101671120A (en)* | 2009-10-21 | 2010-03-17 | 上海交通大学 | Preparation method of proton conducting material |
| CN101901917A (en)* | 2010-06-30 | 2010-12-01 | 上海交通大学 | Proton conductive composite glass film and preparation method thereof |
| US20130323613A1 (en)* | 2011-04-01 | 2013-12-05 | The Hong Kong University Of Science And Technology | Graphene-based self-humidifying membrane and self-humidifying fuel cell |
| CN102315463A (en)* | 2011-08-05 | 2012-01-11 | 上海交通大学 | Preparation method for flexible inorganic/organic composite proton exchange membrane |
| CN104163932A (en)* | 2013-05-16 | 2014-11-26 | 北京航空航天大学 | Meso-structural chitosan-phosphotungstic acid proton exchange membrane and preparation method thereof |
| CN103849011A (en)* | 2014-03-13 | 2014-06-11 | 天津大学 | Chitosan/in-situ amphoteric silicon-titanium hybrid film as well as preparation method and application thereof |
| CN103897221A (en)* | 2014-03-13 | 2014-07-02 | 天津大学 | Chitosan/phosphorylated silicon dioxide particle hybrid film as well as preparation and application thereof |
| CN104485470A (en)* | 2014-12-16 | 2015-04-01 | 武汉理工大学 | Polysiloxane- and polyphosphonic acid-doped chitosan high-temperature proton exchange film and preparation method thereof |
| CN104538657A (en)* | 2014-12-16 | 2015-04-22 | 武汉理工大学 | High-temperature crosslinked chitosan/nitrogenous phosphonic acid polysiloxane proton exchange membrane and preparation method thereof |
| Publication number | Publication date |
|---|---|
| CN108155406B (en) | 2021-04-06 |
| Publication | Publication Date | Title |
|---|---|---|
| CN110041552A (en) | Compound high temperature proton exchange film and preparation method thereof based on sulfonation aryl oxide type polybenzimidazoles Yu sulfonation polysilsesquioxane | |
| CN107556247A (en) | A kind of functional form crosslinking agent, preparation method and the phosphate-doped cross-linking type polybenzimidazoles film of height prepared therefrom | |
| CN104993110B (en) | A kind of preparation method of composite negative electrode material of lithium ion battery | |
| CN102532572B (en) | Preparation method of quaternized chitosan anion hybrid membrane doped with positive polystyrene latex | |
| CN101787140B (en) | Preparation method of silicotungstic acid/silicon dioxide polyvinyl alcohol proton exchange membrane | |
| CN113078322A (en) | Graphene-silicon negative electrode material with lithium battery cycling stability and preparation method thereof | |
| CN102850564B (en) | Method for preparing phosphotungstic acid-polyvinylidene fluoride composite proton exchange membrane | |
| CN111525187B (en) | Sulfonated polyvinyl alcohol solid polymer electrolyte membrane for lithium battery and preparation method thereof | |
| CN110010966B (en) | Preparation method of biopolymer electrolyte with water as solvent | |
| CN110993914B (en) | Nickel-hydrogen battery cathode slurry and preparation method thereof | |
| CN107180705A (en) | Modified PVA electrolytic thin-membrane, its preparation method and application for flexible super capacitor | |
| CN104163932B (en) | A kind of shitosan phosphotungstic acid compound proton exchange membrane of meso-hole structure and preparation method thereof | |
| CN106830058B (en) | A kind of cellular tin dioxide material and preparation method thereof | |
| CN108155406A (en) | Temperature proton exchange film and preparation method thereof in a kind of phosphorosilicate glass doping chitosan | |
| CN106784949A (en) | A kind of preparation method of the full interpenetrating type anion-exchange membranes of crosslinking QCS CM Guanidine | |
| CN105826585B (en) | A kind of preparation method of high temperature compound proton exchange membrane for fuel cell | |
| CN112759657A (en) | Lithium carboxymethyl cellulose, preparation method and application thereof | |
| CN107353422A (en) | A kind of preparation method of the alkaline negative ion exchange composite film of high inorganics doped amount | |
| CN106558422A (en) | A kind of graphitized carbon nano pipe paper solid electrolyte ultracapacitor and preparation method | |
| CN103490085B (en) | Preparation method of konjac glucomannan/heteropoly acid composite proton conductive film | |
| CN110635127A (en) | Lithium-ion battery electrode materials based on metal molybdate compound nanomaterials | |
| CN102074363B (en) | Copolymer anion membrane for super-capacitor and preparation method thereof | |
| CN105575676B (en) | A kind of all-solid-state supercapacitor based on PBI KOH anion conducting polymer electrolyte and preparation method thereof | |
| CN104497328B (en) | Method for preparing modified polyvinyl alcohol-based alkaline polymer electrolyte membrane | |
| CN107248584A (en) | Chitosan phosphotungstic acid ionic liquid compound proton exchange membrane of novel porous structure and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |