CN117133955A - An organic phosphonic acid proton exchange membrane and its preparation method and application - Google Patents
An organic phosphonic acid proton exchange membrane and its preparation method and application Download PDFInfo
- Publication number
- CN117133955A CN117133955A CN202310945868.8A CN202310945868A CN117133955A CN 117133955 A CN117133955 A CN 117133955A CN 202310945868 A CN202310945868 A CN 202310945868A CN 117133955 A CN117133955 A CN 117133955A
- Authority
- CN
- China
- Prior art keywords
- organic phosphonic
- phosphonic acid
- acid
- proton exchange
- exchange membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Fuel Cell (AREA)
Abstract
本发明提供一种有机膦酸质子交换膜及其制备方法与应用，该方法包括：S01、将有机膦酸和碱性物质溶解于去离子水中，得到有机膦酸溶液；所述有机膦酸和所述碱性物质的质量比为0.5～3；以所述有机膦酸溶液的质量为100％计，所述有机膦酸的质量分数为5％～80％；S02、将氮杂环聚合物膜浸泡于步骤S01的有机膦酸溶液中，于50℃～100℃加热8h～36h，真空干燥，得到聚合物膜；S03、将S02的聚合物膜浸泡于酸溶液中，于50℃～100℃加热4h～36h，真空干燥，得到有机膦酸质子交换膜。本申请制备方法简便，制得的有机膦酸质子交换膜在高温下具有较强的机械稳定性、低渗氢率、高保酸率和高导电性。The invention provides an organic phosphonic acid proton exchange membrane and its preparation method and application. The method includes: S01, dissolving organic phosphonic acid and alkaline substances in deionized water to obtain an organic phosphonic acid solution; the organic phosphonic acid and The mass ratio of the alkaline substance is 0.5 to 3; based on the mass of the organic phosphonic acid solution being 100%, the mass fraction of the organic phosphonic acid is 5% to 80%; S02, nitrogen heterocyclic polymer The membrane is soaked in the organic phosphonic acid solution in step S01, heated at 50°C to 100°C for 8h to 36h, and dried in vacuum to obtain a polymer film; S03. Soak the polymer film of S02 in the acid solution, and heated at 50°C to 100°C. Heat at ℃ for 4h to 36h and dry in vacuum to obtain an organic phosphonic acid proton exchange membrane. The preparation method of the present application is simple, and the prepared organic phosphonic acid proton exchange membrane has strong mechanical stability, low hydrogen permeation rate, high acid retention rate and high conductivity at high temperatures.
Description
技术领域Technical field
本发明属于电池技术领域，尤其涉及一种有机膦酸质子交换膜及其制备方法与应用。The invention belongs to the field of battery technology, and in particular relates to an organic phosphonic acid proton exchange membrane and its preparation method and application.
背景技术Background technique
燃料电池是将化学能转化为电能的装置。近年来，以磷酸掺杂质子交换膜为核心的高温燃料电池逐渐进入燃料电池的主流市场，其简化的水热管理系统、提升的催化活性和强耐CO特性，使其在分布式电源系统里有较大的优势。其中，磷酸掺杂膜的热稳定性、经济性以及高导电率使之成为了高温燃料电池中的主流质子交换膜。A fuel cell is a device that converts chemical energy into electrical energy. In recent years, high-temperature fuel cells with phosphoric acid-doped proton exchange membranes as the core have gradually entered the mainstream fuel cell market. Their simplified hydrothermal management system, improved catalytic activity and strong CO resistance make them popular in distributed power systems. There are greater advantages. Among them, the thermal stability, economy and high conductivity of phosphoric acid-doped membranes make it the mainstream proton exchange membrane in high-temperature fuel cells.
目前，现有的磷酸掺杂质子交换膜存在高温下磷酸分子容易挥发的问题；而且，在停机和冷启动的过程中，磷酸小分子也会被水挤出质子交换膜或被水溶解流失；磷酸流失容易导致高温燃料电池性能骤降，寿命缩短。并且，除磷酸外，其余质子导体也存在易挥发、成本高、难以掺杂等多种问题。另外，掺杂的酸性小分子过量容易导致膜溶胀、机械性能下降、渗氢增加等多种问题，严重影响膜寿命。受限于质子交换膜的高分子基材，掺杂质子的方法通常不具有普适性，很难进行推广应用。Currently, existing phosphoric acid-doped proton exchange membranes have the problem that phosphoric acid molecules are easily volatilized at high temperatures; moreover, during shutdown and cold start, small phosphoric acid molecules will also be squeezed out of the proton exchange membrane by water or dissolved and lost by water; The loss of phosphoric acid can easily lead to a sudden drop in performance and shortened service life of high-temperature fuel cells. Moreover, except for phosphoric acid, other proton conductors also have various problems such as being volatile, high cost, and difficult to dope. In addition, excessive amounts of doped acidic small molecules can easily lead to membrane swelling, reduced mechanical properties, increased hydrogen permeation and other problems, seriously affecting membrane life. Limited by the polymer substrate of the proton exchange membrane, the method of doping protons is usually not universal and difficult to promote and apply.
发明内容Contents of the invention
本发明实施例提供一种有机膦酸质子交换膜及其制备方法与应用，旨在解决现有磷酸掺杂类质子交换膜存在磷酸容易流失导致高温燃料电池性能骤降、寿命缩短，制备成本高，制备复杂、普适性差等问题。Embodiments of the present invention provide an organic phosphonic acid proton exchange membrane and its preparation method and application, aiming to solve the problem of the easy loss of phosphoric acid in existing phosphoric acid-doped proton exchange membranes, which leads to a sudden drop in the performance of high-temperature fuel cells, a shortened lifespan, and high preparation costs. , problems such as complex preparation and poor universality.
