技术领域Technical field
本发明是关于电化学技术，特别是关于一种非均相阴离子交换膜及装置。The present invention relates to electrochemical technology, and in particular to a heterogeneous anion exchange membrane and device.
背景技术Background technique
阴离子交换膜在电解、电渗析以及燃料电池技术等领域中扮演着重要角色。当前的阴离子交换膜大部分是通过将多种非离子型化合物的单体进行共聚得到，其中具有卤甲基官能团的单体在聚合后会进一步和含氮碱通过门舒特金反应形成季铵盐，如WO2020250057A1，WO2021204890A1等。但是聚合后的体系往往会残留部分未反应的卤甲基官能团，如WO2018204242A1等。对于阴离子交换膜而言，阴离子的跨膜传递是导电能力的关键。残留的未反应的卤甲基官能团并不能促进导电能力，同时可能阻碍环胺官能团之间的Π相互作用，限制微晶区的形成，进而影响膜本身导电性能的提升。同时，残留的苄氯可能会置换成苄醇，进一步可能会交联。因此使得膜制备在控制上变得难以进行。Anion exchange membranes play an important role in electrolysis, electrodialysis and fuel cell technology. Most of the current anion exchange membranes are obtained by copolymerizing monomers of various non-ionic compounds. After polymerization, the monomers with halomethyl functional groups will further react with nitrogen-containing bases through Menschutekin to form quaternary ammonium. Salt, such as WO2020250057A1, WO2021204890A1, etc. However, the polymerized system often retains some unreacted halomethyl functional groups, such as WO2018204242A1, etc. For anion exchange membranes, the transport of anions across the membrane is the key to electrical conductivity. The remaining unreacted halomethyl functional groups cannot promote the conductivity, and may hinder the Π interaction between the cyclic amine functional groups and limit the formation of microcrystalline regions, thereby affecting the improvement of the conductive properties of the film itself. At the same time, residual benzyl chloride may be replaced by benzyl alcohol, which may further be cross-linked. This makes membrane preparation difficult to control.
此外，对于均相阴离子交换膜而言,薄的结构往往能带来更优的电化学性能，但是同时会导致机械强度偏低的问题。因此在阴离子交换膜领域，开发具有更优电化学性能，同时兼具机械强度的可控可规模化的膜材料是商业化发展中的重要挑战。In addition, for homogeneous anion exchange membranes, thin structures often bring better electrochemical performance, but at the same time lead to the problem of low mechanical strength. Therefore, in the field of anion exchange membranes, developing controllable and scalable membrane materials with better electrochemical performance and mechanical strength is an important challenge in commercial development.
公开于该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域一般技术人员所公知的现有技术。The information disclosed in this Background section is merely intended to enhance an understanding of the general background of the invention and should not be construed as an admission or in any way implying that the information constitutes prior art that is already known to a person of ordinary skill in the art.
发明内容Contents of the invention
本发明的目的在于提供一种非均相阴离子交换膜及装置，通过优化非均相阴离子交换膜的组成和结构，有效改善了产品在离子交换、电化学、强度等多方面的性能。The purpose of the present invention is to provide a heterogeneous anion exchange membrane and device. By optimizing the composition and structure of the heterogeneous anion exchange membrane, the performance of the product in ion exchange, electrochemistry, strength and other aspects is effectively improved.
为实现上述目的，本发明的实施例提供了非均相阴离子交换膜，包括聚合物层以及形成于所述聚合物层上的无机物，聚合物层的组成材料的重复单元包括、，聚合物层的组成材料的通式为:/>，其中， m:n=(0.5-9):1；R1为带正电的环胺基；X选自羟基、氯离子、溴离子、碘离子、对甲苯磺酰氧基、三氟甲磺酸基、甲磺酰氧基。In order to achieve the above object, embodiments of the present invention provide a heterogeneous anion exchange membrane, including a polymer layer and an inorganic substance formed on the polymer layer. The repeating unit of the constituent material of the polymer layer includes , , the general formula of the composition material of the polymer layer is:/> , where m:n=(0.5-9):1; R1 is a positively charged cyclic amine group; Acid group, methanesulfonyloxy group.
在本发明的一个或多个实施方式中，非均相阴离子交换膜包括聚合物层以及形成于聚合物层上的无机物，聚合物层的组成材料的重复单元包括、/>、，聚合物层的组成材料的通式为:In one or more embodiments of the present invention, the heterogeneous anion exchange membrane includes a polymer layer and an inorganic substance formed on the polymer layer, and the repeating unit of the constituent material of the polymer layer includes ,/> , , the general formula of the composition material of the polymer layer is:
， ,
其中， m:n=(0.5-9):1；并且满足n、m、q共同限定使得R2对应单体在聚合物层中总质量不超过0.295%；R2选自烷基及其卤素单取代基团，烷基选自甲基、乙基、丙基、异丙基，卤素选自氯、碘、溴；R1为带正电的环胺基；X选自羟基、氯离子、溴离子、碘离子、对甲苯磺酰氧基、三氟甲磺酸基、甲磺酰氧基。优选的，m:n=(1.5-3):1。进一步优选的，m:n=(1.8-2.5):1。优选的，q/n≤0.95%。优选的，R2选自氯甲基。Among them, m:n=(0.5-9):1; and meet the joint limitations of n, m, and q such that the total mass of the monomer corresponding to R2 in the polymer layer does not exceed 0.295%; R2 is selected from alkyl and its halogen monosubstitution Group, the alkyl group is selected from methyl, ethyl, propyl, isopropyl, the halogen is selected from chlorine, iodine, bromine; R1 is a positively charged cyclic amine group; X is selected from hydroxyl, chloride ion, bromide ion, Iodide ion, p-toluenesulfonyloxy group, triflate group, methanesulfonyloxy group. Preferably, m:n=(1.5-3):1. Further preferably, m:n=(1.8-2.5):1. Preferably, q/n≤0.95%. Preferably, R2 is selected from chloromethyl.
需要说明的是，上述结构式中“”指重复单元的断链位置。It should be noted that in the above structural formula, " ” refers to the position of the chain break of the repeating unit.
在本发明的一个或多个实施方式中，R1选自咪唑鎓、吡啶鎓、吡唑鎓、吡咯烷鎓、吡咯鎓、嘧啶鎓、哌啶鎓、吲哚鎓和三嗪鎓。优选的，R1选自咪唑鎓。进一步优选的，R1选自四甲基咪唑鎓。In one or more embodiments of the invention, R1 is selected from the group consisting of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrrolium, pyrimidinium, piperidinium, indolium and triazinium. Preferably, R1 is selected from imidazolium. Further preferably, R1 is selected from tetramethylimidazolium.
