CN108417870B - Organic high-temperature proton exchange membrane and preparation method thereof - Google Patents

Organic high-temperature proton exchange membrane and preparation method thereof Download PDF

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CN108417870B
CN108417870B CN201810206255.1A CN201810206255A CN108417870B CN 108417870 B CN108417870 B CN 108417870B CN 201810206255 A CN201810206255 A CN 201810206255A CN 108417870 B CN108417870 B CN 108417870B
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胡金波
何正标
陈佳孝
祝传贺
邓玲
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Shanghai Institute of Organic Chemistry of CAS
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    • H—ELECTRICITY
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    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
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    • H—ELECTRICITY
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Abstract

The invention relates to an organic high-temperature proton exchange membrane and a preparation method thereof, in particular to a polybenzimidazole compound A, another basic polymer B and an organic polymer cross-linking agent C which are used as raw materials to be compounded, wherein the molar ratio nA to nB of the polybenzimidazole compound A to B is 1:0.01-99.99, and the molar ratio nA to C of the polybenzimidazole compound A to C is 1: 0.01-10.00. The invention also provides a preparation method of the organic high-temperature proton exchange membrane. The organic high-temperature proton exchange membrane has high proton conductivity, high mechanical strength, high thermal stability, high oxidation resistance stability and low swelling ratio, and is very suitable for proton exchange membrane fuel cells.

Description

Organic high-temperature proton exchange membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to an organic high-temperature proton exchange membrane and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are an efficient, environmentally friendly power generation device. The device utilizes clean energy as fuel and can directly and continuously convert the chemical energy of the fuel into electric energy. The power generation process does not involve combustion, so the method is not limited by Carnot cycle, the energy conversion rate is high, the theoretical thermal efficiency can reach 86 percent, and the theoretical thermal efficiency is far higher than that of a traditional heat engine (the thermal efficiency of the traditional heat engine is about 45 percent). Meanwhile, the system has the advantages of high efficiency, small pollution, short factory building time, good reliability and maintainability and the like, is very suitable for various purposes such as transportation, power stations, movable power supply automobiles, submarines and the like, and has wide market prospect. The U.S. government classified it as one of 27 key technology areas critical to U.S. economic development and national safety compliance; the canadian government developed the fuel cell industry as one of the mainstay industries of the national knowledge economy; automobile companies such as GM, Ford, Chryster, Dajmier-Benz in Germany, and Toytomotor in Japan invest a great deal of investment in developing PEMFC automobiles.
A High Temperature Proton Exchange Membrane Fuel cell (HT-PEMFC) has become a trend of development of a Proton Exchange Membrane Fuel cell because it has advantages of active electrochemical reaction, good CO tolerance, High waste heat utilization rate, simple hydrothermal management, and the like. The most central part of the proton exchange membrane fuel cell for realizing high-temperature operation is a high-temperature proton exchange membrane (HT-PEM).
Currently, the high-temperature proton exchange membranes widely used are of the PBI (polybenzimidazole) type, which are doped with inorganic phosphoric acid and used together, with obvious drawbacks: (a) the loss of inorganic phosphoric acid is serious; (b) after the proton exchange membrane is soaked in inorganic phosphoric acid, the mechanical strength is greatly reduced, and the dimensional stability and the service life of the membrane are seriously influenced.
In summary, there is still no high temperature proton exchange membrane with high proton conductivity, high mechanical strength, high thermal stability, high oxidation stability, and long-term stable lifetime.
Disclosure of Invention
The invention aims to provide a high-temperature proton exchange membrane which has high proton conductivity, high mechanical strength, high thermal stability, high oxidation resistance stability and long-term stable service life.
In a first aspect of the present invention, there is provided an organic high temperature proton exchange membrane, which is prepared by compounding a polybenzimidazole compound a, another basic polymer B and an organic polymer crosslinking agent C as raw materials, wherein the molar ratio nA of a to B is 1:0.01 to 99.99, and the molar ratio nA of a to C is 1:0.01 to 10.00.
In another preferred embodiment, the organic polymer cross-linking agent C is selected from the group consisting of:
Figure BDA0001595973260000021
wherein X is Cl or Br; m is 2-10000.
In another preferred embodiment, the polybenzimidazole based polymer a is selected from the group consisting of:
Figure BDA0001595973260000022
wherein n is 2-10000;
p is 0, 1,2 or 3;
r is selected from the group consisting of: none, O, S, NH, C (O), S (O)2Unsubstituted or halogenated C1-C6 alkylene, unsubstituted or halogenated C2-C6 alkenylene;
each R is1Each independently selected from the group consisting of:
Figure BDA0001595973260000031
in another preferred embodiment, the polybenzimidazole type compound a is selected from the group consisting of:
Figure BDA0001595973260000032
wherein R is1As defined above.
In another preferred embodiment, the basic polymer B is selected from the group consisting of:
Figure BDA0001595973260000041
wherein n is 2-10000.
In another preferred embodiment, the molar ratio of a to B, nA: nB, is 1: 0.1-20, and the molar ratio of A to C nC is 1: 0.02-10.00.
In another preferred embodiment, the molar ratio of a to C, nA: nC, is 1:0.02 to 1.00.
