CN112018418B - High-temperature modified polybenzimidazole proton exchange membrane and preparation method thereof - Google Patents
High-temperature modified polybenzimidazole proton exchange membrane and preparation method thereof Download PDFInfo
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- 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
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- 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
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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- 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
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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Abstract
The invention discloses a high-temperature modified polybenzimidazole proton exchange membrane and a preparation method thereof, wherein the preparation method comprises the following steps: s1, dissolving polybenzimidazole in an organic solvent to form a polybenzimidazole solution with the concentration of 0.15-0.45 mol/L; s2, pouring the polybenzimidazole solution on a template to form a film, and drying to obtain a film; s3, placing the film in a mixed solution of phosphoric acid and phosphotungstic acid for acidic modification; and S4, drying the acidic modified film in a vacuum environment to obtain the high-temperature modified polybenzimidazole proton exchange membrane. The invention realizes the low-cost, high-efficiency and large-scale commercial production of the high-temperature proton exchange membrane.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a high-temperature modified polybenzimidazole proton exchange membrane and a preparation method thereof.
Background
With the development and popularization of renewable clean energy power generation technology, a proton exchange membrane fuel cell power generation mode is the best option, has the advantages of strong environmental adaptability, high energy density, capacity of cogeneration, excellent low-temperature performance, high conversion efficiency, no noise, low radiation and the like, and is generally accepted as the best power source of traffic equipment and portable electronics. The proton exchange membrane is a core component of the proton exchange membrane fuel cell and plays a key role in the performance of the fuel cell. In order to solve the technical problem of high cost of the current fuel cell, it is urgent to develop a proton exchange membrane material with low cost and long service life.
The common exchange membrane of the fuel cell is a perfluorosulfonic acid membrane electrolyte membrane (such as a product of gore corporation, komon corporation), and the normal operating temperature must be maintained at 60-80 ℃ because the proton conductivity of the exchange membrane is strongly correlated with the water content. The temperature is too low, the electrochemical reaction rate is low, and the battery power is low. When the fuel cell works at 100 ℃, the wettability of the proton exchange membrane is sharply reduced, so that the internal resistance of the proton exchange membrane is increased, the power performance of the fuel cell is sharply reduced, and the service life of the proton exchange membrane is sharply reduced while the power of the fuel cell is reduced. Therefore, the proton exchange membrane represented by the perfluorinated sulfonic acid proton exchange membrane has the characteristics of strong correlation between the proton conductivity and the water content and temperature, and limits the working conditions of the cell, so that the working temperature of the proton exchange membrane fuel cell is in the range of 60-80 ℃. The working temperature of 60-80 ℃ brings about a plurality of technical problems: firstly, at 80 ℃, water in the battery exists in a gas-liquid two-phase state, the problems of unstable battery performance and reliability caused by the instability of the gas-liquid two-phase state become technical problems, the gas-liquid two-phase flow is quite complex, and the problem difficulty is increased by coupling with an electrode process. Second, when the temperature is lower than 80 ℃, the electrochemical reaction rate of the fuel cell is low, and the cathode electrochemical polarization is relatively serious, which affects the performance of the cell catalyst. Thirdly, the difference between the working temperature of 60-80 ℃ and the ambient temperature is not large, so that the fuel cell is not beneficial to the intense diffusion of heat, the requirement on a cooling system is increased, and the volume power density of the cell can be reduced by a cooling part.