在本发明的一个或多个实施方式中，无机物选自氧化锆、二氧化钛、硫酸钡、氢氧化镁、氢氧化镍、水滑石、碳酸钙。优选的，无机物选自氧化锆、水滑石、硫酸钡。进一步优选的，无机物选自水滑石、氧化锆，即优选为两者的一种或者两种组合物。进一步的，水滑石优选为MgAl-LDH或CaAl-LDH或ZnAl-LDH。进一步的，水滑石为Mg12Al6(OH)36(Mo7O24)H2O。In one or more embodiments of the invention, the inorganic substance is selected from zirconium oxide, titanium dioxide, barium sulfate, magnesium hydroxide, nickel hydroxide, hydrotalcite, and calcium carbonate. Preferably, the inorganic substance is selected from zirconium oxide, hydrotalcite, and barium sulfate. Further preferably, the inorganic substance is selected from hydrotalcite and zirconia, that is, preferably one or two combinations of the two. Furthermore, the hydrotalcite is preferably MgAl-LDH or CaAl-LDH or ZnAl-LDH. Further, the hydrotalcite is Mg12 Al6 (OH)36 (Mo7 O24 )H2 O.
在本发明的一个或多个实施方式中，无机物用量不超过聚合物层的60wt.%。优选的，无机物用量占聚合物层的10-30wt.%。优选的，无机物颗粒尺寸大小在1nm-1μm之间。进一步优选为，无机物颗粒尺寸大小在5nm-500nm之间。进一步优选为，无机物颗粒尺寸大小在5nm-200nm之间。In one or more embodiments of the invention, the amount of inorganic matter does not exceed 60 wt.% of the polymer layer. Preferably, the amount of inorganic substances accounts for 10-30wt.% of the polymer layer. Preferably, the size of the inorganic particles is between 1 nm and 1 μm. It is further preferred that the size of the inorganic particles is between 5nm and 500nm. It is further preferred that the size of the inorganic particles is between 5nm and 200nm.
在本发明的一个或多个实施方式中，离子交换膜还包括多孔支撑层，聚合物层形成于多孔支撑层。In one or more embodiments of the present invention, the ion exchange membrane further includes a porous support layer, and the polymer layer is formed on the porous support layer.
在本发明的一个或多个实施方式中，多孔支撑层的材料选自聚丙烯 (PP) 、聚乙烯 (PE) 、聚砜 (PS) 、聚苯硫醚(PPS)、聚酰胺/尼龙 (PA)、聚醚砜 (PES)、聚苯硫醚(PPS)、聚对苯二甲酸乙二醇酯 (PET) 、聚醚醚酮 (PEEK)、磺化聚醚醚酮 (s-PEEK)、膨体聚四氟乙烯(E-PTFE)，三氟氯乙烯 (CTFE)、乙烯与四氟乙烯(ETFE)的共聚物、乙烯与三氟氯乙烯(ECTFE)的共聚物、聚酰亚胺、聚醚酰亚胺和间芳族聚酰胺(m-aramide)。优选为EPTFE。优选的，多孔支撑层为织物或非织物(如多孔膜材等)。In one or more embodiments of the present invention, the material of the porous support layer is selected from polypropylene (PP), polyethylene (PE), polysulfone (PS), polyphenylene sulfide (PPS), polyamide/nylon ( PA), polyethersulfone (PES), polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polyetheretherketone (PEEK), sulfonated polyetheretherketone (s-PEEK) , expanded polytetrafluoroethylene (E-PTFE), chlorotrifluoroethylene (CTFE), copolymers of ethylene and tetrafluoroethylene (ETFE), copolymers of ethylene and chlorotrifluoroethylene (ECTFE), polyimide , polyetherimide and meta-aromatic polyamide (m-aramide). EPTFE is preferred. Preferably, the porous support layer is fabric or non-woven fabric (such as porous membrane material, etc.).
在本发明的一个或多个实施方式中，多孔支撑层的厚度为1-60μm。进一步优选的，多孔支撑层的厚度为2μm-40μm。In one or more embodiments of the invention, the thickness of the porous support layer is 1-60 μm. Further preferably, the thickness of the porous support layer is 2 μm-40 μm.
在本发明的一个或多个实施方式中，多孔支撑层的孔隙率为40-90%。优选的，多孔支撑层的孔隙率为50-80%。In one or more embodiments of the invention, the porous support layer has a porosity of 40-90%. Preferably, the porosity of the porous support layer is 50-80%.
在本发明的一个或多个实施方式中，膜的厚度为10-100μm。In one or more embodiments of the invention, the film has a thickness of 10-100 μm.
在本发明的一个或多个实施方式中，非均相阴离子交换膜的制备方法，包括如下步骤:准备聚合物层的高分子原料、无机物，并分散于溶剂，形成均匀无泡的铸膜液；铸膜液经成膜、干燥即得到非均相阴离子交换膜。优选的，溶剂可以是甲苯、乙醇、DMF、DMAc，DMSO、NMP其中的一种或几种的组合。优选的，铸膜液中高分子原料的浓度范围为12-25%。优选的，无机物占聚合物的质量分数10-30%。In one or more embodiments of the present invention, the preparation method of a heterogeneous anion exchange membrane includes the following steps: preparing polymer raw materials and inorganic substances for the polymer layer, and dispersing them in a solvent to form a uniform and bubble-free cast membrane. liquid; the casting liquid is formed into a film and dried to obtain a heterogeneous anion exchange membrane. Preferably, the solvent may be one or a combination of toluene, ethanol, DMF, DMAc, DMSO, and NMP. Preferably, the concentration range of the polymer raw material in the film casting liquid is 12-25%. Preferably, the inorganic matter accounts for 10-30% of the mass fraction of the polymer.
在本发明的一个或多个实施方式中，成膜时，铸膜液均匀涂覆到基底表面即可。优选的，成膜时，基底表面铺设多孔支撑层后，铸膜液均匀涂覆到基底表面即可。In one or more embodiments of the present invention, when forming a film, the casting liquid is evenly applied to the surface of the substrate. Preferably, during film formation, after the porous support layer is laid on the surface of the substrate, the casting liquid is evenly applied to the surface of the substrate.
在本发明的一个或多个实施方式中，装置，包括如前述的非均相阴离子交换膜。本发明的装置，可以为成套设备或者构成成套设备的功能设备或者器件零部件等，主要体现了对阴离子交换膜在电化学领域的应用，即其可以作为用于电化学过程中的部件。该电化学过程可以为包括而不限于水电解、电渗析以及燃料电池等。In one or more embodiments of the present invention, the device includes a heterogeneous anion exchange membrane as described above. The device of the present invention can be a complete set of equipment or functional equipment or device parts constituting a complete set of equipment. It mainly embodies the application of anion exchange membranes in the field of electrochemistry, that is, it can be used as a component in the electrochemical process. The electrochemical process may include, but is not limited to, water electrolysis, electrodialysis, and fuel cells.