In another preferred example, the tensile strength of the organic high-temperature proton exchange membrane is more than 125 MPa.
In another preferred example, the thickness of the organic high-temperature proton exchange membrane is 20 to 40 micrometers.
In another preferred embodiment, the organic high-temperature proton exchange membrane TgIs 290 to 320 ℃.
The second aspect of the present invention provides a method for preparing an organic high temperature proton exchange membrane according to the first aspect, wherein the method for preparing the organic high temperature proton exchange membrane comprises the following steps:
providing a polybenzimidazole type compound A and a basic polymer B;
under the protection of inert gas, dissolving the mixture of the two in an organic solvent, and heating and dissolving to prepare a mixed solution;
adding an organic polymer cross-linking agent C into the mixed solution, and uniformly stirring; preferably, before adding the organic polymer cross-linking agent C, cooling the mixed solution to room temperature (20-40 ℃);
filtering to remove insoluble substances to obtain mixed filtrate;
degassing the mixed filtrate;
and forming a membrane from the mixed filtrate subjected to degassing treatment to obtain the organic high-temperature proton exchange membrane.
In another preferred embodiment, the molar ratio of polybenzimidazole type compound a to basic polymer B is 1: 0.1 to 20, and/or the molar ratio nA of the polybenzimidazole compound A to the organic polymer crosslinking agent C is 1: 0.02-10.0.
In another preferred embodiment, the molar ratio nA of said compound a to said compound C is 1:0.02 to 1.00.
In another preferred embodiment, the organic solvent is a strongly polar organic solvent, and is more preferably selected from the group consisting of: DMSO (dimethyl sulfoxide), DMF (N, N-dimethylformamide), DMAC (N, N-dimethylacetamide), or NMP (N-methylpyrrolidone), or a combination thereof.
In another preferred embodiment, the solid content of the mixed solution is 1-30 wt%; preferably, the solids content of the formulated solution is 1 to 20% by weight.
In another preferred embodiment, the mixed solution after the organic polymer cross-linking agent C is added is stirred for 1 to 10 hours; preferably, stirring is carried out for 1 to 3 hours.
In another preferred embodiment, the film formation comprises: and coating a film on a glass plate or a plastic film and drying to form the organic high-temperature proton exchange membrane.
In another preferred embodiment, the coating method is a casting method.
In another preferred embodiment, the drying includes: after primary drying at 70-90 ℃, heating to 100-140 ℃ for secondary drying, and then heating to 160-300 ℃ for third drying.
In another preferred embodiment, the preliminary drying is performed for 1 to 3 hours, the preliminary drying is performed for 0.5 to 2 hours, and the third drying is performed for 0.5 to 2 hours.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
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FIG. 1 is a comparison graph of proton conductivity of the organic high temperature proton exchange membrane and PBI membrane of the present invention with temperature change. .
Fig. 2 is a graph comparing the proton conductivity of the organic composite high-temperature proton exchange membrane and the PBI membrane of patent application No. 201710084102.X with the temperature change (the numbers of the examples in the figure are the numbers of the examples in the patent).
FIG. 3 is a graph comparing the swelling ratio of the organic high temperature proton exchange membrane and PBI membrane of the present invention with temperature.
Fig. 4 is a graph comparing the swelling ratio of an organic composite high-temperature proton exchange membrane and a PBI membrane of patent application No. 201710084102.X with the change of temperature (the numbers of the examples in the figure are the numbers of the examples in the patent).
Fig. 5 is a cell model.
Fig. 6 is a graph showing the operation stability of the organic high temperature proton exchange membrane No. 6 (example 6) of the present invention, the membrane No. 13 (example 13) of patent 201710084102.X, and the PBI membrane assembled single cell.
Detailed Description
After long-term and intensive research, the inventor of the invention unexpectedly finds that after the polybenzimidazole polymer A and another alkaline polymer B are prepared into a solution, an organic macromolecular cross-linking agent C is added, the solution is uniformly mixed and then cast into a film, and after drying, the high-temperature proton exchange membrane with high proton conductivity, high mechanical strength, high thermal stability, high oxidation resistance stability and low swelling rate can be obtained, so the high-temperature proton exchange membrane is very suitable for being used as a proton exchange membrane of a high-temperature proton conducting membrane fuel cell. Based on the above findings, the inventors have completed the present invention.
Organic high-temperature proton exchange membrane
The invention provides an organic high-temperature proton exchange membrane which is prepared by compounding a polybenzimidazole compound A, another basic polymer B and an organic polymer cross-linking agent C serving as raw materials, wherein the molar ratio nA to nB is 1:0.01-99.99, and the molar ratio nA to nC is 1: 0.01-10.00.
In another preferred embodiment, the polybenzimidazole based polymer a is selected from the group consisting of:
Figure BDA0001595973260000061
wherein n is 2-10000;
r is selected from the group consisting of: none, O, S, NH, C (O), S (O)2Unsubstituted or halogenated C1-C6 alkylene, unsubstituted or halogenated C2-C6 alkenylene;
R1selected from the group consisting of:
Figure BDA0001595973260000071
in another preferred embodiment, the polybenzimidazole type compound a is selected from the group consisting of:
Figure BDA0001595973260000072
wherein R is1As defined above.