为了达到上述目的，一方面，本发明实施例提供一种有机膦酸质子交换膜的制备方法，包括如下步骤：In order to achieve the above objects, on the one hand, embodiments of the present invention provide a method for preparing an organic phosphonic acid proton exchange membrane, which includes the following steps:
S01、将有机膦酸和碱性物质溶解于去离子水中，得到有机膦酸溶液；所述有机膦酸和所述碱性物质的质量比为(0.5～3)：1；以所述有机膦酸溶液的质量为100％计，所述有机膦酸的质量分数为5％～80％；S01. Dissolve organic phosphonic acid and alkaline substances in deionized water to obtain an organic phosphonic acid solution; the mass ratio of the organic phosphonic acid and the alkaline substance is (0.5~3):1; When the mass of the acid solution is 100%, the mass fraction of the organic phosphonic acid is 5% to 80%;
S02、将氮杂环聚合物膜浸泡于步骤S01的有机膦酸溶液中，于50℃～100℃加热8h～36h，真空干燥，得到聚合物膜；S02. Soak the nitrogen heterocyclic polymer film in the organic phosphonic acid solution of step S01, heat at 50°C to 100°C for 8h to 36h, and dry in vacuum to obtain a polymer film;
S03、将S02的聚合物膜浸泡于酸溶液中，于50℃～100℃加热4h～36h，真空干燥，得到有机膦酸质子交换膜。S03. Soak the polymer membrane of S02 in an acid solution, heat it at 50°C to 100°C for 4h to 36h, and dry it under vacuum to obtain an organic phosphonic acid proton exchange membrane.
作为优选的实施方式，步骤S01中，As a preferred implementation, in step S01,
所述有机膦酸为四元有机膦酸。The organic phosphonic acid is a quaternary organic phosphonic acid.
所述四元有机膦酸为乙二胺四甲叉膦酸或/和己二胺四甲叉膦酸。The quaternary organic phosphonic acid is ethylenediaminetetramethylenephosphonic acid or/and hexamethylenediaminetetramethylenephosphonic acid.
以有机膦酸作为质子导体，能够形成高浓度水溶液，从而使有机膦酸能够顺利掺杂进聚合物膜。该有机膦酸质子导体既可以作为单一质子导体，也可配合等其余质子导体(如磷酸、磷钨酸等)形成双质子导体质子交换膜。Using organic phosphonic acid as a proton conductor can form a high-concentration aqueous solution, so that organic phosphonic acid can be doped into the polymer film smoothly. The organic phosphonic acid proton conductor can be used as a single proton conductor, or can be combined with other proton conductors (such as phosphoric acid, phosphotungstic acid, etc.) to form a dual proton conductor proton exchange membrane.
本申请的有机膦酸含有多个膦酸基团，通过氢键与聚合物膜的高分子基材产生物理交联，从而保证膜的机械性能和气密性，同时未交联的侧链-OH基团可提升质子导电性。有机膦酸的熔点大于210℃，在水中的溶解度≤5wt％，不易流失，能够很好的适用现有高温质子交换膜燃料电池。The organic phosphonic acid of the present application contains multiple phosphonic acid groups, which are physically cross-linked with the polymer substrate of the polymer film through hydrogen bonds, thereby ensuring the mechanical properties and air tightness of the film. At the same time, the uncross-linked side chain -OH groups improve proton conductivity. The melting point of organic phosphonic acid is greater than 210°C, the solubility in water is ≤5wt%, and it is not easily lost. It can be well applied to existing high-temperature proton exchange membrane fuel cells.
所述碱性物质为K2CO3、Na2CO3、NaOH和KOH中的一种或至少两种的混合物。The alkaline substance is one or a mixture of at least two of K 2 CO 3 , Na 2 CO 3 , NaOH and KOH.
所述有机膦酸和所述碱性物质的质量比为1。The mass ratio of the organic phosphonic acid and the alkaline substance is 1.
以所述有机膦酸溶液的质量为100％计，所述有机膦酸的质量分数为30％。When the mass of the organic phosphonic acid solution is 100%, the mass fraction of the organic phosphonic acid is 30%.
所述溶解的温度为25℃～100℃，优选为90℃。The dissolution temperature is 25°C to 100°C, preferably 90°C.
作为优选的实施方式，步骤S02中，As a preferred implementation, in step S02,
所述氮杂环聚合物膜为聚苯并咪唑膜、多孔聚苯并咪唑膜、聚吡啶膜、多孔聚吡啶膜、聚吡咯烷酮膜和聚三唑膜中的一种或至少两种的混合物。The nitrogen heterocyclic polymer film is one or a mixture of at least two of polybenzimidazole films, porous polybenzimidazole films, polypyridine films, porous polypyridine films, polypyrrolidone films and polytriazole films.
所述加热优选为于95℃加热24h。The heating is preferably at 95°C for 24 hours.
所述真空干燥的温度为60℃～150℃(可以为60℃、75℃、90℃、100℃、150℃等等)，优选为100℃；所述真空干燥的时间为12h～36h(可以为12h、18h、24h、30h、36h等等)，优选为12h。The vacuum drying temperature is 60°C to 150°C (can be 60°C, 75°C, 90°C, 100°C, 150°C, etc.), preferably 100°C; the vacuum drying time is 12h to 36h (can be 12h, 18h, 24h, 30h, 36h, etc.), preferably 12h.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
作为优选的实施方式，步骤S03中，As a preferred implementation, in step S03,
所述酸溶液为含有10wt％～98wt％(可以为10wt％、30wt％、50wt％、70wt％、80wt％或98wt％等)酸的酸水溶液，优选为饱和浓度的酸水溶液。The acid solution is an acid aqueous solution containing 10wt% to 98wt% (can be 10wt%, 30wt%, 50wt%, 70wt%, 80wt% or 98wt%, etc.) acid, preferably an acid aqueous solution with a saturated concentration.