水滑石材料属于阴离子型层状化合物。层状化合物是指具有层状结构、层间离子具有可交换性的一类化合物，利用层状化合物主体在强极性分子作用下所具有的可插层性和层间离子的可交换性，将一些功能性客体物质引入层间空隙并将层板距离撑开从而形成层柱化合物。水滑石类化合物(LDHs) 是一类具有层状结构的新型无机功能材料, LDHs的主体层板化学组成与其层板阳离子特性、层板电荷密度或者阴离子交换量、超分子插层结构等因素密切相关。Hydrotalcite materials are anionic layered compounds. Layered compounds refer to a class of compounds with a layered structure and exchangeability of interlayer ions. By utilizing the intercalability and exchangeability of interlayer ions under the action of strong polar molecules, layered compounds are used to Some functional guest substances are introduced into the interlayer gaps and the distance between the layers is spread to form layer pillar compounds. Hydrotalcite compounds (LDHs) are a new type of inorganic functional materials with a layered structure. The chemical composition of the main layer of LDHs is closely related to factors such as the cationic properties of the layer, the charge density of the layer or anion exchange capacity, and the supramolecular intercalation structure. Related.
与现有技术相比，根据本发明实施方式的非均相阴离子交换膜及装置，通过提供一种比例控制精准的高离子导率高分子结构、亲水性无机填料的优化组合，在此基础上还可以进一步地附加形成高强度多孔支撑层的优化组合，可以实现一种具有优异的电化学性能和良好的机械强度的非均相阴离子交换膜结构，避免了残留的卤甲基化官能团对于离子导率和电化学性能，以及对膜制备的平行性和品控性的影响。本方案选用一种不含或者含有微量的卤甲基官能团残留的结构理论上能进一步提升膜的离子导率同时便于对膜结构进行控制。Compared with the existing technology, the heterogeneous anion exchange membrane and device according to the embodiment of the present invention provide an optimized combination of high ion conductivity polymer structure and hydrophilic inorganic filler with precise proportion control. On top of this, an optimized combination of high-strength porous support layers can be further added to achieve a heterogeneous anion exchange membrane structure with excellent electrochemical properties and good mechanical strength, avoiding the impact of residual halomethylated functional groups on Ionic conductivity and electrochemical performance, as well as the impact on the parallelism and quality control of membrane preparation. This solution selects a structure that does not contain or contains trace amounts of residual halomethyl functional groups, which can theoretically further improve the ionic conductivity of the membrane and facilitate control of the membrane structure.
附图说明Description of drawings
图1是根据本发明一实施方式（实施例A7）的离子膜电性能测试图；Figure 1 is a test chart of the electrical performance of an ion membrane according to an embodiment of the present invention (Embodiment A7);
具体实施方式Detailed ways
下面结合附图，对本发明的具体实施方式进行详细描述，但应当理解本发明的保护范围并不受具体实施方式的限制。The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.
除非另有其它明确表示，否则在整个说明书和权利要求书中，术语“包括”或其变换如“包含”或“包括有”等等将被理解为包括所陈述的元件或组成部分，而并未排除其它元件或其它组成部分。Unless expressly stated otherwise, throughout the specification and claims, the term "comprises" or its variations such as "comprises" or "comprising" will be understood to include the stated elements or components, and to Other elements or other components are not excluded.
说明：包括而不限于如下实施例中，对于引发剂的限定为以整个过程中单体总物质量为基础，如“AIBN引发剂的量单体总物质量的1%mol”指引发剂用量指占体系中所有单体的物质量的百分比，即这里可以视作(m+n+q)1%mol，由于q很小或者不存在时，则可以近似为(m+n)1%mol。Note: Including but not limited to the following examples, the limit for initiators is based on the total mass of monomers in the entire process. For example, "the amount of AIBN initiator is 1% mol of the total mass of monomers" refers to the amount of initiator. Refers to the percentage of the mass of all monomers in the system, that is, it can be regarded as (m+n+q)1%mol. Since q is very small or does not exist, it can be approximated as (m+n)1%mol. .
阴离子交换膜的制备Preparation of anion exchange membrane
将上述得到的高分子，重新提纯后溶于DMF中。其中高分子聚合物的浓度范围为12-25%，氧化锆占聚合物的质量分数10-30%，溶剂可以是甲苯、乙醇、DMF、DMAc，DMSO、NMP其中的一种或它们的组合。聚合物与氧化锆以及DMF的份数分别为2/0.3/10，浆料搅拌均匀，真空脱除气泡。将ePTFE膜平整的铺在玻璃基底上，使用迈耶棒将浆料均匀的涂敷在ePTFE上，再放入120 ℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到最终的膜产物。The polymer obtained above was re-purified and dissolved in DMF. The concentration range of the polymer is 12-25%, zirconia accounts for 10-30% of the mass fraction of the polymer, and the solvent can be one of toluene, ethanol, DMF, DMAc, DMSO, NMP or a combination thereof. The proportions of polymer, zirconia and DMF are 2/0.3/10 respectively. The slurry is stirred evenly and the bubbles are removed under vacuum. Spread the ePTFE membrane flatly on the glass substrate, use a Meyer rod to evenly apply the slurry on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. Place the dried composite membrane in deionized water to remove the membrane. , to obtain the final membrane product.
电化学性能测试Electrochemical performance testing
阴离子膜电化学测试过程:将制备得到的阴离子膜置于30% KOH 溶液中24 h，使离子全部置换为氢氧根。将离子膜搭载市售商用Ru/C催化剂，阳极通30% KOH，阴极直接通空气，进行电解水电化学测试。Anionic membrane electrochemical test process: Place the prepared anionic membrane in a 30% KOH solution for 24 hours to replace all ions with hydroxyl radicals. The ion membrane was equipped with a commercially available Ru/C catalyst, 30% KOH was passed through the anode, and air was directly passed through the cathode, and the electrochemical test of water electrolysis was carried out.
实施例A1:Example A1:
（A）聚合物的合成(A) Synthesis of polymers
将1:1.2物质当量的四甲基咪唑和对氯甲基苯乙烯，以乙腈为溶剂，80℃反应1.5天后停止反应。纯化固体，得到乙烯基苄基-R1单体，R1为四甲基咪唑鎓。将苯乙烯和乙烯基苄基-R1单体和自由基引发剂溶于400μL的甲苯和400μL的乙醇的混合溶剂中。苯乙烯与乙烯基苄基-R1的物质的量比m:n为2:1。乙烯基苄基-R1的质量为400mg。AIBN引发剂的量单体总物质量的1%mol。反应温度为80℃，反应时间12h。将得到的聚合物通过重沉淀的方式提纯之后溶于DMF，DMF和聚合物的质量比例为10:2，加入交联剂二乙烯基苯(DVB)。二乙烯基苯的用量为10μL，80度反应12h。Add 1:1.2 material equivalents of tetramethylimidazole and p-chloromethylstyrene, using acetonitrile as the solvent, and react at 80°C for 1.5 days before stopping the reaction. The solid was purified to obtain vinylbenzyl-R1 monomer, and R1 was tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomers and free radical initiators were dissolved in a mixed solvent of 400 μL of toluene and 400 μL of ethanol. The mass ratio m:n of styrene and vinylbenzyl-R1 is 2:1. The mass of vinylbenzyl-R1 is 400 mg. The amount of AIBN initiator is 1% mol of the total monomer mass. The reaction temperature was 80°C and the reaction time was 12h. The obtained polymer was purified by reprecipitation and then dissolved in DMF. The mass ratio of DMF to polymer was 10:2, and the cross-linking agent divinylbenzene (DVB) was added. The dosage of divinylbenzene is 10 μL, and the reaction is carried out at 80 degrees for 12 hours.