In another preferred embodiment, the basic polymer B is selected from the group consisting of:
Figure BDA0001595973260000081
Figure BDA0001595973260000082
wherein n is 2-10000.
In another preferred embodiment, the organic polymer cross-linking agent C is selected from the group consisting of:
Figure BDA0001595973260000083
wherein m is 2-10000
In another preferred embodiment, the molar ratio of a to B, nA: nB, is 1: 0.1-20, and the molar ratio of A to C nC is 1: 0.02-10.00.
Preparation method of organic high-temperature proton exchange membrane
The invention provides a preparation method of an organic high-temperature proton exchange membrane, which comprises the following steps:
providing a polybenzimidazole type compound A and a basic polymer B;
under the protection of inert gas, dissolving the mixture of the two in an organic solvent, and heating and dissolving to prepare a mixed solution with a certain solid content;
cooling the mixed solution to room temperature, adding the organic polymer cross-linking agent C, stirring for two hours, and uniformly stirring;
filtering to remove insoluble substances to obtain mixed filtrate;
degassing the mixed filtrate;
and forming a membrane from the mixed filtrate subjected to degassing treatment to obtain the organic high-temperature proton exchange membrane.
In another preferred embodiment, the molar ratio of polybenzimidazole type compound a to basic polymer B is 1: 0.1 to 20, and/or the molar ratio nA of the polybenzimidazole compound A to the organic polymer crosslinking agent C is 1: 0.02-10.0.
In another preferred embodiment, the organic solvent is a strongly polar organic solvent, and is more preferably selected from the group consisting of: DMSO (dimethyl sulfoxide), DMF (N, N-dimethylformamide), DMAC (N, N-dimethylacetamide), or NMP (N-methylpyrrolidone), or a combination thereof.
In another preferred embodiment, the prepared solution has a solid content of 1-30 wt%.
In another preferred embodiment, the film formation comprises: and coating a film on a glass plate or a plastic film and drying to form the organic high-temperature proton exchange membrane.
In another preferred embodiment, the coating method is a casting method.
In another preferred embodiment, the drying includes: after primary drying at 70-90 ℃, heating to 100-140 ℃ for secondary drying, and then heating to 160-300 ℃ for third drying.
The main advantages of the invention include:
1) compared with the traditional Polybenzimidazole (PBI) type high-temperature proton exchange membrane, the membrane of the invention has higher mechanical strength;
2) compared with the traditional Polybenzimidazole (PBI) type high-temperature proton exchange membrane, the swelling rate of the membrane material is reduced after the membrane material is soaked in inorganic phosphoric acid;
3) compared with the traditional Polybenzimidazole (PBI) type high-temperature proton exchange membrane, the thermal stability and the oxidation resistance stability of the membrane material are obviously enhanced;
4) compared with the traditional Polybenzimidazole (PBI) type high-temperature proton exchange membrane, the polymer membrane has the advantages that the glass transition temperature is increased, and the high-temperature resistant working performance is better;
5) compared with the traditional Polybenzimidazole (PBI) type high-temperature proton exchange membrane, the membrane material of the invention has the advantages that the dimensional stability of the membrane is obviously enhanced under the conditions of heating and oxidation;
therefore, the organic high-temperature proton exchange membrane has higher mechanical strength, higher proton conductivity, higher dimensional stability, higher working stability and durability, and is beneficial to promoting the commercial development of high-temperature fuel cells.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are percentages and parts by weight.
Example 1
m-PBI, poly (N-vinylimidazole) and organic macromolecular crosslinking agent C1(molar ratio 1:1: 0.05) preparation of composite membrane:
Figure BDA0001595973260000101
dried m-PBI (308.4mg,1mmol) and poly (N-vinylimidazole) (94.1mg,1mmol) were weighed out in a molar ratio of 1:1: 0.05. Under the protection of nitrogen, dissolving the mixture of the two in dry DMSO (dimethyl sulfoxide, 7.648g), heating and stirring to prepare a solution with the solid content of 5%, cooling to room temperature, adding organic polymer cross-linking agent C1(26.2mg,0.05mmol), stirring for 2 hours, filtering after uniform stirring, filtering out insoluble substances, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm after degassing treatment, then drying for two hours in a blast oven at the temperature of 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 200 ℃ for drying for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 26 μm (micrometers) and a DSC test showed a glass transition temperature Tg315 ℃, the tensile strength of which is 129MPa as shown by mechanical property tests.
Example 2
p-PBI, poly (2-vinylimidazole) and organic macromolecular crosslinking agent C2(molar ratio 1:0.2: 0.1) preparation of composite membrane:
Figure BDA0001595973260000111
dried p-PBI (308.4mg,1mmol) and poly (2-vinylimidazole) (18.9mg,0.2mmol) were weighed out in a molar ratio of 1:0.2: 0.1. Under the protection of nitrogen, dissolving the mixture of the two in dry DMAC (N, N-dimethylacetamide, 5.126g), heating and stirring to prepare a solution with the solid content of 6%, cooling to room temperature, and adding an organic polymer cross-linking agent C2(67.9mg,0.1mmol), stirring for 2 hours, filtering after uniform stirring, filtering out insoluble substances, carrying out degassing treatment on the filtrate, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm, then placing the glass plate in a blast oven to dry for two hours at the temperature of 80 ℃, further heating to 120 ℃ to dry for one hour, and finally heating to 180 ℃ to dry for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 24 μm (micrometers) and a DSC test showed a glass transition temperature Tg299 ℃, the tensile strength of the material is 128MPa according to the mechanical property test.
