阅读说明：本技术 高温质子交换膜及制备方法、电化学设备 (High-temperature proton exchange membrane, preparation method and electrochemical equipment ) 是由 肖丽香 陈春华 陈世明 陈爽 赵国庆 杨旗 王珉 于 2020-11-17 设计创作，主要内容包括：本申请涉及一种用于电化学设备的高温质子交换膜,其特征在于,包括：酸性电解质；聚唑聚合物,占所述高温质子交换膜总重量10％以上。本申请的高温质子交换膜具有优异的化学稳定性以及优异的机械完整性,同时,也有较低的制作成本。(The present application relates to a high temperature proton exchange membrane for an electrochemical device, comprising: an acidic electrolyte; and the polyazole polymer accounts for more than 10 percent of the total weight of the high-temperature proton exchange membrane. The high-temperature proton exchange membrane has excellent chemical stability and mechanical integrity, and simultaneously has lower manufacturing cost.)

1. A high temperature proton exchange membrane for an electrochemical device, comprising:

an acidic electrolyte;

and the polyazole polymer accounts for more than 10 percent of the total weight of the high-temperature proton exchange membrane.

2. A high temperature proton exchange membrane according to claim 1 wherein said polyazole polymer comprises greater than 15% of the total weight of the high temperature proton exchange membrane.

3. A high temperature proton exchange membrane according to claim 1 wherein said acidic electrolyte is selected from polyphosphoric acid.

4. A high temperature proton exchange membrane according to claim 1 wherein said polyazole polymer comprises: a polymer obtained by polymerizing an aromatic tetraamino monomer and a diaminocarboxylic acid monomer, a polymer obtained by polymerizing an aromatic dicarboxylic acid monomer, or a polymer obtained by polymerizing an aromatic tricarboxylic acid and a tetracarboxylic acid monomer.

5. A high temperature proton exchange membrane according to claim 1 wherein said high temperature proton exchange membrane comprises 30% to 55% by weight of polyazole polymer.

6. A high temperature proton exchange membrane according to claim 1 wherein said high temperature proton exchange membrane has a thickness of 25-250 μm.

7. A high temperature proton exchange membrane according to claim 1 wherein said high temperature proton exchange membrane has a proton conductivity of 0.07 to 0.15S/cm.

8. A high temperature proton exchange membrane according to claim 1 wherein said high temperature proton exchange membrane has a young's modulus of 85 to 150 mpa.

9. A preparation method of a high-temperature proton exchange membrane for a fuel cell is characterized by comprising the following steps:

dissolving a polyazole monomer in polyphosphoric acid;

casting a polyazole monomer polyphosphoric acid solution on a flat surface to form a liquid film;

heating the liquid film in air or inert gas atmosphere to enable the liquid film to generate polymerization reaction;

cooling the liquid film after the polymerization reaction;

the cooled liquid film was placed in a phosphoric acid solution.

10. A method of making a high temperature proton exchange membrane according to claim 9 wherein said planar surface comprises:

plates, dishes or electrodes.

Technical Field

The application relates to the field of fuel cells, in particular to a high-temperature proton exchange membrane for a fuel cell, a preparation method thereof and electrochemical equipment.

Background

In recent years, the demand for clean power from non-fossil fuels has increased dramatically. A fuel cell is a chemical device that can directly convert chemical energy of fuel into electric energy, and is also called an electrochemical generator. The fuel cell uses fuel and oxygen as raw materials, and has no mechanical transmission parts, so that the fuel cell has no pollution and discharges few harmful gases. It follows that fuel cells are the most promising power generation technology from the viewpoint of energy conservation and ecological environment conservation.

This need has focused on many technologies, such as proton exchange membrane fuel cells. Currently, proton exchange membrane fuel cells are generally divided into two categories, namely low-temperature proton exchange membrane fuel cells (working temperature is 60-80 ℃) and high-temperature proton exchange membranes (working temperature is 120-160 ℃).