所述酸为磷酸、焦磷酸、三磷酸、磷钨酸、磷钼酸或硅钨酸中的一种或至少两种的混合物。The acid is one or a mixture of at least two of phosphoric acid, pyrophosphoric acid, triphosphoric acid, phosphotungstic acid, phosphomolybdic acid or silicotungstic acid.
所述加热优选为于80℃加热12h。The heating is preferably at 80°C for 12 hours.
所述真空干燥的温度为60℃～150℃(可以为60℃、75℃、90℃、100℃、150℃等等)，优选为100℃；所述真空干燥的时间为12h～36h(可以为12h、18h、24h、30h、36h等等)，优选为12h。The vacuum drying temperature is 60°C to 150°C (can be 60°C, 75°C, 90°C, 100°C, 150°C, etc.), preferably 100°C; the vacuum drying time is 12h to 36h (can be 12h, 18h, 24h, 30h, 36h, etc.), preferably 12h.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
另一方面，本发明实施例还提供由上述制备方法制备得到的有机膦酸质子交换膜。On the other hand, embodiments of the present invention also provide an organic phosphonic acid proton exchange membrane prepared by the above preparation method.
再一方面，本发明实施例还提供所述有机膦酸质子交换膜的应用，所述有机膦酸质子交换膜可在燃料电池中进行应用。On the other hand, embodiments of the present invention also provide applications of the organic phosphonic acid proton exchange membrane, and the organic phosphonic acid proton exchange membrane can be used in fuel cells.
作为优选的实施方式，所述燃料电池为高温(120℃～200℃)质子膜燃料电池。As a preferred embodiment, the fuel cell is a high-temperature (120°C to 200°C) proton membrane fuel cell.
作为优选的实施方式，所述高温质子膜燃料电池可用于分布式热电联用系统、甲醇催化重振燃料电池系统、液氨制氢燃料电池系统或风冷燃料电池系统中。As a preferred embodiment, the high-temperature proton membrane fuel cell can be used in a distributed combined heat and power system, a methanol catalytic revitalization fuel cell system, a liquid ammonia hydrogen production fuel cell system, or an air-cooled fuel cell system.
本申请通过加入碱性物质，能够有效溶解有机膦酸，使得有机膦酸能够高效掺杂进入氮杂环聚合物膜中，并与氮杂环聚合物膜的高分子骨架产生物理交联作用。制备得到的有机膦酸质子交换膜在高温下仍然具有较强的机械稳定性、低渗氢率、高保酸率和高导电性等特点，可以适用于冷启动、急停、潮湿等多种复杂工况环境，特别适合用于120℃～200℃的高温质子交换膜燃料电池，能够简化水热管理系统，增强CO耐受性，从而能够有效提升能量利用效率。本申请的制备工艺简单易行、操作方便、成本较低、制备时间短，易于实现大规模的工业化生产。并且，本申请制备方法不受限于膜的形态、高分子骨架种类、膜孔隙率、孔径大小等因素，可以作为氮杂环类聚合物膜掺杂酸的通用方法进行应用。This application can effectively dissolve organic phosphonic acid by adding alkaline substances, so that organic phosphonic acid can be efficiently doped into the nitrogen heterocyclic polymer film and produce physical cross-linking with the polymer skeleton of the nitrogen heterocyclic polymer film. The prepared organic phosphonic acid proton exchange membrane still has strong mechanical stability, low hydrogen permeation rate, high acid retention rate and high conductivity at high temperatures, and can be applied to various complex applications such as cold start, emergency stop, and humidity. Working environment, it is especially suitable for high-temperature proton exchange membrane fuel cells of 120°C to 200°C. It can simplify the water and heat management system, enhance CO tolerance, and thus effectively improve energy utilization efficiency. The preparation process of the present application is simple, easy to operate, low in cost, short in preparation time, and easy to realize large-scale industrial production. Moreover, the preparation method of the present application is not limited to membrane morphology, polymer skeleton type, membrane porosity, pore size and other factors, and can be applied as a general method for acid doping of nitrogen heterocyclic polymer membranes.
具体实施方式Detailed ways
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only some of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of the present invention.
需要说明，若本发明实施例中有涉及方向性指示(诸如上、下、左、右、前、后、顶、底……)，则该方向性指示仅用于解释在某一特定姿态下各部件之间的相对位置关系、运动情况等，如果该特定姿态发生改变时，则该方向性指示也相应地随之改变。It should be noted that if the embodiments of the present invention involve directional indications (such as up, down, left, right, front, back, top, bottom...), then the directional indications are only used to explain what to do in a certain posture. The relative positional relationship between the components, the movement status, etc., if the specific posture changes, the directional indication will also change accordingly.
在本申请中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或成一体；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系，除非另有明确的限定。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本申请中的具体含义。In this application, unless otherwise clearly stated and limited, the terms "installation", "connection", "connection", "fixing" and other terms should be understood in a broad sense. For example, it can be a fixed connection or a detachable connection. , or integrated into one; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be an internal connection between two elements or an interactive relationship between two elements, unless otherwise specified restrictions. For those of ordinary skill in the art, the specific meanings of the above terms in this application can be understood according to specific circumstances.