Example 3
OO-PBI, poly (N-vinyl pyrazole) and organic polymer cross-linking agent C3(molar ratio 1:2:0.15) preparation of composite membranes:
Figure BDA0001595973260000112
dried OO-PBI (493.6mg,1mmol) and poly (N-vinylpyrazole) (188.2mg, 2.0mmol) were weighed in a molar ratio of 1:2: 0.15. Dissolving the mixture in dry NMP (N-methylpyrrolidone 64.498g) under nitrogen protection, heating and stirring to obtain solution with solid content of 1%, cooling to room temperature, adding organic polymer crosslinking agent C3(90.0mg,0.15mmol), stirring for 2 hr, stirring, filtering, removing insoluble substances, degassing, casting onto glass plate of 10cm × 10cm, drying at 80 deg.C for two hours in a forced air oven, further heating to 120 deg.C for one hour, and finally heating to 250 deg.C for dryingAnd (5) obtaining the organic high-temperature proton exchange membrane after hours. The film had a thickness of 24 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength of the alloy is 120MPa as shown by a mechanical property test at 296 ℃.
Example 4
SO2PBI, poly (5-vinyl triazole) and organic polymer cross-linking agent C4(molar ratio 1:4:0.3) preparation of composite membranes:
Figure BDA0001595973260000121
weighing dried SO at a molar ratio of 1:4:0.32PBI (493.6mg,1mmol) and poly (5-vinyltriazole) (380.4mg,4.0 mmol). Under the protection of nitrogen, dissolving the mixture of the two in dry DMAC (N, N-dimethylacetamide, 16.606g), heating and stirring to prepare a solution with the solid content of 5%, cooling to room temperature, and adding an organic polymer cross-linking agent C4(220.2mg,0.3mmol), stirring for 2 hours, filtering after uniform stirring, filtering out insoluble substances, carrying out degassing treatment on the filtrate, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm, then placing the glass plate in a blast oven to dry for two hours at the temperature of 80 ℃, further heating to 120 ℃ to dry for one hour, and finally heating to 230 ℃ to dry for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 28 μm (micrometers) and a DSC test showed a glass transition temperature Tg299 ℃, the tensile strength of the material is 125MPa according to the mechanical property test.
Example 5
Py-O-PBI, poly (N-vinyl triazole) and organic polymer cross-linking agent C5(molar ratio 1:6:0.1) preparation of composite membranes:
Figure BDA0001595973260000131
dried Py-O-PBI (355.4mg,1mmol) and poly (N-vinyltriazole) (570.6mg,6mmol) were weighed in a molar ratio of 1:6: 0.1. Under the protection of nitrogen, the mixture of the two is dissolved in dry DMF (N, N-dimethylformamide 45.374g), heating and stirring to prepare a solution with the solid content of 2%, cooling to room temperature, and adding an organic polymer cross-linking agent C5(66.4mg,0.1mmol), stirring for 2 hours, filtering after even stirring, filtering out insoluble substances, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm after degassing treatment, then drying for two hours in a blast oven at the temperature of 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 240 ℃ for drying for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 27 μm (micrometers) and a DSC test showed a glass transition temperature Tg298 ℃, the tensile strength of which is 130MPa according to the mechanical property test.
Example 6
O-PBI, poly (1-vinyl-1H-1, 2, 3-triazole) and organic polymer cross-linking agent C6(molar ratio 1:8:0.05) preparation of composite membranes:
Figure BDA0001595973260000132
dried O-PBI (400.5mg,1mmol) and poly (1-vinyl-1H-1, 2, 3-triazole) (760.8mg,8mmol) were weighed in a molar ratio of 1:8: 0.05. Under the protection of nitrogen, dissolving the mixture of the two in dry DMF (N, N-dimethylformamide 37.549g), heating and stirring to prepare a solution with the solid content of 3%, cooling to room temperature, adding an organic polymer cross-linking agent C6(39.9mg,0.05mmol), stirring for 2 hours, filtering after uniform stirring, filtering out insoluble substances, carrying out degassing treatment on the filtrate, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm, then placing the glass plate in a blast oven to dry for two hours at the temperature of 80 ℃, further heating to 120 ℃ to dry for one hour, and finally heating to 210 ℃ to dry for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 33 μm (micrometers) and a DSC test showed a glass transition temperature TgThe mechanical property test shows that the tensile strength is 135MPa at 303 ℃.