Low temperature pem fuel cells typically use a covalently bonded sulfate group containing fluoropolymer and water as the electrolyte. Currently, the low temperature proton exchange membrane mainly comprises a Nafion membrane of DuPont and a commercial membrane of Aciplex-S membrane of Dow chemical company. The loss of water results in the loss of proton conductivity, so that the operating temperature of the low-temperature proton exchange membrane fuel cell is limited to about 80 ℃.

Compared with the low-temperature proton exchange membrane and the fuel cell thereof, the high-temperature proton exchange membrane and the corresponding fuel cell have the following advantages:

first, the activity of the noble metal catalyst on the electrodes of the pem stack increases in high temperature operating environments. Due to the more effective resistance of noble metal catalysts to carbon monoxide "poisoning" at higher temperatures, the cost of hydrocarbon reforming and purification of fuel cells on natural gas and other hydrocarbon fuels can be effectively simplified and reduced.

Secondly, the use of proton exchange membrane fuel cell electrodes at higher temperatures can also reduce the loading of precious metals in the catalyst layer.

In addition, another advantage of high temperature pem fuel cells is that higher quality heat can be provided. For example, heating at a temperature of 140 ℃ is far more useful and efficient than capturing heat only at 80 ℃, typically only 80 ℃ for low temperature fuel cell operation based on fluoropolymer water film.

In addition, substantially similar systems are generally more electrically efficient when operated at higher temperatures. Based on the above advantages, the high temperature proton exchange membrane fuel cell system has obvious cost advantage.

The above information in the background section is only for enhancement of understanding of the background of the application and therefore it may contain information that does not constitute prior art that is known to a person of ordinary skill in the art.

Disclosure of Invention

The present application provides a high temperature proton exchange membrane for a fuel cell. The films produced by the film polymerization process of the present invention have excellent chemical properties and excellent mechanical integrity.

According to one aspect of the present application, there is provided a high temperature proton exchange membrane for an electrochemical device, comprising: an acidic electrolyte; and the polyazole polymer accounts for more than 10 percent of the total weight of the high-temperature proton exchange membrane.

According to some embodiments of the present application, the polyazole polymer comprises more than 15% of the total weight of the high temperature proton exchange membrane.

According to some embodiments of the present application, the acidic electrolyte is selected from polyphosphoric acid.

According to some embodiments of the present application, the polyazole polymer comprises: a polymer obtained by polymerizing an aromatic tetraamino monomer and a diaminocarboxylic acid monomer, a polymer obtained by polymerizing an aromatic dicarboxylic acid monomer, or a polymer obtained by polymerizing an aromatic tricarboxylic acid and a tetracarboxylic acid monomer. Preferably, the polyazole polymer is a polymer polymerized from an aromatic tetraamino monomer and an aromatic dicarboxylic acid monomer, optionally with the addition of a certain component of a crosslinking agent.

According to some embodiments of the present application, the high temperature proton exchange membrane comprises 30% to 55% by weight of polyazole polymer.

According to some embodiments of the present application, the high temperature proton exchange membrane further comprises a cross-linking agent; the cross-linking agent accounts for 0.06-29% of the weight of the membrane, and preferably the cross-linking agent accounts for 0.09-10% of the weight of the membrane.

According to some embodiments of the present application, the high temperature proton exchange membrane has a thickness of 25-250 μm.

According to some embodiments of the present application, the proton conductivity of the high temperature proton exchange membrane is 0.07-0.15S/cm.

According to some embodiments of the present application, the high temperature proton exchange membrane has a young's modulus in the range of 85-150 megapascals (MPa).

According to another aspect of the present application, there is also provided a method for preparing a high-temperature proton exchange membrane for a fuel cell, including: dissolving a polyazole monomer in polyphosphoric acid; casting a polyazole monomer/polyphosphoric acid solution on a flat surface to form a liquid film; heating the liquid film in air or inert gas atmosphere to enable the liquid film to generate polymerization reaction; cooling the liquid film after the polymerization reaction; the cooled liquid film was placed in a phosphoric acid solution.

According to some embodiments of the present application, the dissolution of the polyazole monomers in the polyphosphoric acid process further comprises adding a crosslinking agent to the polyphosphoric acid process.

According to some embodiments of the application, the planar surface comprises: plates, dishes or electrodes.