需要说明的是，当元件被称为“固定于”或“设置于”另一个元件，它可以直接在另一个元件上或者也可以存在居中的元件。当一个元件被认为是“连接”另一个元件，它可以是直接连接到另一个元件或者可能同时存在居中元件。It should be noted that when an element is referred to as being "mounted" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. When an element is said to be "connected" to another element, it can be directly connected to the other element or there may also be intervening elements present.
另外，若本发明实施例中有涉及“第一”、“第二”等的描述，则该“第一”、“第二”等的描述仅用于描述目的，而不能理解为指示或暗示其相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。另外，各个实施例之间的技术方案可以相互结合，但是必须是以本领域普通技术人员能够实现为基础，当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在，也不在本发明要求的保护范围之内。In addition, if there are descriptions involving “first”, “second”, etc. in the embodiments of the present invention, the descriptions of “first”, “second”, etc. are only for descriptive purposes and shall not be understood as indications or implications. Its relative importance or implicit indication of the number of technical features indicated. Therefore, features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In addition, the technical solutions in various embodiments can be combined with each other, but it must be based on the realization by those of ordinary skill in the art. When the combination of technical solutions is contradictory or cannot be realized, it should be considered that such a combination of technical solutions does not exist. , nor within the protection scope required by the present invention.
实施例1Example 1
一种有机膦酸质子交换膜的制备方法，包括如下步骤：A method for preparing an organic phosphonic acid proton exchange membrane, including the following steps:
S01、将有机膦酸和碱性物质溶解于去离子水中，得到有机膦酸溶液；所述有机膦酸和所述碱性物质的质量比为1：1；以所述有机膦酸溶液的质量为100％计，所述有机膦酸的质量分数为30％；S01. Dissolve organic phosphonic acid and alkaline substances in deionized water to obtain an organic phosphonic acid solution; the mass ratio of the organic phosphonic acid and the alkaline substance is 1:1; based on the mass of the organic phosphonic acid solution Based on 100%, the mass fraction of the organic phosphonic acid is 30%;
S02、将氮杂环聚合物膜浸泡于步骤S01的有机膦酸溶液中，于95℃加热24h，真空干燥，得到聚合物膜；S02. Soak the nitrogen heterocyclic polymer film in the organic phosphonic acid solution of step S01, heat at 95°C for 24 hours, and dry under vacuum to obtain a polymer film;
S03、将S02的聚合物膜浸泡于酸溶液中，于80℃加热12h，真空干燥，得到有机膦酸质子交换膜。S03. Soak the polymer membrane of S02 in an acid solution, heat it at 80°C for 12 hours, and dry it under vacuum to obtain an organic phosphonic acid proton exchange membrane.
步骤S01中，In step S01,
所述有机膦酸为四元有机膦酸。所述四元有机膦酸为乙二胺四甲叉膦酸。The organic phosphonic acid is a quaternary organic phosphonic acid. The quaternary organic phosphonic acid is ethylenediaminetetramethylenephosphonic acid.
所述碱性物质为NaOH。The alkaline substance is NaOH.
所述溶解的温度为90℃。The dissolution temperature is 90°C.
步骤S02中，In step S02,
所述氮杂环聚合物膜为聚苯并咪唑膜(m-PBI薄膜)。The nitrogen heterocyclic polymer film is a polybenzimidazole film (m-PBI film).
所述真空干燥的温度为100℃；所述真空干燥的时间为12h。The vacuum drying temperature is 100°C; the vacuum drying time is 12 hours.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
步骤S03中，In step S03,
所述酸溶液为含有85wt％酸的酸水溶液。所述酸为磷酸。The acid solution is an aqueous acid solution containing 85 wt% acid. The acid is phosphoric acid.
所述真空干燥的温度为100℃；所述真空干燥的时间为12h0。The vacuum drying temperature is 100°C; the vacuum drying time is 12h0.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
所述有机膦酸质子交换膜可在燃料电池中进行应用。所述燃料电池为高温(120℃～200℃)质子膜燃料电池。所述高温质子膜燃料电池可用于分布式热电联用系统、甲醇催化重振燃料电池系统、液氨制氢燃料电池系统或风冷燃料电池系统中。The organic phosphonic acid proton exchange membrane can be used in fuel cells. The fuel cell is a high-temperature (120°C to 200°C) proton membrane fuel cell. The high-temperature proton membrane fuel cell can be used in a distributed combined heat and power system, a methanol catalytic revitalization fuel cell system, a liquid ammonia hydrogen production fuel cell system or an air-cooled fuel cell system.
实施例2Example 2
一种有机膦酸质子交换膜的制备方法，包括如下步骤：A method for preparing an organic phosphonic acid proton exchange membrane, including the following steps:
S01、将有机膦酸和碱性物质溶解于去离子水中，得到有机膦酸溶液；所述有机膦酸和所述碱性物质的质量比为1:1；以所述有机膦酸溶液的质量为100％计，所述有机膦酸的质量分数为50％；S01. Dissolve organic phosphonic acid and alkaline substances in deionized water to obtain an organic phosphonic acid solution; the mass ratio of the organic phosphonic acid and the alkaline substance is 1:1; based on the mass of the organic phosphonic acid solution Based on 100%, the mass fraction of the organic phosphonic acid is 50%;
S02、将氮杂环聚合物膜浸泡于步骤S01的有机膦酸溶液中，于95℃加热24h，真空干燥，得到聚合物膜；S02. Soak the nitrogen heterocyclic polymer film in the organic phosphonic acid solution of step S01, heat at 95°C for 24 hours, and dry under vacuum to obtain a polymer film;
S03、将S02的聚合物膜浸泡于酸溶液中，于80℃加热12h，真空干燥，得到有机膦酸质子交换膜。S03. Soak the polymer membrane of S02 in an acid solution, heat it at 80°C for 12 hours, and dry it under vacuum to obtain an organic phosphonic acid proton exchange membrane.