Example 7
ABPBI, poly (4-vinylimidazole) and organic polymer cross-linking agent C7(molar ratio 1:10:0.5) compoundingPreparation of the film:
Figure BDA0001595973260000141
dried ABPBI (58.1mg,0.5mmol) and poly (4-vinylimidazole) (470.1mg,5mmol) were weighed out in a molar ratio of 1:10: 0.5. Under the protection of nitrogen, dissolving the mixture of the two in dry DMAC (N, N-dimethylacetamide, 25.901g), heating and stirring to prepare a solution with the solid content of 2%, cooling to room temperature, and adding an organic polymer cross-linking agent C7(47.0mg,0.25mmol), stirring for 2 hours, filtering after uniform stirring, filtering out insoluble substances, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm after degassing treatment, then drying for two hours in a blast oven at the temperature of 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 280 ℃ for drying for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 32 μm (micrometers) and a DSC test showed a glass transition temperature TgThe mechanical property test shows that the tensile strength is 134MPa at 313 ℃.
Example 8
F6PBI, poly (N-methyl-5-vinyl triazole) and organic polymer cross-linking agent C8(molar ratio 1:0.5:0.1) preparation of composite membranes:
Figure BDA0001595973260000142
dry F was weighed in a molar ratio of 1:0.5:0.16PBI (534.0mg,1mmol) and poly (N-methyl-5-vinyltriazole) (54.6mg,0.5 mmol). Dissolving the mixture in dry NMP (N-methylpyrrolidone 14.125g) under nitrogen protection, heating and stirring to obtain solution with solid content of 4%, cooling to room temperature, adding organic polymer crosslinking agent C8(27.8mg,0.1mmol), stirring for 2 hours, stirring well, filtering to remove insoluble substances, degassing, casting onto a glass plate of 10cm × 10cm, drying in a forced air oven at 80 deg.C for two hours, and further heating to 120 deg.CDrying at 260 deg.C for one hour, and drying at 260 deg.C for one hour to obtain the final product. The film had a thickness of 21 μm (micrometers) and a DSC test showed a glass transition temperature TgThe mechanical property test shows that the tensile strength is 134MPa at 307 ℃.
Example 9
OSO2PBI with poly (N-methyl-2-vinylimidazole) and organic macromolecular crosslinker C9(molar ratio 1:5:0.4) preparation of composite membranes:
Figure BDA0001595973260000151
the dry OSO was weighed in a molar ratio of 1:5:0.42PBI (464.1mg,1mmol) and poly (N-methyl-2-vinylimidazole) (540.3mg,5 mmol). Under the protection of nitrogen, dissolving the mixture of the two in dry DMAC (N, N-dimethylacetamide, 24.107g), heating and stirring to prepare a solution with a solid content of 4%, cooling to room temperature, and adding an organic polymer cross-linking agent C9(60.8mg,0.4mmol), stirring for 2 hours, filtering after uniform stirring, filtering out insoluble substances, carrying out degassing treatment on the filtrate, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm, then placing the glass plate in a blast oven to dry for two hours at the temperature of 80 ℃, further heating to 120 ℃ to dry for one hour, and finally heating to 260 ℃ to dry for one hour, thus obtaining the organic high-temperature proton exchange membrane. The film had a thickness of 29 μm (micrometers) and a DSC test showed a glass transition temperature Tg288 ℃, the mechanical property test shows that the tensile strength is 128 MPa.
Example 10
Py-PBI, poly (2-vinyl benzimidazole) and organic polymer cross-linking agent C10(molar ratio 1:20:1) preparation of composite membranes:
Figure BDA0001595973260000152
dried Py-PBI (154.6mg,0.5mmol) and poly (2-vinylbenzimidazole) (14) were weighed in a 1:20:1 molar ratio42.3mg,10 mmol). Under the protection of nitrogen, dissolving the mixture of the two in dry DMF (N, N-dimethylformamide 25.018g), heating and stirring to prepare a solution with the solid content of 6%, cooling to room temperature, adding an organic polymer cross-linking agent C10(76.0mg,0.5mmol), stirring for 2 hours, filtering after even stirring, filtering out insoluble substances, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm after degassing treatment, then drying for two hours in a blast oven at the temperature of 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 250 ℃ for drying for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 39 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength of the alloy is 132MPa as shown by a mechanical property test at 296 ℃.
Example 11
S-PBI, poly (N-methyl-2-vinyl benzimidazole) and organic polymer cross-linking agent C9(molar ratio 1:18:1) preparation of composite membranes:
Figure BDA0001595973260000161
dried S-PBI (208.1mg,0.5mmol) and poly (N-methyl-2-vinylbenzimidazole) (1423.8mg,9mmol) were weighed out in a molar ratio of 1:18: 1. Under the protection of nitrogen, dissolving the mixture of the two in dry DMAC (N, N-dimethylacetamide, 9.247g), heating and stirring to prepare a solution with a solid content of 15%, cooling to room temperature, and adding an organic polymer cross-linking agent C9(76.0mg,0.5mmol), stirring for 2 hours, filtering after even stirring, filtering out insoluble substances, casting the filtrate on a glass plate with the thickness of 10 multiplied by 10cm after degassing treatment, then drying for two hours in a blast oven at the temperature of 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 275 ℃ for drying for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 24 μm (micrometers) and a DSC test showed a glass transition temperature TgThe mechanical property test shows that the tensile strength is 128MPa when the temperature is 301 ℃.