According to some embodiments of the present application, the temperature at which the polyazole monomer is dissolved in the polyphosphoric acid is 100-.

According to some embodiments of the present application, the liquid film is heated in the air or inert gas atmosphere for 1-24 hours at a temperature of 200-250 ℃.

According to some embodiments of the present application, placing the cooled liquid film in a phosphoric acid solution is: and putting the cooled liquid film into a phosphoric acid solution with the concentration of 30% -90%.

According to some embodiments of the present application, the cooled liquid film is placed in a 30% -90% phosphoric acid solution at a temperature ranging from 0-100 ℃.

According to another aspect of the present application, there is also provided an electrochemical device comprising a high temperature proton exchange membrane as described above.

The application of the scheme of each embodiment of the application can obtain the high-temperature proton exchange membrane with high solid content, high physical property and high chemical property. These high performance physical characteristics enable the high temperature proton exchange membranes provided herein to be used as proton conductors in membrane-sealed electrode assemblies. Such membranes are also capable of withstanding much higher pressure differentials than the prior art, which are not found in prior art membranes. In addition, the technical scheme of the invention also reduces the manufacturing cost of the membrane electrode. The membrane electrode made using the membrane of the present invention also exhibits superior durability in use.

Drawings

Fig. 1 is a process flow of a method of preparing a high temperature proton exchange membrane according to an example embodiment of the present application.

Detailed Description

In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present application.

In previous studies, a method for preparing a proton exchange membrane has been proposed, which comprises the following steps: firstly, azole monomers are dissolved in polyphosphoric acid; then carrying out high-temperature polymerization on the monomer while stirring the solution in a polymerization reaction vessel; after the polymerization is complete, the very viscous solution is cast on a flat surface and the ready-to-prepare film is then hydrolyzed in an aqueous solution of phosphoric acid of the desired concentration. However, this process, and the films produced therefrom, have considerable limitations, among which are, on the one hand, the problems of the process including the temperature sensitivity during the polymerization. For example, if the entire system within the reactor is gelled near the end of the reaction, the thickness of the subsequently cast film is difficult to control, and the production cost is greatly increased; in addition, even if the polymer is controlled to be less than 5% by weight, gelation easily occurs in such exothermic polymerization reaction.

The present application provides a high temperature proton exchange membrane for a fuel cell and a method for preparing the same, wherein the exchange membrane comprises: an acidic electrolyte; and the polyazole polymer accounts for more than 10 percent of the total weight of the high-temperature proton exchange membrane. The high polymer proportion in the high-temperature proton exchange membrane can improve the mechanical strength of the membrane and prolong the service life of the membrane.

According to an example embodiment of the present application, the acidic electrolyte may be selected from polyphosphoric acid.

According to an exemplary embodiment of the present application, a polyazole polymer includes: a polymer obtained by polymerizing an aromatic tetraamino monomer and a diaminocarboxylic acid monomer, a polymer obtained by polymerizing an aromatic dicarboxylic acid monomer, or a polymer obtained by polymerizing an aromatic tricarboxylic acid or tetracarboxylic acid monomer.

According to an exemplary embodiment of the present application, a polyazole polymer includes: polymers polymerized from one or more aromatic tetraamino monomers and diamino carboxylic acid monomers. Aromatic tetraamino monomers include: 3,3',4,4' -tetraaminobiphenyl; 1,2,4, 5-tetraaminobenzene; 3,3',4,4' -tetraaminodiphenyl sulfone; 3,3',4,4' -tetraaminobenzophenone; 3,3',4,4' -tetraaminodiphenyl ether; 2,3,5, 6-tetraaminopyridine and/or acid salts thereof. The diamino carboxylic acid monomers include: 3, 4-diaminobenzoic acid; 6, 7-diamino-2-naphthoic acid; 3, 4-diamino-4' -carboxybiphenyl; 3, 4-diamino-4' -carboxydiphenyl sulfide; 3, 4-diamino-4' -carboxydiphenyl sulfoxide; 3, 4-diamino-4' -carboxydiphenyl sulfone; 3, 4-diamino-4' -carboxydiphenyl ether; 3, 4-diamino-4' -carboxybenzophenone.