The high-temperature modified proton exchange membrane fuel cell can thoroughly solve the problems of the low-temperature fuel cell, and comprises the following components: 1. the water of the cell reaction product exists in a gaseous state, which is beneficial to simplifying the heat management; 2. the humidification requirement on the exchange membrane is reduced; 3. the electrode reaction speed is improved, and the electrochemical polarization overpotential of the cathode is effectively reduced. In addition, the high-temperature proton exchange membrane fuel cell simplifies a cooling system of the fuel cell to a certain extent and improves the energy density of the fuel cell. High temperature proton exchange membranes are therefore the focus of current research and development. The modified polybenzimidazole proton exchange membrane is taken as an important large class of high-temperature proton exchange membranes, is paid considerable attention, and is the key work of the next generation of fuel cells.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-temperature modified polybenzimidazole proton exchange membrane and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the high-temperature modified polybenzimidazole proton exchange membrane comprises the following steps:
s1, dissolving polybenzimidazole in an organic solvent to form a polybenzimidazole solution with the concentration of 0.15-0.45 mol/L;
s2, pouring the polybenzimidazole solution on a template to form a film, and drying to obtain a film;
s3, placing the film in a mixed solution of phosphoric acid and phosphotungstic acid for acidic modification;
and S4, drying the acidic modified film in a vacuum environment to obtain the high-temperature modified polybenzimidazole proton exchange membrane.
Preferably, in step S1, the polybenzimidazole has a number average molecular weight of 15000-40000.
Preferably, in step S1, polybenzimidazole is dissolved in an organic solvent at 40 to 75 ℃;
the organic solvent is one or more of dimethyl sulfoxide, N-dimethylacetamide and dimethylformamide.
Preferably, in step S2, the film has a thickness of 10 to 15 μm.
Preferably, in step S2, the surface temperature of the template is 40 to 60 ℃ during casting; controlling the film forming speed to be 10 cm/min-25 cm/min;
the drying temperature is 40-80 ℃ and the drying time is 4-8 h.
Preferably, in step S2, the cast product is dried under infrared drying lamp or microwave.
Preferably, in step S3, the phosphoric acid and phosphotungstic acid mixed solution is a saturated solution formed by dissolving phosphotungstic acid in a phosphoric acid solution with a mass concentration of 85%;
the temperature of the acid modification is 35-65 ℃, and the time is 4-6 h.
Preferably, the step S3 is performed in a closed environment.
Preferably, in step S4, the degree of vacuum is-0.0.08 MPa to 0.1 MPa.
Preferably, in step S4, the film is placed in a vacuum oven and dried at 60-100 ℃ for 6-8 h.
Preferably, step S2 further includes: and placing the film in a vacuum oven for aging treatment.
The invention also provides a high-temperature modified polybenzimidazole proton exchange membrane prepared by the preparation method.
The invention has the beneficial effects that: 1. compared with the traditional proton exchange membrane, the process is simplified, the conditions are moderate, nitrogen protection is not needed, the cost is low, and the method is more favorable for commercial large-scale application; 2. compared with the prior phosphoric acid treatment technology, the method reduces the loss of phosphoric acid micromolecules from a proton exchange membrane, thereby having good proton conduction stability; the linear swelling rate of the obtained proton exchange membrane is less than 3 percent. 3. As a result of purification, the structure of the membrane is uniform, and the obtained proton exchange membrane has good mechanical capacity (the tensile strength reaches 30-50 MPa). The proton conductivity reaches 0.02-0.004S/cm when tested under the national standard.
The invention realizes the low-cost, high-efficiency and large-scale commercial production of the high-temperature proton exchange membrane, can be beneficial to the localization of the fuel cell industry and is beneficial to the autonomous process and the income of the membrane electrode enterprise.
Detailed Description
The preparation method of the high-temperature modified polybenzimidazole proton exchange membrane comprises the following steps:
s1, dissolving the polybenzimidazole in an organic solvent to form a polybenzimidazole solution with the concentration of 0.15-0.45 mol/L.
Wherein, the polybenzimidazole is dissolved in an organic solvent with the temperature of 40-75 ℃ and is purified. The organic solvent is one or more of dimethyl sulfoxide, N-dimethylacetamide and dimethylformamide.
The number average molecular weight of polybenzimidazole is 15000-40000. Polybenzimidazole is dissolved in an organic solvent to form a polybenzimidazole solution, so that a polymer body with uniform molecular weight is obtained.
And S2, pouring the polybenzimidazole solution on the template to form a film, and drying to obtain the film.
The template can be a flat plate, and further can be a glass flat plate with smooth surface; cleaning and drying are needed before pouring.