Example 12
Poly [2, 2'- (m-phenylene) -5, 5' -bis (benzimidazolyl) sulfone]With poly (3-vinyl triazole) and organic polymer cross-linking agent C1(molar ratio 1:12:0.4) preparation of composite membranes:
Figure BDA0001595973260000171
weighing dried poly [2,2 '- (m-phenylene) -5, 5' -bis (benzimidazolyl) sulfone in a molar ratio of 1:12:0.4](186.1mg,0.5mmol) and poly (3-vinyltriazole) (570.6mg,6 mmol). Under the protection of nitrogen, dissolving the mixture of the two in dry DMAC (N, N-dimethylacetamide, 14.377g), heating and stirring to prepare a solution with the solid content of 5%, cooling to room temperature, and adding an organic polymer cross-linking agent C1(104.8mg,0.2mmol), stirring for 2 hours, filtering after uniform stirring, filtering out insoluble substances, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm after degassing treatment, then drying for two hours in a blast oven at the temperature of 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 230 ℃ for drying for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 30 μm (micrometers) and a DSC test showed a glass transition temperature Tg289 ℃, and 127MPa tensile strength shown by mechanical property tests.
Example 13
Poly [2,2 '- (m-phenylene) -5, 5' -bis (benzimidazolyl) ketone]With poly (1-vinyl-1, 3, 4-triazole) and organic polymer cross-linking agent C4(molar ratio 1:7:0.3) preparation of composite membranes:
Figure BDA0001595973260000172
weighing dried poly [2,2 '- (m-phenylene) -5, 5' -bis (benzimidazolyl) one in a molar ratio of 1:7:0.3](168.1mg,0.5mmol) and poly (1-vinyl-1, 3, 4-triazole) (332.9mg,3.5 mmol). Under the protection of nitrogen, the mixture of the two was dissolved in dry DMAC (N, N-dimethylacetamide, 16.197g), heated and stirred to prepare a solution with a solid content of 3%, and cooledCooling to room temperature, adding organic polymer cross-linking agent C4(110.1mg,0.15mmol), stirring for 2 hours, filtering after uniform stirring, filtering out insoluble substances, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm after degassing treatment, then drying for two hours in a blast oven at the temperature of 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 240 ℃ for drying for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 29 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength of the alloy is 130MPa according to the mechanical property test at 308 ℃.
Example 14
Poly [2,6- [4 ', 4' -methylene (diphenylmethane)]-benzodiimidazole]With poly (4-vinylpyridine) and an organic macromolecular crosslinking agent C6(molar ratio 1:4:0.1) preparation of composite membranes:
Figure BDA0001595973260000181
the dried poly [2,6- [ 4', 4 "-methylene (diphenylmethane) was weighed in a molar ratio of 1:4:0.1]-Benzodiimidazole](322.4mg,1mmol) and poly (N-vinyltriazole) (420.4mg,4 mmol). Under the protection of nitrogen, dissolving the mixture of the two in dry DMAC (N, N-dimethylacetamide, 6.685g), heating and stirring to prepare a solution with the solid content of 10%, cooling to room temperature, and adding an organic polymer cross-linking agent C6(79.8mg,0.1mmol), stirring for 2 hours, filtering after uniform stirring, filtering out insoluble substances, carrying out degassing treatment on the filtrate, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm, then placing the glass plate in a blast oven to dry for two hours at the temperature of 80 ℃, further heating to 120 ℃ to dry for one hour, and finally heating to 230 ℃ to dry for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 28 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength of the alloy is 127MPa as shown by mechanical property test at 297 ℃.
Example 15
Poly [2,6- [4 ', 4' -phenylene (diphenyl ether)]-benzodiimidazole]Cross-linking with 4, 6-polypyrimidine and organic polymerCoupling agent C2(molar ratio 1:6:0.5) preparation of composite membranes:
Figure BDA0001595973260000191
the dried poly [2,6- [4 ', 4' -phenylene (diphenyl ether) was weighed in a molar ratio of 1:6:0.5]-Benzodiimidazole](324.3mg, 1mmol) and 4, 6-polypyrimidine (468.3mg, 6 mmol). Under the protection of nitrogen, dissolving the mixture of the two in dry DMAC (N, N-dimethylacetamide, 19.022g), heating and stirring to prepare a solution with a solid content of 4%, cooling to room temperature, and adding an organic polymer cross-linking agent C2(339.5mg,0.5mmol), stirring for 2 hours, filtering after even stirring, filtering out insoluble substances, casting the filtrate on a glass plate with the thickness of 10cm multiplied by 10cm after degassing treatment, then drying for two hours in a blast oven at the temperature of 80 ℃, then further heating to 120 ℃ for drying for one hour, and finally heating to 250 ℃ for drying for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 26 μm (micrometers) and a DSC test showed a glass transition temperature TgThe mechanical property test shows that the tensile strength is 130MPa when the temperature is 307 ℃.