According to an exemplary embodiment of the present application, the aromatic dicarboxylic acid monomer includes: terephthalic acid; isophthalic acid; naphthalene-1, 4-dicarboxylic acid; naphthalene-1, 3-dicarboxylic acid; naphthalene-1, 5-dicarboxylic acid; naphthalene-2, 6-dicarboxylic acid; 4,4' -dicarboxybiphenyl; 3,3' -dicarboxybiphenyl; 3,4' -dicarboxybiphenyl; 4,4' -dicarboxydiphenylsulfone; 3,3' -dicarboxydiphenylsulfone; 3,4' -dicarboxydiphenylsulfone; pyridine-2, 5-dicarboxylic acid; pyridine-2, 4-dicarboxylic acid; pyridine-2, 6-dicarboxylic acid; pyridine-3, 5-dicarboxylic acid.

According to example embodiments of the present application, the aromatic tricarboxylic acid and tetracarboxylic acid monomers include: trimer acid (1,3, 5-tricarboxybenzene), 1,3, 5-tris (4-carboxyphenyl) benzene, 3,5,4 '-tricarboxybiphenyl, 3,5,3',5 '-tetracarboxylbiphenyl, 3,5,4' -tricarboxybiphenyl, 3,5,3 '-tricarboxybiphenyl, 3,5,5' -tetracarboxylbiphenyl, 3,5,4 '-tricarboxybiphenyl sulfone, 3,5,3',5 '-tetracarboxylbiphenyl sulfone, 3,5,4' -tricarboxybenzophenone, 3,5,3',5' -tetracarboxylbenzophenone, naphthalene-1, 4, 5-tricarboxylic acid, naphthalene-1, 4, 6-tricarboxylic acid, naphthalene-1, 4, 7-tricarboxylic acid, naphthalene-1, 3, 5-tricarboxylic acid, naphthalene-1, 3, 6-tricarboxylic acid, naphthalene-1, 3, 7-tricarboxylic acid, naphthalene-1, 3,5, 7-tetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid, piperidine-2, 4, 6-tricarboxylic acid and 1,3, 5-triazine-2, 4, 6-tricarboxylic acid.

Fig. 1 is a process flow of a method of preparing a high temperature proton exchange membrane according to an example embodiment of the present application.

Referring to fig. 1, according to an exemplary embodiment, in S101, a polyazole monomer is dissolved in polyphosphoric acid. Wherein the temperature range of the polyazole monomer dissolving process is controlled at 190 ℃ and 100 ℃, and the solution can be slowly stirred and heated until the solution is completely dissolved. According to some embodiments, dissolving the polyazole monomers in the polyphosphoric acid process further comprises adding a crosslinking agent to the polyphosphoric acid process. In this example, 1,3, 5-tricarboxylic acid benzene can be used as the crosslinking agent.

In S103, the polyazole monomer/polyphosphoric acid solution is cast onto a flat surface, for example, a surface of a plate, a petri dish, an electrode, or the like, to form a liquid film.

In S105, the liquid film is heated in air or an inert gas atmosphere to cause a polymerization reaction of the liquid film. Wherein the liquid film is placed in air or inert gas for heating for 1-24 hours at the temperature of 200-250 ℃.

In S107, the liquid film after the polymerization reaction is cooled.

In S109, the cooled liquid film is placed in a phosphoric acid solution, wherein the cooled liquid film is placed in a phosphoric acid solution having a concentration of 30% to 90%, the temperature ranges from 0 ℃ to 100 ℃, and the concentration of phosphoric acid in the liquid film may be the same as the concentration of the phosphoric acid solution.

The membrane polymerization process can realize the high-temperature proton exchange membrane with higher solid content, and the method adopts a casting mode before polymerization, so that the solution viscosity does not need to be considered in the preparation process, the membrane can be as thin as possible, and the thinner proton exchange membrane can produce a thinner membrane electrode, thereby improving the electric density of the fuel cell.