步骤S01中，In step S01,
所述有机膦酸为四元有机膦酸。所述四元有机膦酸为乙二胺四甲叉膦酸。The organic phosphonic acid is a quaternary organic phosphonic acid. The quaternary organic phosphonic acid is ethylenediaminetetramethylenephosphonic acid.
所述碱性物质为NaOH。The alkaline substance is NaOH.
所述溶解的温度为90℃。The dissolution temperature is 90°C.
步骤S02中，In step S02,
所述氮杂环聚合物膜为多孔聚苯并咪唑膜。The nitrogen heterocyclic polymer membrane is a porous polybenzimidazole membrane.
所述真空干燥的温度为100℃；所述真空干燥的时间为12h。The vacuum drying temperature is 100°C; the vacuum drying time is 12 hours.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
步骤S03中，In step S03,
所述酸溶液为含有85wt％酸的酸水溶液。所述酸为磷酸。The acid solution is an aqueous acid solution containing 85 wt% acid. The acid is phosphoric acid.
所述真空干燥的温度为100℃；所述真空干燥的时间为12h。The vacuum drying temperature is 100°C; the vacuum drying time is 12 hours.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
所述有机膦酸质子交换膜可在燃料电池中进行应用。所述燃料电池为高温(120℃～200℃)质子膜燃料电池。所述高温质子膜燃料电池可用于分布式热电联用系统、甲醇催化重振燃料电池系统、液氨制氢燃料电池系统或风冷燃料电池系统中。The organic phosphonic acid proton exchange membrane can be used in fuel cells. The fuel cell is a high-temperature (120°C to 200°C) proton membrane fuel cell. The high-temperature proton membrane fuel cell can be used in a distributed combined heat and power system, a methanol catalytic revitalization fuel cell system, a liquid ammonia hydrogen production fuel cell system or an air-cooled fuel cell system.
实施例3Example 3
一种有机膦酸质子交换膜的制备方法，包括如下步骤：A method for preparing an organic phosphonic acid proton exchange membrane, including the following steps:
S01、将有机膦酸和碱性物质溶解于去离子水中，得到有机膦酸溶液；所述有机膦酸和所述碱性物质的质量比为1:1；以所述有机膦酸溶液的质量为100％计，所述有机膦酸的质量分数为30％；S01. Dissolve organic phosphonic acid and alkaline substances in deionized water to obtain an organic phosphonic acid solution; the mass ratio of the organic phosphonic acid and the alkaline substance is 1:1; based on the mass of the organic phosphonic acid solution Based on 100%, the mass fraction of the organic phosphonic acid is 30%;
S02、将氮杂环聚合物膜浸泡于步骤S01的有机膦酸溶液中，于95℃加热36h，真空干燥，得到聚合物膜；S02. Soak the nitrogen heterocyclic polymer film in the organic phosphonic acid solution of step S01, heat at 95°C for 36 hours, and dry under vacuum to obtain a polymer film;
S03、将S02的聚合物膜浸泡于酸溶液中，于80℃加热12h，真空干燥，得到有机膦酸质子交换膜。S03. Soak the polymer membrane of S02 in an acid solution, heat it at 80°C for 12 hours, and dry it under vacuum to obtain an organic phosphonic acid proton exchange membrane.
步骤S01中，In step S01,
所述有机膦酸为四元有机膦酸。所述四元有机膦酸为乙二胺四甲叉膦酸。The organic phosphonic acid is a quaternary organic phosphonic acid. The quaternary organic phosphonic acid is ethylenediaminetetramethylenephosphonic acid.
所述碱性物质为NaOH。The alkaline substance is NaOH.
所述溶解的温度为90℃。The dissolution temperature is 90°C.
步骤S02中，In step S02,
所述氮杂环聚合物膜为聚吡啶膜。The nitrogen heterocyclic polymer film is a polypyridine film.
所述真空干燥的温度为100℃；所述真空干燥的时间为12h。The vacuum drying temperature is 100°C; the vacuum drying time is 12 hours.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
步骤S03中，In step S03,
所述酸溶液为含有50wt％酸的酸水溶液。所述酸为焦磷酸。The acid solution is an aqueous acid solution containing 50 wt% acid. The acid is pyrophosphoric acid.
所述真空干燥的温度为100℃；所述真空干燥的时间为12h。The vacuum drying temperature is 100°C; the vacuum drying time is 12 hours.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
所述有机膦酸质子交换膜可在燃料电池中进行应用。所述燃料电池为高温(120℃～200℃)质子膜燃料电池。所述高温质子膜燃料电池可用于分布式热电联用系统、甲醇催化重振燃料电池系统、液氨制氢燃料电池系统或风冷燃料电池系统中。The organic phosphonic acid proton exchange membrane can be used in fuel cells. The fuel cell is a high-temperature (120°C to 200°C) proton membrane fuel cell. The high-temperature proton membrane fuel cell can be used in a distributed combined heat and power system, a methanol catalytic revitalization fuel cell system, a liquid ammonia hydrogen production fuel cell system or an air-cooled fuel cell system.