Example 16
Poly [2,6- [4 ', 4' -methylene (diphenylmethane)]-benzodiimidazole]With 3, 5-polypyridine and an organic polymer crosslinking agent C3(molar ratio 1:5:0.4) preparation of composite membranes:
Figure BDA0001595973260000192
the dried poly [2,6- [ 4', 4 "-methylene (diphenylmethane) was weighed in a molar ratio of 1:5:0.4]-benzodiimidazole](322.4mg,1mmol) and 3, 5-polypyridine (385.0mg,5 mmol). Under the protection of nitrogen, dissolving the mixture of the two in dry DMAC (N, N-dimethylacetamide, 34.662g), heating and stirring to prepare a solution with the solid content of 2%, cooling to room temperature, and adding an organic polymer cross-linking agent C3(240.0mg,0.4mmol), stirring for 2 hours, stirring well, filtering to remove insoluble substances, filtering to obtain filtrateAnd after degassing treatment, casting the mixture on a glass plate with the thickness of 10cm multiplied by 10cm, then drying the mixture in a blast oven at the temperature of 80 ℃ for two hours, further heating the mixture to the temperature of 120 ℃ for drying for one hour, and finally heating the mixture to the temperature of 260 ℃ for drying for one hour to obtain the organic high-temperature proton exchange membrane. The film had a thickness of 28 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength of the alloy is 134MPa according to the mechanical property test at 316 ℃.
Test examples:
mechanical Property (tensile Strength) test
The test result is shown in each embodiment by the INSTRON-5566 universal material tester.
Proton conductivity test
The proton conductivity Test of the PBI Membrane and, in this application, Membrane No. 4, Membrane No. 5, Membrane No. 6, Membrane No. 7, Membrane No. 9, and Membrane No. 12 was performed by a two-electrode method using a Membrane Test System 740 apparatus.
The test method comprises the following steps:
(1) pretreatment in testing:
and (3) soaking the membranes in 85% phosphoric acid at 60 ℃, taking out and drying after 48 hours of soaking, and testing.
(2) Formal Test (Test equipment Membrane Test System 740):
1. cutting a sample film to be detected into a shape of 1cm multiplied by 3 cm;
2. adhering a GDE with a Pt/C catalyst on the metal sheets of the two electrode clamps by using conductive adhesive, namely, gluing the GDE with the Pt/C catalyst on the metal sheets of the two electrode clamps, arranging the cut membrane to be tested in the middle of the GDE, and clamping the clamps;
3. the MTS740 was powered on and the fixture with the film to be tested was placed in the test chamber of the apparatus.
4. The testing program of the instrument is opened, and the pipeline connecting the gas cylinder and the instrument is connected. Regulating N2The pipeline pressure is 0.5MPa, H2When the pipeline pressure reaches 0.4MPa, the indication of each indicator lamp in the inspection program is normal, and the connection between the chemical workstation and the 740 operation cavity is inspected;
5. when the film sample is initially tested, N should be introduced first2Purging for 10min to remove air from the chamber, purgingThe speed is 500sccm/min, and the test can be started when the temperature and humidity (relative humidity is 2%) reach the set values and are stable during the operation of the instrument.
6. An impedance spectrum is automatically obtained by using an MTS740 program, and a membrane resistance value R is obtained from the spectrum.
7. Data processing: the conductivity is calculated from ρ ═ L/(Rs × a).
L is the film thickness;
rs is membrane resistance for reading impedance spectrum
A is measured area
8. At the end of the test, N must be used2Purging for 15min to remove water vapor in the instrument, and finally turning off the power supply of the instrument and the program.
The results are shown in FIG. 1. The results show that the conductivity of each conductive membrane of the present application is significantly higher than that of the control group PBI and the organic composite high-temperature proton exchange membrane developed before (patent application No. 201710084102.X, the proton conductivity test result is shown in fig. 2, the test method is the same as that of the present application, wherein each embodiment number in fig. 2 is the embodiment number in the patent application).
Swelling Rate test
PBI membrane was measured separately from membrane No. 4, membrane No. 5, membrane No. 6, membrane No. 7, membrane No. 9 and membrane No. 12 (each of which is a reference)
Membranes prepared in example 4, example 5, example 6, example 7, example 9 and example 12).
PBI membrane with No. 4, No. 5, No. 6, No. 7, No. 9, and No. 12 membranes (examples 4, respectively,
Films prepared in example 5, example 6, example 7, example 9 and example 12)) swelling ratio test experiment:
1. cutting each group of membranes to be detected into a shape of 5cm multiplied by 5 cm;
2. measuring the thickness of each film to be measured by using a thickness meter;
3. calculating the initial volume (length x width x thickness) of each group of membranes to be measured;
4. soaking the membranes in 85% phosphoric acid, heating the phosphoric acid to a test temperature, taking out the membranes after the membranes are saturated with the phosphoric acid, and wiping the membranes to dry;
5. measuring the length, width and height of each group of films again;
6. calculating the volume of each group of membranes after swelling;
7. the swelling ratio was calculated (calculation formula is as follows)
Figure BDA0001595973260000211
The test results are shown in fig. 3, and show that the swelling ratio of the conductive membrane in various embodiments of the present application is below 50% (which may be below 30% in some preferred embodiments) at up to 200 ℃, which is much lower than that of the PBI membrane and the organic composite high temperature proton exchange membrane in patent 201710084102.X (the test results are shown in fig. 4; wherein the individual embodiment numbers in fig. 4 are the embodiment numbers in the patent application), indicating that the conductive membrane of the present application has a lower swelling ratio.