成膜film formation
上述得到的溶液中加入水滑石MgAl-LDH（Mg12Al6(OH)36(Mo7O24)H2O，下同），聚合物、水滑石和DMF的质量比为2:0.3:10。水滑石颗粒尺寸为50nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为70%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Hydrotalcite MgAl-LDH (Mg12 Al6 (OH)36 (Mo7 O24 )H2 O, the same below) was added to the solution obtained above. The mass ratio of polymer, hydrotalcite and DMF was 2:0.3:10. . The particle size of hydrotalcite is 50nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 70%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.78 V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 1.78 V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
对比例：（B）聚合物的合成Comparative Example: (B) Synthesis of Polymer
同实施例A1。Same as Example A1.
成膜film formation
上述得到的溶液中加入水滑石MgAl-LDH，聚合物、水滑石和DMF的质量比为2:0.3:10。水滑石颗粒尺寸为50nm，浆料搅拌均匀，真空脱除气泡。在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷成膜，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Hydrotalcite MgAl-LDH was added to the solution obtained above, and the mass ratio of polymer, hydrotalcite and DMF was 2:0.3:10. The particle size of hydrotalcite is 50nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. On the glass substrate, use a 100 μm Meyer rod to evenly apply the casting solution to form a film, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite film is placed in deionized water to remove the film to obtain the thickness of the film. About 20μm.
性能测试Performance Testing
在没有多孔支撑层的作用下，膜极易碎，难以进行电化学测试Without a porous support layer, the membrane is extremely fragile and difficult to conduct electrochemical testing.
实施例A1中提供的对照实施例表明，在无支撑层的情况下，离子交换膜的机械强度会受到显著影响。The comparative example provided in Example A1 shows that in the absence of a support layer, the mechanical strength of the ion exchange membrane is significantly affected.
对比例：（C）聚合物的合成Comparative Example: (C) Synthesis of Polymer
同实施例A1。Same as Example A1.
成膜film formation
上述得到的溶液中加入水滑石MgAl-LDH（元素含量：C：5 wt%； O：63 wt%；Mg：20wt%；Al：12wt%），聚合物、水滑石和DMF的质量比为2:0.3:10。水滑石颗粒尺寸为50nm，浆料搅拌均匀，真空脱除气泡。在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷成膜，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Hydrotalcite MgAl-LDH (element content: C: 5 wt%; O: 63 wt%; Mg: 20 wt%; Al: 12 wt%) was added to the solution obtained above. The mass ratio of polymer, hydrotalcite and DMF was 2 :0.3:10. The particle size of hydrotalcite is 50nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. On the glass substrate, use a 100 μm Meyer rod to evenly apply the casting solution to form a film, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite film is placed in deionized water to remove the film to obtain the thickness of the film. About 20μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.97 V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 1.97 V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A2:Example A2:
聚合物的合成Synthesis of polymers
同实施例A1。Same as Example A1.
成膜film formation
上述得到的溶液中加入水滑石MgAl-LDH，聚合物、水滑石和DMF的质量比为2:0.3:10。水滑石颗粒尺寸为1μm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为70%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Hydrotalcite MgAl-LDH was added to the solution obtained above, and the mass ratio of polymer, hydrotalcite and DMF was 2:0.3:10. The hydrotalcite particle size is 1 μm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 70%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.30 V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 2.30 V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A3:Example A3:
（A）聚合物的合成(A) Synthesis of polymers
同实施例A1。Same as Example A1.
成膜film formation
上述得到的溶液中加入水滑石MgAl-LDH，聚合物、水滑石和DMF的质量比为2:0.3:10。水滑石颗粒尺寸为200nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为70%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Hydrotalcite MgAl-LDH was added to the solution obtained above, and the mass ratio of polymer, hydrotalcite and DMF was 2:0.3:10. The particle size of hydrotalcite is 200nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 70%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.95 V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 1.95 V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A4:Example A4:
（A）聚合物的合成(A) Synthesis of polymers
同实施例A1。Same as Example A1.
成膜film formation
上述得到的溶液中加入水滑石MgAl-LDH，聚合物、水滑石和DMF的质量比为2:0.3:10。水滑石颗粒尺寸为500nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为70%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Hydrotalcite MgAl-LDH was added to the solution obtained above, and the mass ratio of polymer, hydrotalcite and DMF was 2:0.3:10. The particle size of hydrotalcite is 500nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 70%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.21 V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 2.21 V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A5:Example A5:
聚合物的合成Synthesis of polymers
同实施例A1。Same as Example A1.
成膜film formation
上述得到的溶液中加入水滑石CaAl-LDH（4CaO-Al2O3-[Ca2Al(OH)6]，下同），聚合物、水滑石和DMF的质量比为2:0.3:10。水滑石颗粒尺寸为200nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为70%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Hydrotalcite CaAl-LDH (4CaO-Al2 O3 -[Ca2 Al(OH)6 ], the same below) was added to the solution obtained above. The mass ratio of polymer, hydrotalcite and DMF was 2:0.3:10. The particle size of hydrotalcite is 200nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 70%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.97 V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 1.97 V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A6:Example A6:
聚合物的合成Synthesis of polymers
同实施例A1。Same as Example A1.
成膜film formation
上述得到的溶液中加入水滑石，聚合物、水滑石ZnAl-LDH（Zn0.5Al0.5（CO3）0.25(OH)2·H2O,下同）和DMF的质量比为2:0.3:10。水滑石颗粒尺寸为200nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为70%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Hydrotalcite was added to the solution obtained above. The mass ratio of polymer, hydrotalcite ZnAl-LDH (Zn0.5 Al0.5 (CO3)0.25 (OH)2 ·H2 O, the same below) and DMF was 2:0.3:10. The particle size of hydrotalcite is 200nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 70%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.03 V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 2.03 V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A7:Example A7:
聚合物的合成Synthesis of polymers
同实施例A1。Same as Example A1.
成膜film formation
上述得到的溶液中加入氧化锆，聚合物、氧化锆和DMF的质量比为2:0.3:10。氧化锆颗粒尺寸为50nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为70%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Zirconium oxide was added to the solution obtained above, and the mass ratio of polymer, zirconium oxide and DMF was 2:0.3:10. The particle size of zirconia is 50nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 70%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.77 V，500小时内槽压上升未超过5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic tank pressure was maintained at 1.77 V, and the tank pressure did not increase by more than 5% within 500 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A8:Example A8:
聚合物的合成Synthesis of polymers
同实施例A1。Same as Example A1.