实施例4Example 4
一种有机膦酸质子交换膜的制备方法，包括如下步骤：A method for preparing an organic phosphonic acid proton exchange membrane, including the following steps:
S01、将有机膦酸和碱性物质溶解于去离子水中，得到有机膦酸溶液；所述有机膦酸和所述碱性物质的质量比为0.5：1；以所述有机膦酸溶液的质量为100％计，所述有机膦酸的质量分数为5％；S01. Dissolve organic phosphonic acid and alkaline substances in deionized water to obtain an organic phosphonic acid solution; the mass ratio of the organic phosphonic acid and the alkaline substance is 0.5:1; based on the mass of the organic phosphonic acid solution Based on 100%, the mass fraction of the organic phosphonic acid is 5%;
S02、将氮杂环聚合物膜浸泡于步骤S01的有机膦酸溶液中，于50℃加热36h，真空干燥，得到聚合物膜；S02. Soak the nitrogen heterocyclic polymer film in the organic phosphonic acid solution of step S01, heat at 50°C for 36 hours, and dry under vacuum to obtain a polymer film;
S03、将S02的聚合物膜浸泡于酸溶液中，于100℃加热4h，真空干燥，得到有机膦酸质子交换膜。S03. Soak the polymer membrane of S02 in an acid solution, heat it at 100°C for 4 hours, and dry it under vacuum to obtain an organic phosphonic acid proton exchange membrane.
步骤S01中，In step S01,
所述有机膦酸为四元有机膦酸。所述四元有机膦酸为己二胺四甲叉膦酸。The organic phosphonic acid is a quaternary organic phosphonic acid. The quaternary organic phosphonic acid is hexamethylene diamine tetramethylene phosphonic acid.
所述碱性物质为K2CO3。The alkaline substance is K 2 CO 3 .
所述溶解的温度为25℃。The dissolution temperature is 25°C.
步骤S02中，In step S02,
所述氮杂环聚合物膜为聚吡咯烷酮膜。The nitrogen heterocyclic polymer film is a polypyrrolidone film.
所述真空干燥的温度为150℃；所述真空干燥的时间为12h。The vacuum drying temperature is 150°C; the vacuum drying time is 12 hours.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
步骤S03中，In step S03,
所述酸溶液为含有10wt％酸的酸水溶液。所述酸为磷钨酸。The acid solution is an aqueous acid solution containing 10 wt% acid. The acid is phosphotungstic acid.
所述真空干燥的温度为60℃；所述真空干燥的时间为36h。The vacuum drying temperature is 60°C; the vacuum drying time is 36 hours.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
所述有机膦酸质子交换膜可在燃料电池中进行应用。所述燃料电池为高温(120℃～200℃)质子膜燃料电池。所述高温质子膜燃料电池可用于分布式热电联用系统、甲醇催化重振燃料电池系统、液氨制氢燃料电池系统或风冷燃料电池系统中。The organic phosphonic acid proton exchange membrane can be used in fuel cells. The fuel cell is a high-temperature (120°C to 200°C) proton membrane fuel cell. The high-temperature proton membrane fuel cell can be used in a distributed combined heat and power system, a methanol catalytic revitalization fuel cell system, a liquid ammonia hydrogen production fuel cell system or an air-cooled fuel cell system.
实施例5Example 5
一种有机膦酸质子交换膜的制备方法，包括如下步骤：A method for preparing an organic phosphonic acid proton exchange membrane, including the following steps:
S01、将有机膦酸和碱性物质溶解于去离子水中，得到有机膦酸溶液；所述有机膦酸和所述碱性物质的质量比为3：1；以所述有机膦酸溶液的质量为100％计，所述有机膦酸的质量分数为80％；S01. Dissolve organic phosphonic acid and alkaline substances in deionized water to obtain an organic phosphonic acid solution; the mass ratio of the organic phosphonic acid and the alkaline substance is 3:1; based on the mass of the organic phosphonic acid solution Based on 100%, the mass fraction of the organic phosphonic acid is 80%;
S02、将氮杂环聚合物膜浸泡于步骤S01的有机膦酸溶液中，于100℃加热8h，真空干燥，得到聚合物膜；S02. Soak the nitrogen heterocyclic polymer film in the organic phosphonic acid solution of step S01, heat at 100°C for 8 hours, and dry under vacuum to obtain a polymer film;
S03、将S02的聚合物膜浸泡于酸溶液中，于50℃加热36h，真空干燥，得到有机膦酸质子交换膜。S03. Soak the polymer membrane of S02 in an acid solution, heat it at 50°C for 36 hours, and dry it under vacuum to obtain an organic phosphonic acid proton exchange membrane.
步骤S01中，In step S01,
所述有机膦酸为四元有机膦酸。所述四元有机膦酸为己二胺四甲叉膦酸。The organic phosphonic acid is a quaternary organic phosphonic acid. The quaternary organic phosphonic acid is hexamethylene diamine tetramethylene phosphonic acid.
所述碱性物质为Na2CO3。The alkaline substance is Na 2 CO 3 .
所述溶解的温度为100℃。The dissolution temperature is 100°C.
步骤S02中，In step S02,
所述氮杂环聚合物膜为聚三唑膜。The nitrogen heterocyclic polymer film is a polytriazole film.
所述真空干燥的温度为60℃；所述真空干燥的时间为36h。The vacuum drying temperature is 60°C; the vacuum drying time is 36 hours.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
步骤S03中，In step S03,
所述酸溶液为含有98wt％酸的酸水溶液。The acid solution is an aqueous acid solution containing 98 wt% acid.
所述酸为硅钨酸。The acid is silicotungstic acid.