During pouring, the surface temperature of the template is kept between 40 and 60 ℃ so as to keep the temperature consistent with that of the polybenzimidazole solution; the film forming speed is controlled to be 10 cm/min-25 cm/min.
After the pouring is finished, the template with the film can be placed under an infrared drying lamp or microwave for drying. The drying temperature is 40-80 ℃, the drying time is 4-8 h, the thickness of the film is controlled to be uniform, and the temperature is kept to be uniformly dispersed. The thickness of the membrane is preferably 10 μm to 15 μm to ensure a small proton transfer resistance.
In order to avoid environmental pollution, the pouring, drying and the like are carried out in an isolated space.
Further, step S2 further includes: and (3) placing the film in a vacuum oven for aging treatment. The aging temperature can be 80 ℃, and can be increased or decreased according to the actual situation, and the time is determined according to the actual situation.
After the completion, the film is peeled off from the template for subsequent treatments such as acidic modification.
S3, placing the film in a mixed solution of phosphoric acid and phosphotungstic acid for acidic modification.
Wherein the mixed solution of phosphoric acid and phosphotungstic acid is a saturated solution formed by dissolving phosphotungstic acid in a phosphoric acid solution with the mass concentration of 85%.
And immersing the film into a mixed solution of phosphoric acid and phosphotungstic acid for acidic modification. The acidity modification is carried out in a closed environment, so that the influence of impurities, moisture and the like in the air on the acidity of the mixed solution is avoided, and the modification effect is further influenced. The temperature of the acid modification is 35-65 ℃, and the time is 4-6 h.
And the film is endowed with heat conduction and electric conduction performances through acidic modification treatment.
And S4, drying the acidic modified film in a vacuum environment to obtain the high-temperature modified polybenzimidazole proton exchange membrane.
Wherein, drying is carried out in a vacuum environment, so as to avoid the surface of the film from being oxidized and influencing the conductive capability. The vacuum degree can be-0.0.08 MPa to 0.1MPa, and is preferably-0.1 MPa.
Alternatively, the film is placed in a vacuum oven and dried at 60-100 ℃ for 6-8 h.
The present invention is further illustrated by the following specific examples.
Example 1
1) Polybenzimidazole (number average molecular weight 20000, amount of structural unit substance 0.0015mol, 0.4596g) was dissolved in N, N-dimethylacetamide organic solvent at a molar concentration of 0.15 mol/L: firstly weighing 0.4596g of benzimidazole polymer powder with uniform granularity; dripping a dropper into the N, N-dimethylacetamide solvent with the temperature of 40 ℃, and keeping the constant temperature for 3 hours to obtain a polymer body with uniform molecular weight.
2) And pouring the glass flat plate to form a film. Before pouring, cleaning the glass flat plate by absolute ethyl alcohol, then drying, keeping the surface temperature at 40 ℃, pouring the solution obtained in the step 1) in a constant temperature state, and controlling the film forming speed to be 10 cm/min.
3) After the completion, under the action of an infrared drying lamp, the mixture is quickly dried, the temperature is controlled to be 40 ℃, and the mixture is kept for 6 hours. Then transferring the mixture to a vacuum oven, and aging the mixture for 4 hours at 80 ℃ under a certain vacuum degree.
4) After film forming, the film is placed in a mixed saturated solution of phosphoric acid and phosphotungstic acid for acidic soaking modification in a closed environment. And after the modification is finished, putting the membrane into a vacuum oven, and curing at 85 ℃ for 4 hours under a certain vacuum degree to obtain the high-temperature modified polybenzimidazole proton exchange membrane.
Through tests, the linear swelling coefficient of the proton exchange membrane prepared by the embodiment at normal temperature is 2.8%, the tensile strength is 38MPa, and the proton conductivity is 0.028S/cm measured according to the national standard requirements.
Example 2
1) Polybenzimidazole (number average molecular weight 15000, amount of constitutional unit substance 0.002mol, 0.6164g) was dissolved in N, N-dimethylacetamide organic solvent at a molar concentration of 0.2 mol/L: 0.6164g of benzimidazole polymer powder is weighed, dropwisely added into 40mL of N, N-dimethylacetamide solvent at 40 ℃ by a dropper while the benzimidazole polymer powder is hot, and kept for 3 hours at constant temperature to obtain a polymer body with uniform molecular weight.