成膜film formation
上述得到的溶液中加入硫酸钡，聚合物、硫酸钡和DMF的质量比为2:0.3:10。硫酸钡颗粒尺寸为50nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为70%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Barium sulfate was added to the solution obtained above, and the mass ratio of polymer, barium sulfate and DMF was 2:0.3:10. The barium sulfate particle size is 50nm, the slurry is stirred evenly, and the bubbles are removed under vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 70%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.82V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.82V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A9:Example A9:
聚合物的合成Synthesis of polymers
同实施例A1。Same as Example A1.
成膜film formation
上述得到的溶液中加入氢氧化镍、水滑石MgAl-LDH质量比为1:1的无机混合物，聚合物、无机混合物和DMF的质量比为2:0.3:10。无机混合物颗粒尺寸为200nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为70%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。To the solution obtained above was added an inorganic mixture with a mass ratio of nickel hydroxide and hydrotalcite MgAl-LDH of 1:1, and a mass ratio of polymer, inorganic mixture and DMF of 2:0.3:10. The particle size of the inorganic mixture is 200nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 70%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.10 V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 2.10 V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A10:Example A10:
聚合物的合成Synthesis of polymers
同实施例A1。Same as Example A1.
成膜film formation
上述得到的溶液中加入氢氧化镁、碳酸锌、氢氧化镍质量比1:1:1的无机混合物，聚合物、无机混合物和DMF的质量比为2:0.3:10。无机混合物颗粒尺寸为200nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为70%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。An inorganic mixture with a mass ratio of magnesium hydroxide, zinc carbonate, and nickel hydroxide was added to the solution obtained above, with a mass ratio of 1:1:1. The mass ratio of the polymer, inorganic mixture, and DMF was 2:0.3:10. The particle size of the inorganic mixture is 200nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 70%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.13 V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 2.13 V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
通过上述实施例A1-A10的对比可以知道，通过优化筛选的水滑石MgAl-LDH、CaAl-LDH、ZnAl-LDH和氧化锆等均对本方案的聚合物的质子传导能力所体现良好增效协同作用，相较于其它类型的无机物作为增强质子传导添加材料，水滑石结构和氧化锆具有更为显著的效能，而可以在整体上增强交换膜材料的。From the comparison of the above Examples A1-A10, it can be known that the optimized and screened hydrotalcites MgAl-LDH, CaAl-LDH, ZnAl-LDH and zirconia all have a good synergistic effect on the proton conductivity of the polymer of this solution. , compared with other types of inorganic substances as additive materials for enhancing proton conduction, hydrotalcite structure and zirconia have more significant effectiveness, and can enhance the overall exchange membrane material.
实施例A11:Example A11:
聚合物的合成Synthesis of polymers
将1:1.2物质当量的四甲基咪唑和对氯甲基苯乙烯，以乙腈为溶剂，80℃反应1.5天后停止反应。纯化固体，得到乙烯基苄基-R1单体，R1为四甲基咪唑鎓。将苯乙烯和乙烯基苄基-R1单体和自由基引发剂溶于400μL的甲苯和400μL的乙醇的混合溶剂中。苯乙烯与乙烯基苄基-R1的物质的量比m:n为0.5:1。乙烯基苄基-R1的质量为400mg。AIBN引发剂的量单体总物质量的1%mol。反应温度为80℃，反应时间12h。将得到的聚合物通过重沉淀的方式提纯之后溶于DMF，DMF和聚合物的质量比例为10:2，加入交联剂二乙烯基苯(DVB)。二乙烯基苯的用量为10μL，80度反应12h。Add 1:1.2 material equivalents of tetramethylimidazole and p-chloromethylstyrene, using acetonitrile as the solvent, and react at 80°C for 1.5 days before stopping the reaction. The solid was purified to obtain vinylbenzyl-R1 monomer, and R1 was tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomers and free radical initiators were dissolved in a mixed solvent of 400 μL of toluene and 400 μL of ethanol. The mass ratio m:n of styrene and vinylbenzyl-R1 is 0.5:1. The mass of vinylbenzyl-R1 is 400 mg. The amount of AIBN initiator is 1% mol of the total monomer mass. The reaction temperature was 80°C and the reaction time was 12h. The obtained polymer was purified by reprecipitation and then dissolved in DMF. The mass ratio of DMF to polymer was 10:2, and the cross-linking agent divinylbenzene (DVB) was added. The dosage of divinylbenzene is 10 μL, and the reaction is carried out at 80 degrees for 12 hours.
成膜film formation
上述得到的溶液中加入氧化锆，聚合物、氧化锆和DMF的质量比为2:1.2:10。氧化锆颗粒尺寸为50nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为80%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Zirconium oxide was added to the solution obtained above, and the mass ratio of polymer, zirconium oxide and DMF was 2:1.2:10. The particle size of zirconia is 50nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 80%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.95 V。100h内槽压上升5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 1.95 V. The tank pressure increased by 5% within 100 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A12:Example A12:
聚合物的合成Synthesis of polymers
将1:1.2物质当量的四甲基咪唑和对氯甲基苯乙烯，以乙腈为溶剂，80℃反应1.5天后停止反应。纯化固体，得到乙烯基苄基-R1单体，R1为四甲基咪唑鎓。将苯乙烯和乙烯基苄基-R1单体和自由基引发剂溶于400μL的甲苯和400μL的乙醇的混合溶剂中。苯乙烯与乙烯基苄基-R1的物质的量比m:n为:9:1。乙烯基苄基-R1的质量为400mg。AIBN引发剂的量单体总物质量的1%mol。反应温度为80℃，反应时间12h。将得到的聚合物通过重沉淀的方式提纯之后溶于DMF，DMF和聚合物的质量比例为10:2，加入交联剂二乙烯基苯(DVB)。二乙烯基苯的用量为10μL，80度反应12h。Add 1:1.2 material equivalents of tetramethylimidazole and p-chloromethylstyrene, using acetonitrile as the solvent, and react at 80°C for 1.5 days before stopping the reaction. The solid was purified to obtain vinylbenzyl-R1 monomer, and R1 was tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomers and free radical initiators were dissolved in a mixed solvent of 400 μL of toluene and 400 μL of ethanol. The mass ratio m:n of styrene and vinylbenzyl-R1 is: 9:1. The mass of vinylbenzyl-R1 is 400 mg. The amount of AIBN initiator is 1% mol of the total monomer mass. The reaction temperature was 80°C and the reaction time was 12h. The obtained polymer was purified by reprecipitation and then dissolved in DMF. The mass ratio of DMF to polymer was 10:2, and the cross-linking agent divinylbenzene (DVB) was added. The dosage of divinylbenzene is 10 μL, and the reaction is carried out at 80 degrees for 12 hours.