所述真空干燥的温度为150℃；所述真空干燥的时间为12h。The vacuum drying temperature is 150°C; the vacuum drying time is 12 hours.
所述真空干燥在真空干燥箱中进行。The vacuum drying is performed in a vacuum drying oven.
所述有机膦酸质子交换膜可在燃料电池中进行应用。所述燃料电池为高温(120℃～200℃)质子膜燃料电池。所述高温质子膜燃料电池可用于分布式热电联用系统、甲醇催化重振燃料电池系统、液氨制氢燃料电池系统或风冷燃料电池系统中。The organic phosphonic acid proton exchange membrane can be used in fuel cells. The fuel cell is a high-temperature (120°C to 200°C) proton membrane fuel cell. The high-temperature proton membrane fuel cell can be used in a distributed combined heat and power system, a methanol catalytic revitalization fuel cell system, a liquid ammonia hydrogen production fuel cell system or an air-cooled fuel cell system.
将本申请实施例1至实施例5制备的有机膦酸质子交换膜应用于120℃～200℃的高温质子交换膜燃料电池中，经实验发现，在高温下，本申请制得的有机膦酸质子交换膜具有较好的机械性能、化学稳定性、尺寸稳定性以及低渗氢率，导电性和单电池性能良好，而且使用寿命长，其能够简化水热管理系统，增强CO耐受性，从而能够有效提升能量利用效率。The organic phosphonic acid proton exchange membrane prepared in Examples 1 to 5 of the present application was applied to a high-temperature proton exchange membrane fuel cell of 120°C to 200°C. It was experimentally found that at high temperatures, the organic phosphonic acid prepared in the present application The proton exchange membrane has good mechanical properties, chemical stability, dimensional stability, low hydrogen permeation rate, good electrical conductivity and single cell performance, and long service life. It can simplify the hydrothermal management system and enhance CO tolerance. This can effectively improve energy utilization efficiency.
本申请通过加入碱性物质(如果缺失碱性物质或碱性物质的用量控制不好，会大大影响有机膦酸的掺杂效果，使得有机膦酸不能很好的掺杂到氮杂环聚合物膜中，影响有机膦酸与氮杂环聚合物膜的物理交联作用，进而影响制得的膜的性能)，能够有效溶解有机膦酸，形成高浓度水溶液，使得有机膦酸能够高效、顺利掺杂进入氮杂环聚合物膜中，并与氮杂环聚合物膜的高分子骨架产生物理交联作用。This application adds alkaline substances (if the alkaline substances are missing or the dosage of alkaline substances is not well controlled, it will greatly affect the doping effect of organic phosphonic acid, making it impossible for organic phosphonic acid to be well doped into nitrogen heterocyclic polymers. In the membrane, it affects the physical cross-linking between the organic phosphonic acid and the nitrogen heterocyclic polymer membrane, thereby affecting the performance of the produced membrane), which can effectively dissolve the organic phosphonic acid and form a high-concentration aqueous solution, so that the organic phosphonic acid can be efficiently and smoothly It is doped into the nitrogen heterocyclic polymer film and produces physical cross-linking with the polymer skeleton of the nitrogen heterocyclic polymer film.
制备得到的有机膦酸质子交换膜在高温下仍然具有较强的机械稳定性、低渗氢率、高保酸率和高导电性等特点，可以适用于冷启动、急停、潮湿等多种复杂工况环境，特别适合用于120℃～200℃的高温质子交换膜燃料电池，能够简化水热管理系统，增强CO耐受性，从而能够有效提升能量利用效率。本申请的制备工艺简单易行、操作方便、成本较低、制备时间短，易于实现大规模的工业化生产。并且，本申请制备方法不受限于膜的形态、高分子骨架种类、膜孔隙率、孔径大小等因素，可以作为氮杂环类聚合物膜掺杂酸的通用方法进行应用。The prepared organic phosphonic acid proton exchange membrane still has strong mechanical stability, low hydrogen permeation rate, high acid retention rate and high conductivity at high temperatures, and can be applied to various complex applications such as cold start, emergency stop, and humidity. Working environment, it is especially suitable for high-temperature proton exchange membrane fuel cells of 120°C to 200°C. It can simplify the water and heat management system, enhance CO tolerance, and thus effectively improve energy utilization efficiency. The preparation process of the present application is simple, easy to operate, low in cost, short in preparation time, and easy to realize large-scale industrial production. Moreover, the preparation method of the present application is not limited to factors such as membrane morphology, polymer skeleton type, membrane porosity, pore size, etc., and can be applied as a general method for acid doping of nitrogen heterocyclic polymer membranes.
在本说明书的描述中，参考术语“一实施例”、“示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。In the description of this specification, reference to the terms "an embodiment," "example," etc., means that a particular feature, structure, material or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. middle. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example.