In order to characterize the excellent properties of the high temperature proton exchange membrane obtained by the above method, the performance of the high temperature proton exchange membrane was tested using the following method.

Composition test method of the membrane:

a circular film having a diameter of 2.5 cm was punched out, and the total weight m of the sample was weighed₀And placed in a beaker containing 100 ml of water. The acid released by the sample was titrated to the first equivalence point with a 0.1 molar fraction of sodium hydroxide solution using a volume of V. The sample was then removed, excess water wiped off and dried at 160 ℃ for 4 hours. The dry weight m of the sample is then measured₁. The composition of the film is described by the following formula:

polymer% ═ m₁/m₀*100

Phosphoric acid%₀*100

Water% — 100-polymer% -phosphoric acid%.

In addition, in order to verify that the high-temperature proton exchange membrane generated by the reaction is polymerized and crosslinked (cross link), a prepared punched sample is subjected to a shaking test under the condition that the sample is placed in concentrated sulfuric acid and is shaken at a certain frequency for 24 hours, and if the sample is not dissolved, the high-temperature proton exchange membrane is polymerized and crosslinked.

The anhydrous proton conductivity test method of the membrane comprises the following steps:

the frequency range was scanned by a four-probe through planar measurements using an ac impedance spectrometer from 1Hz (hertz) to 100KHz (kilohertz). A rectangular film sample (3.5 cm. times.7.0 cm) was placed in a glass or polysulfone cell with four platinum wire electrodes. The two outer electrodes were 6.0cm apart, providing current to the cell, while the two inner electrodes measured the voltage drop relative to the membrane at 2.0cm apart. The proton conductivity is calculated as follows:

σ＝D/(L*B*R)

where D is the distance between the two test current electrodes, L is the thickness of the film, B is the width of the film, and R is the measured resistance. At 180 deg.c, the anhydrous proton conductivity of the film is 0.08-0.15S/cm.

Tensile properties (young's modulus) test method:

the mechanical properties of the films were measured by cutting a dog-bone type pattern (ASTM D683v type) from the films using a shear press. Tensile properties were measured using a tensile tester. All measurements were performed at room temperature.

The membrane electrode assembly manufacturing and performance testing method comprises the following steps:

membrane electrode assemblies consist of a polymer membrane sandwiched between two electrodes. The membrane prepared in the example of the present application was hot-pressed between the anode and the cathode at 150 c and 2000 kg for 90-150 seconds to prepare a membrane electrode. Electrode load 1.0mg/cm²A platinum (Pt) catalyst. The fuel cell is manufactured by assembling the following cell components: an end plate; an anode current collector; an anode flow field; a membrane electrode; a cathode flow field; a cathode current collector; and an end plate. Gaskets are used on both sides of the membrane electrode to control compression. After assembly, the cells were uniformly tightened.

The performance of the Fuel Cell was tested at 50cm using a testing station purchased from Fuel Cell Technologies, Inc²(effective area 45.15cm²) A single stack of fuel cells. With hydrogen as fuel and different oxidants (air or oxygen), polarization curves were obtained at different temperatures. Prior to measuring the polarization curve, the fuel cell was operated at a temperature of 180 ℃ and 0.2A/cm²(amps/cm) for at least 100 hours (break-in period). At a constant flow of hydrogen (1.2 stoichiometry) and air (2.0 stoichiometry) at 0.2A/cm²And a long-term stability test is carried out at a temperature of 180 ℃.

Example one:

3, 4-diaminobenzoic acid (15.215 g) and polyphosphoric acid (86.2 g) were added to a 250 ml three-neck flask, stirred and heated to 150 ℃ for 2 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 220 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a 65% phosphoric acid bath at room temperature and hydrolyzed for 4 hours to obtain a film. The film thickness was 95 μm.

The composition of the membrane in this example was 49.2 wt% polymer, 18.7 wt% water and 32.1 wt% phosphoric acid. The proton conductivity was 0.08S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 130 MPa (MPa).