成膜film formation
上述得到的溶液中加入氧化锆，聚合物、氧化锆和DMF的质量比为2:1.2:10。氧化锆颗粒尺寸为50nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为80%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Zirconium oxide was added to the solution obtained above, and the mass ratio of polymer, zirconium oxide and DMF was 2:1.2:10. The particle size of zirconia is 50nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 80%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.10V，300小时槽压上升约5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic tank pressure was maintained at 2.10V, and the tank pressure increased by approximately 5% after 300 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A13：Example A13:
聚合物的合成Synthesis of polymers
将1:1.2物质当量的四甲基咪唑和对氯甲基苯乙烯，以乙腈为溶剂，80℃反应1.5天后停止反应。纯化固体，得到乙烯基苄基-R1单体，R1为四甲基咪唑鎓。将苯乙烯和乙烯基苄基-R1单体和自由基引发剂溶于400μL的甲苯和400μL的乙醇的混合溶剂中。苯乙烯与乙烯基苄基-R1的物质的量比m:n为1.5:1。乙烯基苄基-R1的质量为400mg。AIBN引发剂的量单体总物质量的1%mol。反应温度为80℃，反应时间12h。将得到的聚合物通过重沉淀的方式提纯之后溶于DMF，DMF和聚合物的质量比例为10:2，加入交联剂二乙烯基苯(DVB)。二乙烯基苯的用量为10μL，80度反应12h。Add 1:1.2 material equivalents of tetramethylimidazole and p-chloromethylstyrene, using acetonitrile as the solvent, and react at 80°C for 1.5 days before stopping the reaction. The solid was purified to obtain vinylbenzyl-R1 monomer, and R1 was tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomers and free radical initiators were dissolved in a mixed solvent of 400 μL of toluene and 400 μL of ethanol. The mass ratio m:n of styrene and vinylbenzyl-R1 is 1.5:1. The mass of vinylbenzyl-R1 is 400 mg. The amount of AIBN initiator is 1% mol of the total monomer mass. The reaction temperature was 80°C and the reaction time was 12h. The obtained polymer was purified by reprecipitation and then dissolved in DMF. The mass ratio of DMF to polymer was 10:2, and the cross-linking agent divinylbenzene (DVB) was added. The dosage of divinylbenzene is 10 μL, and the reaction is carried out at 80 degrees for 12 hours.
成膜film formation
上述得到的溶液中加入氧化锆，聚合物、氧化锆和DMF的质量比为2:1.2:10。氧化锆颗粒尺寸为50nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为80%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Zirconium oxide was added to the solution obtained above, and the mass ratio of polymer, zirconium oxide and DMF was 2:1.2:10. The particle size of zirconia is 50nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 80%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.90 V，400小时槽压上升约5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic tank pressure was maintained at 1.90 V, and the tank pressure increased by approximately 5% after 400 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A14:Example A14:
聚合物的合成Synthesis of polymers
将1:1.2物质当量的四甲基咪唑和对氯甲基苯乙烯，以乙腈为溶剂，80℃反应1.5天后停止反应。纯化固体，得到乙烯基苄基-R1单体，R1为四甲基咪唑鎓。将苯乙烯和乙烯基苄基-R1单体和自由基引发剂溶于400μL的甲苯和400μL的乙醇的混合溶剂中。苯乙烯与乙烯基苄基-R1的物质的量比m:n为3:1。乙烯基苄基-R1的质量为400mg。AIBN引发剂的量单体总物质量的1%mol。反应温度为80℃，反应时间12h。将得到的聚合物通过重沉淀的方式提纯之后溶于DMF，DMF和聚合物的质量比例为10:2，加入交联剂二乙烯基苯(DVB)。二乙烯基苯的用量为10μL，80度反应12h。Add 1:1.2 material equivalents of tetramethylimidazole and p-chloromethylstyrene, using acetonitrile as the solvent, and react at 80°C for 1.5 days before stopping the reaction. The solid was purified to obtain vinylbenzyl-R1 monomer, and R1 was tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomers and free radical initiators were dissolved in a mixed solvent of 400 μL of toluene and 400 μL of ethanol. The mass ratio m:n of styrene and vinylbenzyl-R1 is 3:1. The mass of vinylbenzyl-R1 is 400 mg. The amount of AIBN initiator is 1% mol of the total monomer mass. The reaction temperature was 80°C and the reaction time was 12h. The obtained polymer was purified by reprecipitation and then dissolved in DMF. The mass ratio of DMF to polymer was 10:2, and the cross-linking agent divinylbenzene (DVB) was added. The dosage of divinylbenzene is 10 μL, and the reaction is carried out at 80 degrees for 12 hours.
成膜film formation
上述得到的溶液中加入氧化锆，聚合物、氧化锆和DMF的质量比为2:1.2:10。氧化锆颗粒尺寸为50nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为80%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Zirconium oxide was added to the solution obtained above, and the mass ratio of polymer, zirconium oxide and DMF was 2:1.2:10. The particle size of zirconia is 50nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 80%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.95 V，300小时槽压上升约5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic tank pressure was maintained at 1.95 V, and the tank pressure increased by approximately 5% after 300 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A15:Example A15:
聚合物的合成Synthesis of polymers
将1:1.2物质当量的四甲基咪唑和对氯甲基苯乙烯，以乙腈为溶剂，80℃反应1.5天后停止反应。纯化固体，得到乙烯基苄基-R1单体，R1为四甲基咪唑鎓。将苯乙烯和乙烯基苄基-R1单体和自由基引发剂溶于400μL的甲苯和400μL的乙醇的混合溶剂中。苯乙烯与乙烯基苄基-R1的物质的量比m:n为1.8:1。乙烯基苄基-R1的质量为400mg。AIBN引发剂的量单体总物质量的1%mol。反应温度为80℃，反应时间12h。将得到的聚合物通过重沉淀的方式提纯之后溶于DMF，DMF和聚合物的质量比例为10:2，加入交联剂二乙烯基苯(DVB)。二乙烯基苯的用量为10μL，80度反应12h。Add 1:1.2 material equivalents of tetramethylimidazole and p-chloromethylstyrene, using acetonitrile as the solvent, and react at 80°C for 1.5 days before stopping the reaction. The solid was purified to obtain vinylbenzyl-R1 monomer, and R1 was tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomers and free radical initiators were dissolved in a mixed solvent of 400 μL of toluene and 400 μL of ethanol. The mass ratio m:n of styrene and vinylbenzyl-R1 is 1.8:1. The mass of vinylbenzyl-R1 is 400 mg. The amount of AIBN initiator is 1% mol of the total monomer mass. The reaction temperature was 80°C and the reaction time was 12h. The obtained polymer was purified by reprecipitation and then dissolved in DMF. The mass ratio of DMF to polymer was 10:2, and the cross-linking agent divinylbenzene (DVB) was added. The dosage of divinylbenzene is 10 μL, and the reaction is carried out at 80 degrees for 12 hours.