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以适当组合，形成本领域技术人员可以理解的其他实施方式。In addition, it should be understood that although this specification is described in terms of implementations, not each implementation only contains an independent technical solution. This description of the specification is only for the sake of clarity, and those skilled in the art should take the specification as a whole. , the technical solutions in each embodiment can also be appropriately combined to form other implementations that can be understood by those skilled in the art.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310945868.8A CN117133955A (en) | 2023-07-31 | 2023-07-31 | An organic phosphonic acid proton exchange membrane and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310945868.8A CN117133955A (en) | 2023-07-31 | 2023-07-31 | An organic phosphonic acid proton exchange membrane and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117133955A true CN117133955A (en) | 2023-11-28 |
Family
ID=88851825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310945868.8A Pending CN117133955A (en) | 2023-07-31 | 2023-07-31 | An organic phosphonic acid proton exchange membrane and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117133955A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060102463A (en) * | 2005-03-23 | 2006-09-27 | 삼성에스디아이 주식회사 | Manufacturing Method of Fuel Cell Electrolyte, Membrane Electrode Assembly and Fuel Cell Electrolyte |
| CN101775210A (en) * | 2010-01-12 | 2010-07-14 | 山东理工大学 | Preparation method of high-temperature proton conductor composite material |
| CN105789669A (en) * | 2016-05-03 | 2016-07-20 | 武汉理工大学 | Phosphonic acid doped cross-linked sulfonated polyiminobenzimidazole high-temperature proton exchange membrane and preparation method thereof |
| CN109503491A (en) * | 2018-11-12 | 2019-03-22 | 吉林大学 | A kind of imidazole radicals phosphotungstate, preparation method and its preparing the application in proton exchange membrane used for high-temperature fuel cell |
| CN111205641A (en) * | 2020-01-11 | 2020-05-29 | 山东理工大学 | Preparation of Triphosphonate-Doped PBI High-Temperature Proton Exchange Membranes Containing Cyanuric Rings |
| CN115991817A (en) * | 2021-10-18 | 2023-04-21 | 山东东岳未来氢能材料股份有限公司 | Phosphonic acid sulfonic acid copolymer ion exchange membrane and preparation method thereof |
-
2023
- 2023-07-31 CN CN202310945868.8A patent/CN117133955A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060102463A (en) * | 2005-03-23 | 2006-09-27 | 삼성에스디아이 주식회사 | Manufacturing Method of Fuel Cell Electrolyte, Membrane Electrode Assembly and Fuel Cell Electrolyte |
| CN101775210A (en) * | 2010-01-12 | 2010-07-14 | 山东理工大学 | Preparation method of high-temperature proton conductor composite material |
| CN105789669A (en) * | 2016-05-03 | 2016-07-20 | 武汉理工大学 | Phosphonic acid doped cross-linked sulfonated polyiminobenzimidazole high-temperature proton exchange membrane and preparation method thereof |
| CN109503491A (en) * | 2018-11-12 | 2019-03-22 | 吉林大学 | A kind of imidazole radicals phosphotungstate, preparation method and its preparing the application in proton exchange membrane used for high-temperature fuel cell |
| CN111205641A (en) * | 2020-01-11 | 2020-05-29 | 山东理工大学 | Preparation of Triphosphonate-Doped PBI High-Temperature Proton Exchange Membranes Containing Cyanuric Rings |
| CN115991817A (en) * | 2021-10-18 | 2023-04-21 | 山东东岳未来氢能材料股份有限公司 | Phosphonic acid sulfonic acid copolymer ion exchange membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100473693C (en) | Polymer electrolyte and fuel cell using the same | |
| EP2490279B1 (en) | Aromatic polymer ion exchange membrane and its complex membrane and its application for acidic electrolyte flow energy storage battery | |
| CN105131289B (en) | A kind of novel sulfonated polybenzimidazoles copolymer, cross linking membrane, preparation method and applications | |
| CN101814611A (en) | Method for preparing phosphate-doped polybenzimidazole membrane electrode for fuel cell | |
| CN101807678A (en) | Electrolyte membrane and application of composite membrane thereof in liquid-flow energy storage battery with acidic electrolyte | |
| CN101207213A (en) | Method for preparation of organic-inorganic composite type proton exchanging membrane used for high-temperature fuel cell | |
| CN102299353B (en) | Application of Organic-Inorganic Composite Membranes in Acidic Electrolyte Flow Energy Storage Batteries | |
| CN108649255A (en) | Polybenzimidazoles proton exchange membrane and preparation method and application | |
| CN107556247A (en) | A kind of functional form crosslinking agent, preparation method and the phosphate-doped cross-linking type polybenzimidazoles film of height prepared therefrom | |
| CN110993998A (en) | A kind of naphthalene ring-containing polybenzimidazole type proton exchange membrane and its preparation method and application | |
| CN108878933B (en) | Preparation method of Nafion/lignin composite proton exchange membrane | |
| CN105742649B (en) | A kind of high temperature proton exchange film fuel cell membrane electrode and preparation method thereof | |
| CN104743543B (en) | A kind of preparation method of polyaniline/phenolic aldehyde base material with carbon element | |
| CN108912362B (en) | A kind of polyamine functionalized polybenzimidazole cross-linked film and preparation method thereof | |
| CN105742678A (en) | Polymer film applied to flow battery and its preparation method and application | |
| CN109888346A (en) | Preparation method of fuel cell proton exchange membrane using electrospinning technology to support catalyst on membrane fiber surface | |
| CN102146162A (en) | Preparation method and application of polybenzimidazole binder | |
| CN117133955A (en) | An organic phosphonic acid proton exchange membrane and its preparation method and application | |
| CN108134116B (en) | Poly furfuryl alcohol modified fuel cell proton exchange membrane and modification method thereof | |
| Liu | Progress of high temperature polybenzimidazole proton exchange membrane: A systematic review | |
| CN115224333A (en) | Quaternized polybenzimidazole gel type proton exchange membrane with high proton conductivity and stability and preparation method thereof | |
| CN109449468B (en) | Polyfluorene ether ketone-polythiophene fuel cell proton exchange membrane and preparation method thereof | |
| CN115084610B (en) | Proton exchange membrane and preparation method thereof | |
| CN102117920B (en) | Organic-inorganic hybrid proton exchange membrane | |
| CN118919750A (en) | MO modified diaphragm for flow battery and preparation method thereof |
Legal Events
| 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 |