The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 180 ℃ and 0.2A/cm²Shows a fuel cell performance of 0.54V (volts) and a maximum power density of 0.35W/cm²(watts/square centimeter). A back pressure of 45psi (lb/ft) was used²Pounds per square foot) of hydrogen and air at a back pressure of 0psi were further tested against the membrane electrode provided in the present application, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm²The cell was operated continuously for 480 hours with constant operation without any film failure traces.

Example two:

3,3',4,4' -tetramine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (6.645 g) and polyphosphoric acid (136.9 g) were added to a 250 ml three-necked flask, stirred and heated to 170 ℃ for 6 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 250 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a 70% phosphoric acid bath at room temperature and hydrolyzed for 4 hours to obtain a film. The film thickness was 90 microns.

The composition of the membrane in this example was 32.3 wt% polymer, 20.4% water and 47.3 wt% phosphoric acid. The proton conductivity was 0.12S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 92 MPa (MPa).

The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 180 ℃ and 0.2A/cm²Shows a fuel cell performance of 0.60V at a maximum power density of 0.4W/cm². The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm²The cell was operated continuously for 480 hours with constant operation without any film failure traces.

Example three:

3,3',4,4' -tetramine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (6.313 g), 1,3, 5-tricarboxylic acid benzene (0.280 g) and polyphosphoric acid (136.5 g) were added to a 250 ml three-necked flask, stirred and heated to 170 ℃ for 4 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 240 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a 70% phosphoric acid bath at room temperature and hydrolyzed for 4 hours to obtain a film. The film thickness was 100 microns.

The membrane composition in this example was 33.9 wt% polymer, 24.2 wt% water and 41.9 wt% phosphoric acid. The proton conductivity was 0.11S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 132 MPa (MPa).

From the membrane electrode of the membrane member in this example, the hydrogen gas/air stoichiometric ratioAt (1.2): (2.0), 180 deg.C and 0.2A/cm²Shows a fuel cell performance of 0.58V and a maximum power density of 0.38W/cm². The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm²The cell was operated continuously for 480 hours with constant operation without any film failure traces.

Example four:

3,3',4,4' -tetramine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (0.831 g), isophthalic acid (5.814 g) and polyphosphoric acid (136.9 g) were added to a 250 ml three-neck flask, stirred and heated to 190 ℃ for 2 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 250 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a 60% phosphoric acid bath at room temperature and hydrolyzed for 4 hours to obtain a film. The film thickness was 97 μm.

The composition of the membrane in this example was 31.8 wt% polymer, 27.5 wt% water and 40.7 wt% phosphoric acid. The proton conductivity was 0.10S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 113 MPa (MPa).

The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 200 ℃ and 0.2A/cm²Shows a fuel cell performance of 0.61V at a maximum power density of 0.46W/cm². The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm²The cell was operated continuously for 480 hours with constant operation without any film failure traces.

Example five:

3,3',4,4' -tetraamine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (0.789 g), isophthalic acid (5.524 g), 1,3, 5-tricarboxylic acid benzene (0.280 g) and polyphosphoric acid (136.5 g) were added to a 250 ml three-neck flask, stirred and heated to 190 ℃ for 2 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 250 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a room-temperature 50% phosphoric acid bath and hydrolyzed for 4 hours to obtain a film. The film thickness was 94 μm. The composition of the membrane in this example was 33.8 wt% polymer, 32.4% water and 33.8 wt% phosphoric acid. The proton conductivity was 0.10S/cm (180 ℃ C.). Young's modulus at room temperature was 130 MegaPascals (MPa).

The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 180 ℃ and 0.2A/cm²Shows a fuel cell performance of 0.58V and a maximum power density of 0.38W/cm². The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm²The cell was operated continuously for 480 hours with constant operation without any film failure traces.

Example six:

3,3',4,4' -tetramine-1, 1 ' -biphenyl (8.571 g), 2, 5-dihydroxyterephthalic acid (0.941 g), isophthalic acid (5.524 g), 1,3, 5-tricarboxylic acid benzene (0.280 g) and polyphosphoric acid (137.8 g) were added to a 250 ml three-necked flask, stirred and heated to 190 ℃ for 2 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 250 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a room-temperature 50% phosphoric acid bath and hydrolyzed for 4 hours to obtain a film. The film thickness was 102 μm.