成膜film formation
上述得到的溶液中加入氧化锆，聚合物、氧化锆和DMF的质量比为2:1.2:10。氧化锆颗粒尺寸为50nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为80%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Zirconium oxide was added to the solution obtained above, and the mass ratio of polymer, zirconium oxide and DMF was 2:1.2:10. The particle size of zirconia is 50nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 80%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.82 V，500小时槽压上升约5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic tank pressure was maintained at 1.82 V, and the tank pressure increased by approximately 5% after 500 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A16:Example A16:
聚合物的合成Synthesis of polymers
将1:1.2物质当量的四甲基咪唑和对氯甲基苯乙烯，以乙腈为溶剂，80℃反应1.5天后停止反应。纯化固体，得到乙烯基苄基-R1单体，R1为四甲基咪唑鎓。将苯乙烯和乙烯基苄基-R1单体和自由基引发剂溶于400μL的甲苯和400μL的乙醇的混合溶剂中。苯乙烯与乙烯基苄基-R1的物质的量比m:n为2.5:1。乙烯基苄基-R1的质量为400mg。AIBN引发剂的量单体总物质量的1%mol。反应温度为80℃，反应时间12h。将得到的聚合物通过重沉淀的方式提纯之后溶于DMF，DMF和聚合物的质量比例为10:2，加入交联剂二乙烯基苯(DVB)。二乙烯基苯的用量为10μL，80度反应12h。Add 1:1.2 material equivalents of tetramethylimidazole and p-chloromethylstyrene, using acetonitrile as the solvent, and react at 80°C for 1.5 days before stopping the reaction. The solid was purified to obtain vinylbenzyl-R1 monomer, and R1 was tetramethylimidazolium. Styrene and vinylbenzyl-R1 monomers and free radical initiators were dissolved in a mixed solvent of 400 μL of toluene and 400 μL of ethanol. The mass ratio m:n of styrene and vinylbenzyl-R1 is 2.5:1. The mass of vinylbenzyl-R1 is 400 mg. The amount of AIBN initiator is 1% mol of the total monomer mass. The reaction temperature was 80°C and the reaction time was 12h. The obtained polymer was purified by reprecipitation and then dissolved in DMF. The mass ratio of DMF to polymer was 10:2, and the cross-linking agent divinylbenzene (DVB) was added. The dosage of divinylbenzene is 10 μL, and the reaction is carried out at 80 degrees for 12 hours.
成膜film formation
上述得到的溶液中加入氧化锆，聚合物、氧化锆和DMF的质量比为2:1.2:10。氧化锆颗粒尺寸为50nm，浆料搅拌均匀，真空脱除气泡。采用厚度4μm的ePTFE膜作为多孔支撑层，孔隙率约为80%。ePTFE膜平整的铺在玻璃基底上，使用100μm迈耶棒将铸膜液均匀的涂敷在ePTFE上，再放入120℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20μm。Zirconium oxide was added to the solution obtained above, and the mass ratio of polymer, zirconium oxide and DMF was 2:1.2:10. The particle size of zirconia is 50nm, the slurry is stirred evenly, and the bubbles are removed by vacuum. An ePTFE membrane with a thickness of 4 μm is used as the porous support layer, with a porosity of approximately 80%. The ePTFE membrane is spread flatly on the glass substrate. Use a 100 μm Meyer rod to evenly apply the casting liquid on the ePTFE, then place it in a 120°C oven to dry for 3 minutes and then take it out. The dried composite membrane is deionized in deionized water. film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.84V，400小时槽压上升约5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic tank pressure was maintained at 1.84V, and the tank pressure increased by approximately 5% after 400 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A17:Example A17:
与A11的区别仅在于：成膜过程中氧化锆替换为水滑石MgAl-LDH Mg12Al6(OH)36(Mo7O24)H2O。The only difference from A11 is that during the film formation process, zirconium oxide is replaced by hydrotalcite MgAl-LDH Mg12 Al6 (OH)36 (Mo7 O24 )H2 O.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.97 V。100h内槽压上升5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 1.97 V. The tank pressure increased by 5% within 100 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A18:Example A18:
与A12的区别仅在于：成膜过程中氧化锆替换为水滑石MgAl-LDH Mg12Al6(OH)36(Mo7O24)H2O。The only difference from A12 is that during the film formation process, zirconium oxide is replaced by hydrotalcite MgAl-LDH Mg12 Al6 (OH)36 (Mo7 O24 )H2 O.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.11V，300小时槽压上升约5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic tank pressure was maintained at 2.11V, and the tank pressure increased by approximately 5% after 300 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A19：Example A19:
与A13的区别仅在于：成膜过程中氧化锆替换为水滑石MgAl-LDH Mg12Al6(OH)36(Mo7O24)H2O。The only difference from A13 is that during the film formation process, zirconium oxide is replaced by hydrotalcite MgAl-LDH Mg12 Al6 (OH)36 (Mo7 O24 )H2 O.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.93 V，400小时槽压上升约5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic tank pressure was maintained at 1.93 V, and the tank pressure increased by approximately 5% after 400 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A20:Example A20:
与A14的区别仅在于：成膜过程中氧化锆替换为水滑石MgAl-LDH Mg12Al6(OH)36(Mo7O24)H2O。The only difference from A14 is that during the film formation process, zirconium oxide is replaced by hydrotalcite MgAl-LDH Mg12 Al6 (OH)36 (Mo7 O24 )H2 O.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.98 V，300小时槽压上升约5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic tank pressure was maintained at 1.98 V, and the tank pressure increased by approximately 5% after 300 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A21:Example A21:
与A15的区别仅在于：成膜过程中氧化锆替换为水滑石MgAl-LDH Mg12Al6(OH)36(Mo7O24)H2O。The only difference from A15 is that during the film formation process, zirconium oxide is replaced by hydrotalcite MgAl-LDH Mg12 Al6 (OH)36 (Mo7 O24 )H2 O.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.84 V，500小时槽压上升约5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic tank pressure was maintained at 1.84 V, and the tank pressure increased by approximately 5% after 500 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例A22Example A22
与A16的区别仅在于：成膜过程中氧化锆替换为水滑石MgAl-LDH Mg12Al6(OH)36(Mo7O24)H2O。The only difference from A16 is that during the film formation process, zirconium oxide is replaced by hydrotalcite MgAl-LDH Mg12 Al6 (OH)36 (Mo7 O24 )H2 O.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.86V，400小时槽压上升约5%。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic tank pressure was maintained at 1.86V, and the tank pressure increased by approximately 5% after 400 hours. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B11Example B11
与A1（A）的区别仅在于：聚合物的合成中The only difference from A1(A) is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.009(R2的质量分数为0.28%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.009 (the mass fraction of R2 is 0.28%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.83V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.83V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B12Example B12
与A11的区别仅在于：聚合物的合成中The only difference from A11 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.009(R2的质量分数为0.28%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.009 (the mass fraction of R2 is 0.28%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.93V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.93V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B13Example B13
与A17的区别仅在于：聚合物的合成中The only difference from A17 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.009(R2的质量分数为0.28%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.009 (the mass fraction of R2 is 0.28%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.93V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.93V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B14Example B14
与A7的区别仅在于：聚合物的合成中The only difference from A7 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.009(R2的质量分数为0.28%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.009 (the mass fraction of R2 is 0.28%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.83V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.83V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B21Example B21
与A2的区别仅在于：聚合物的合成中The only difference from A2 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.0045(R2的质量分数为0.14%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.0045 (the mass fraction of R2 is 0.14%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.18V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 2.18V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B22Example B22