2) And pouring the glass flat plate to form a film. Before pouring, cleaning the glass flat plate by absolute ethyl alcohol, then drying, keeping the surface temperature at 45 ℃, and pouring the solution obtained in the step 1) in a constant temperature state.
3) After the completion, the mixture is quickly dried under the action of an infrared drying lamp, the temperature is controlled to be 40 ℃, the mixture is kept for 5 hours, and then the mixture is transferred to a vacuum oven, and is aged for 6 hours at 80 ℃ under a certain vacuum degree.
4) After film forming, the film is placed in a mixed saturated solution of phosphoric acid and phosphotungstic acid for acidic soaking modification in a closed environment. And after the modification is finished, putting the membrane into a vacuum oven for curing treatment at 105 ℃ for 4 hours to prepare the high-temperature modified polybenzimidazole proton exchange membrane.
Through tests, the linear swelling coefficient of the proton exchange membrane prepared by the embodiment at normal temperature is 2.46%, the tensile strength is 40MPa, and the proton conductivity is 0.026S/cm measured according to the national standard requirements.
Example 3
1) Polybenzimidazole with the number average molecular weight of 25000 and the amount of structural unit substances of 0.0015mol, 0.3750g is dissolved in N, N-dimethylacetamide organic solvent at the molar concentration of 0.15 mol/L: 0.3750g of benzimidazole polymer powder is weighed firstly, a dropper is used for dropwise adding into 45mL of N, N-dimethylacetamide solvent at the temperature of 40 ℃, the constant temperature is kept for 2.5h, and a polymer body with uniform molecular weight is obtained.
2) And pouring the glass flat plate to form a film. Before pouring, cleaning the glass flat plate by absolute ethyl alcohol, then drying, keeping the surface temperature at 50 ℃, quickly pouring the solution in the step 1) in a constant temperature state.
3) After the completion, the mixture is quickly dried under the action of an infrared drying lamp, the temperature is controlled to be 50 ℃, the mixture is kept for 6 hours, and then the mixture is transferred to a vacuum oven, and is aged for 6 hours at 80 ℃ under a certain vacuum degree.
4) After film forming, the film is placed in a mixed saturated solution of phosphoric acid and phosphotungstic acid for acidic soaking modification in a closed environment. After the modification is finished, the mixture is put into a vacuum oven and is cured at 75 ℃ under a certain vacuum degree. The treatment time is 5h, and the high-temperature modified polybenzimidazole proton exchange membrane is prepared.
Through tests, the linear swelling coefficient of the proton exchange membrane prepared in the embodiment at normal temperature is 3.16%, the tensile strength is 47MPa, and the proton conductivity is 0.018S/cm according to the national standard requirements.
Example 4
1) 0.4500g of polybenzimidazole (average molecular weight 30000, amount of structural unit substance 0.0015mol) was dissolved in N, N-dimethylacetamide organic solvent at a molar concentration of 0.15 mol/L: 0.4500g of benzimidazole polymer powder is weighed firstly, a dropper is used for dropwise adding into 40mL of N, N-dimethylacetamide solvent at 40 ℃, the constant temperature is kept for 4 hours, and a polymer body with uniform molecular weight is obtained.
2) And pouring the glass flat plate to form a film. Before coating, cleaning the glass flat plate by absolute ethyl alcohol, then drying, keeping the surface temperature at 55 ℃, quickly pouring the solution obtained in the step 1) in a constant temperature state.
3) After the completion, the mixture is quickly dried under the action of an infrared drying lamp, the temperature is controlled to be 55 ℃, the mixture is kept for 6 hours, and then the mixture is transferred to a vacuum oven, and is aged for 6 hours at 80 ℃ under a certain vacuum degree.