The composition of the membrane in this example was 33.5 wt% polymer, 32.6 wt% water and 33.9 wt% phosphoric acid. The proton conductivity was 0.12S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 136 MPa (MPa).

The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 220 ℃ and 0.2A/cm²Shows a fuel cell performance of 0.65V, maximum workThe specific density is 0.49W/cm². The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm²The cell was operated continuously for 480 hours with constant operation without any film failure traces.

Comparative example 1:

3,3',4,4' -tetramine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (6.645 g) and polyphosphoric acid (136.9 g) were added to a 250 ml three-necked flask, stirred and heated to 220 ℃ for 5 hours. The solution was highly viscous and could not be cast into a film, so there was no thickness measurement. Part of the polymer is crosslinked into solid state and gelated.

Comparative example 2:

3,3',4,4' -tetraamine-1, 1 ' -biphenyl (4.268 g), terephthalic acid (3.323 g) and polyphosphoric acid (275 g) were added to a 250 ml three-necked flask, heated to 220 ℃ with stirring, and left for 5 hours. The polymer was cooled to room temperature of 30 ℃ and the intrinsic viscosity of the polymer was 8dl/g as measured by viscosity. The glass plate and the film obtained thereon were immersed in a 65% phosphoric acid bath at room temperature, and hydrolyzed for four hours to obtain a film. The film thickness was 95 μm.

The composition of the membrane in comparative example 2 was 4.9% polymer, 38.7% water by weight, and 56.4% phosphoric acid by weight. The proton conductivity was 0.18S/cm (180 ℃ C.) and the Young' S modulus at room temperature was 30 MegaPascals (MPa).

The membrane electrode of the membrane structure produced in comparative example 2 was fabricated at a hydrogen-to-air stoichiometric ratio of (1.2): (2.0), 180 ℃ and 0.2A/cm²Shows a fuel cell performance of 0.65V at a maximum power density of 0.5W/cm². The membrane electrode provided in the present application described above was further tested using hydrogen at a back pressure of 45psi and air at a back pressure of 0psi, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm²The battery was continuously operated for 2 hours with constant operation, and the membrane member was broken.

Comparative example 3:

3,3',4,4' -tetramine-1, 1 ' -biphenyl (8.571 g), terephthalic acid (6.645 g) and polyphosphoric acid (60.9 g) were added to a 250 ml three-necked flask, stirred and heated to 150 ℃ for 2 hours. The reaction solution was poured onto a glass plate, and cast using a gardner blade to control the liquid film thickness. The glass plate and the cast solution were transferred to an oven and heated at 220 ℃ for 12 hours in a nitrogen atmosphere. After cooling to room temperature, the glass plate and the film obtained thereon were immersed in a 65% phosphoric acid bath at room temperature and hydrolyzed for 4 hours to obtain a film. The film thickness was 98 μm.

The composition of the membrane in this example was 65.1 wt% polymer, 12.1 wt% water and 22.8 wt% phosphoric acid. The proton conductivity was 0.02S/cm (180 ℃ C.), and the Young' S modulus at room temperature was 149 MPa (MPa).

The membrane electrode composed of the membrane member in this example had a hydrogen/air stoichiometric ratio of (1.2): 2.0), 180 ℃ and 0.2A/cm²Shows a fuel cell performance of 0.2V (volts) and a maximum power density of 0.08W/cm²(watts/square centimeter). A back pressure of 45psi (lb/ft) was used²Pounds per square foot) of hydrogen and air at a back pressure of 0psi were further tested against the membrane electrode provided in the present application, thereby applying a pressure differential of 45psi across the membrane. At 0.2A/cm²The cell was operated continuously for 480 hours with constant operation without any film failure traces.

The experiments show that the high-temperature proton exchange membrane prepared by the method has high mechanical property, excellent chemical property and durability. Due to the reduction of the manufacturing cost, the cost of the high-temperature proton exchange membrane provided by the application is also reduced.

The above description is only for the purpose of illustrating the preferred embodiments of the present application and is not to be construed as limiting the present application, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present application should be included in the scope of the present application.