Test of working stability
Working stability test of assembled cells of PBI film with film No. 6 (example 6) and film No. 13 in patent 201710084102.X (example 13):
1. film treatment before testing:
a. soaking the membranes in 85% phosphoric acid at 60 deg.C for 48 hr
Drying and testing;
b. cutting the film to be measured into 6.5cm multiplied by 6.5 cm;
preparing MEA (membrane electrode);
a) cutting GDL with model number 29BC from SIGGRACET company into 5 × 5cm size for catalyst spraying;
b) spraying catalyst on the GDL pore layer, wherein the cathode catalyst loading is 2mg/cm2The loading of the anode catalyst is 3mg/cm2Preparing GDE;
c) placing the membrane to be tested in the middle, placing the cathode and anode of GDE on the upper and lower parts respectively, placing into a sandwich structure,
then hot pressing (the hot pressing condition is 135 ℃,10 MPa and 2min) is carried out to obtain MEA;
3. assembling the battery:
the prepared MEA was assembled in a cell model as shown in fig. 5.
4. Single cell testing:
test apparatus Fuel Cell Test System 850e
Connecting the single battery with the testing equipment, and according to the set parameters: anode: hydrogen 500 ml/min; cathode: air 1500 ml/min; and (3) testing temperature: 160 ℃; relative humidity: 2%, constant scan voltage 0.7v. the instrument automatically recorded the current density data under test conditions. The test results are shown in fig. 6.
From the test result (shown in fig. 6), it can be seen that after the cell assembled by the PBI film is tested for more than 900 hours, the performance of the cell assembled by the film No. 13 in the patent 201710084102.X is also reduced to a certain extent, while the performance of the cell assembled by the film No. 6 (example 6) in the application is always stable and not reduced significantly, which indicates that the cell prepared by the conductive film in the application obtains better stability.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims (13)

1. An organic high-temperature proton exchange membrane is characterized in that the organic high-temperature proton exchange membrane is compounded by using (a) a polybenzimidazole type compound A, (B) a basic polymer B and (C) an organic polymer cross-linking agent C as raw materials, wherein the molar ratio nA of A to B is 1:0.5-99.99, and the molar ratio nA of A to C is 1: 0.01-10.00; and is
The organic polymer cross-linking agent C is selected from the following groups:
Figure FDA0002647717960000011
wherein X is Cl or Br; m is 2-10000;
and said basic polymer B is selected from the group consisting of:
Figure FDA0002647717960000012
wherein n is 2-10000.
2. The organic high temperature proton exchange membrane according to claim 1 wherein said organic polymeric cross-linking agent C is selected from the group consisting of:
Figure FDA0002647717960000021
wherein X is Cl or Br; m is 2-10000.
3. An organic high temperature proton exchange membrane according to claim 1 wherein said polybenzimidazole type compound a is selected from the group consisting of:
Figure FDA0002647717960000022
wherein n is 2-10000;
p is 0, 1,2 or 3;
r is selected from the group consisting of: o, S, NH, C (O), S (O)2Unsubstituted or halogenated C1-C6 alkylene, unsubstituted or halogenated C2-C6 alkenylene;
each R is1Each independently selected from the group consisting of:
Figure FDA0002647717960000031
4. the organic high temperature proton exchange membrane according to claim 1 wherein said polybenzimidazole type compound a is selected from the group consisting of:
Figure FDA0002647717960000032
wherein R is1Is as defined in claim 3.
5. An organic high temperature proton exchange membrane according to claim 1 wherein the molar ratio of a to B, nA: nB, is 1: 0.5-20, and the molar ratio of A to C nC is 1: 0.02-10.00.
6. The method of preparing an organic high temperature proton exchange membrane of claim 1, wherein the method of preparing the organic high temperature proton exchange membrane comprises:
providing a polybenzimidazole type compound A and a basic polymer B;
under the protection of inert gas, dissolving the mixture of the two in an organic solvent, and heating and dissolving to prepare a mixed solution;
adding an organic polymer cross-linking agent C into the mixed solution, and uniformly stirring;
filtering to remove insoluble substances to obtain mixed filtrate;
degassing the mixed filtrate;
and forming a membrane from the mixed filtrate subjected to degassing treatment to obtain the organic high-temperature proton exchange membrane.
7. The method according to claim 6, wherein the molar ratio of the polybenzimidazole type compound A to the basic polymer B is 1: 0.5-20, and/or the molar ratio nA of the polybenzimidazole compound A to the organic polymer crosslinking agent C is 1: 0.02-10.0.
8. The method of claim 6, wherein the organic solvent is a strongly polar organic solvent.
9. The method of claim 8, wherein the organic solvent is one or more solvents selected from the group consisting of: dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, or N-methylpyrrolidone.
10. The method according to claim 6, wherein the mixed solution has a solid content of 1 to 30% by weight.
11. The method according to claim 6, wherein the mixed solution has a solid content of 1 to 20 w%.
12. The method according to claim 6, wherein the mixed solution is cooled to room temperature before the organic polymer crosslinking agent C is added.
13. The method of claim 12, wherein the room temperature is 20-40 ℃.
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