与A12的区别仅在于：聚合物的合成中The only difference from A12 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.0045(R2的质量分数为0.14%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.0045 (the mass fraction of R2 is 0.14%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.03V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 2.03V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B23Example B23
与A18的区别仅在于：聚合物的合成中The only difference from A18 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.0045(R2的质量分数为0.14%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.0045 (the mass fraction of R2 is 0.14%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.06V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 2.06V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B24Example B24
与A7的区别仅在于：聚合物的合成中The only difference from A7 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.0045(R2的质量分数为0.14%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.0045 (the mass fraction of R2 is 0.14%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.77V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.77V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B31Example B31
与A3的区别仅在于：聚合物的合成中The only difference from A3 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.003(R2的质量分数为0.10%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.003 (the mass fraction of R2 is 0.10%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.82V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.82V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B32Example B32
与A13的区别仅在于：聚合物的合成中The only difference from A13 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.003(R2的质量分数为0.10%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.003 (the mass fraction of R2 is 0.10%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.83V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.83V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B33Example B33
与A19的区别仅在于：聚合物的合成中The only difference from A19 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.003(R2的质量分数为0.10%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.003 (the mass fraction of R2 is 0.10%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.86V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.86V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
实施例B34Example B34
与A7的区别仅在于：聚合物的合成中The only difference from A7 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.003(R2的质量分数为0.10%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.003 (the mass fraction of R2 is 0.10%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.73V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.73V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
对比例A1Comparative example A1
聚合物的合成Synthesis of polymers
高分子合成步骤完全同实施例A1（A），不使用无机亲水材料，聚合物和DMF的比例为2:10，4μm的ePTFE膜平整的铺在玻璃基底上，直接使用100 μm迈耶棒将铸膜液均匀的涂敷在玻璃基底上，再放入120 ℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20 μm。The polymer synthesis steps are exactly the same as in Example A1 (A). No inorganic hydrophilic material is used. The ratio of polymer to DMF is 2:10. The 4 μm ePTFE membrane is spread flatly on the glass substrate, and a 100 μm Meyer rod is used directly. The casting liquid is evenly applied on the glass substrate, and then placed in a 120°C oven to dry for 3 minutes and then taken out. The dried composite film is placed in deionized water to remove the film, resulting in a film thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.93V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。膜的机械强度弱于加氧化锆的体系。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.93V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V. The mechanical strength of the membrane is weaker than that of the zirconia-added system.
对比例B1Comparative example B1
与B11的区别仅在于：聚合物的合成中The only difference from B11 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.025(R2的质量分数为0.62%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.025 (the mass fraction of R2 is 0.62%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.95V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.95V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
对比例B2Comparative example B2
与B11的区别仅在于：聚合物的合成中The only difference from B11 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.1(R2的质量分数为3.0%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.1 (the mass fraction of R2 is 3.0%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.10V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water pressure is maintained at 2.10V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
对比例B3Comparative example B3
与B14的区别仅在于：聚合物的合成中The only difference from B14 is: in the synthesis of polymer
苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的物质的量比m:n:q为2:1:0.025(R2的质量分数为0.62%)。The mass ratio m:n:q of styrene, vinylbenzyl-R1, and p-vinylbenzyl chloride is 2:1:0.025 (the mass fraction of R2 is 0.62%).
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在1.92V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 1.92V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
对比例B4Comparative example B4
与B14的区别仅在于：聚合物的合成The only difference from B14 is: the synthesis of the polymer
高分子合成过程中，苯乙烯、乙烯基苄基-R1、对乙烯基苄氯的比例为2:1:0.1(3.0%)其他步骤完全同实施例A1（A），聚合物，氧化锆和DMF的比例为2:0.3:10，4μm的ePTFE膜平整的铺在玻璃基底上，直接使用100 μm迈耶棒将铸膜液均匀的涂敷在玻璃基底上，再放入120 ℃烘箱干燥3分钟后取出，将干燥的复合膜放在去离子水中脱膜，得到膜的厚度约为20 μm。During the polymer synthesis process, the ratio of styrene, vinyl benzyl-R1, and p-vinyl benzyl chloride was 2:1:0.1 (3.0%). Other steps were completely the same as in Example A1 (A), polymer, zirconium oxide and The ratio of DMF is 2:0.3:10. The 4 μm ePTFE membrane is spread flatly on the glass substrate. Directly use a 100 μm Meyer rod to evenly apply the casting liquid on the glass substrate, and then place it in a 120 ℃ oven to dry 3 Take it out after 10 minutes, place the dried composite membrane in deionized water to remove the membrane, and obtain a membrane thickness of approximately 20 μm.
性能测试Performance Testing
在400 mA电流密度下，电解水槽压维持在2.06V。同等测试条件下商业膜Fumasep-40的槽压为2.10 V。At a current density of 400 mA, the electrolytic water tank voltage is maintained at 2.06V. Under the same test conditions, the tank pressure of commercial membrane Fumasep-40 is 2.10 V.
通过如上实施例与对比例的一一匹配对照可以知道，本发明方案在通过优化离子膜的高分子结构和无机填料对相应方案的优化，可以有效改善产品的电化学性能。Through a one-to-one comparison of the above examples and comparative examples, it can be known that the solution of the present invention can effectively improve the electrochemical performance of the product by optimizing the polymer structure of the ion membrane and the optimization of the corresponding solution.
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式，并且很显然，根据上述教导，可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用，从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and illustration. These descriptions are not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teachings. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application, thereby enabling others skilled in the art to make and utilize various exemplary embodiments of the invention and various different applications. Choice and change. The scope of the invention is intended to be defined by the claims and their equivalents.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310427665.XACN116272397B (en) | 2023-04-20 | 2023-04-20 | Heterogeneous anion exchange membrane and device |
| Application Number | Priority Date | Filing Date | Title |
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| CN202310427665.XACN116272397B (en) | 2023-04-20 | 2023-04-20 | Heterogeneous anion exchange membrane and device |
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| CN116272397A CN116272397A (en) | 2023-06-23 |
| CN116272397Btrue CN116272397B (en) | 2024-01-05 |
| Application Number | Title | Priority Date | Filing Date |
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| CN202310427665.XAActiveCN116272397B (en) | 2023-04-20 | 2023-04-20 | Heterogeneous anion exchange membrane and device |
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| CN (1) | CN116272397B (en) |
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