4) After film forming, the film is placed in a mixed saturated solution of phosphoric acid and phosphotungstic acid for acidic soaking modification in a closed environment. And after the modification is finished, putting the membrane into a vacuum oven, and curing at 85 ℃ for 4 hours under a certain vacuum degree to obtain the high-temperature modified polybenzimidazole proton exchange membrane.
Through tests, the linear swelling coefficient of the proton exchange membrane prepared in the embodiment at normal temperature is 2.9%, the tensile strength is 55MPa, and the proton conductivity is 0.04S/cm according to the national standard requirements.
In conclusion, the high-temperature modified polybenzimidazole proton exchange membrane has good proton conduction stability and linear swelling rate of less than 3 percent, and is suitable for working environments with the temperature of more than 80 ℃.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (9)
1. A preparation method of a high-temperature modified polybenzimidazole proton exchange membrane is characterized by comprising the following steps:
s1, dissolving polybenzimidazole in an organic solvent to form a polybenzimidazole solution with the concentration of 0.15-0.45 mol/L;
s2, pouring the polybenzimidazole solution on a template to form a film, and drying to obtain a film;
s3, placing the film in a mixed solution of phosphoric acid and phosphotungstic acid for acidic modification, wherein the mixed solution of phosphoric acid and phosphotungstic acid is a saturated solution formed by dissolving phosphotungstic acid in a phosphoric acid solution with the mass concentration of 85%, and the acidic modification temperature is 35-65 ℃ and the acidic modification time is 4-6 h;
and S4, drying the acidic modified film in a vacuum environment to obtain the high-temperature modified polybenzimidazole proton exchange membrane.
2. The method as claimed in claim 1, wherein in step S2, the polybenzimidazole has a number average molecular weight of 15000-40000;
dissolving polybenzimidazole in an organic solvent at the temperature of 40-75 ℃; the organic solvent is one or more of dimethyl sulfoxide, N-dimethylacetamide and dimethylformamide.
3. The method according to claim 1, wherein in step S2, the film has a thickness of 10 to 15 μm.
4. The preparation method according to claim 1, wherein in the step S2, the surface temperature of the template is 40-60 ℃ during casting; controlling the film forming speed to be 10 cm/min-25 cm/min;
the drying temperature is 40-80 ℃ and the drying time is 4-8 h.
5. The method of claim 1, wherein the casting is dried under an infrared drying lamp or microwave in step S2.
6. The method for preparing according to claim 1, wherein the step S3 is performed in a closed environment; in step S4, the vacuum degree is-0.0.08 MPa-0.1 MPa.
7. The method according to claim 1, wherein in step S4, the film is dried in a vacuum oven at 60-100 ℃ for 6-8 h.
8. The method according to any one of claims 1 to 7, wherein the step S2 further includes: and placing the film in a vacuum oven for aging treatment.
9. A high-temperature modified polybenzimidazole proton exchange membrane prepared by the preparation method of any one of claims 1 to 8.
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Citations (3)
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| 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 |
| CN109786794A (en) * | 2019-01-23 | 2019-05-21 | 永兴特种不锈钢股份有限公司 | A kind of electrolyte and preparation method thereof of high conductivity |
| CN111129557A (en) * | 2019-12-11 | 2020-05-08 | 深圳欧陆通电子股份有限公司 | Phosphoric acid modified polybenzimidazole proton exchange membrane and preparation method thereof |
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| CN102376961B (en) * | 2010-08-18 | 2015-06-10 | 北京航空航天大学 | High temperature proton exchange membrane for fuel cell, and preparation method thereof |
| CN110690485A (en) * | 2019-09-20 | 2020-01-14 | 长春工业大学 | Composite high-temperature proton exchange membrane for fuel cell and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN109786794A (en) * | 2019-01-23 | 2019-05-21 | 永兴特种不锈钢股份有限公司 | A kind of electrolyte and preparation method thereof of high conductivity |
| CN111129557A (en) * | 2019-12-11 | 2020-05-08 | 深圳欧陆通电子股份有限公司 | Phosphoric acid modified polybenzimidazole proton exchange membrane and preparation method thereof |
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