CN111129557A - Phosphoric acid modified polybenzimidazole proton exchange membrane and preparation method thereof - Google Patents
Phosphoric acid modified polybenzimidazole proton exchange membrane and preparation method thereof Download PDFInfo
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- CN111129557A CN111129557A CN201911265652.7A CN201911265652A CN111129557A CN 111129557 A CN111129557 A CN 111129557A CN 201911265652 A CN201911265652 A CN 201911265652A CN 111129557 A CN111129557 A CN 111129557A
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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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a phosphoric acid modified polybenzimidazole proton exchange membrane and a preparation method thereof, wherein the preparation method of the phosphoric acid modified polybenzimidazole proton exchange membrane comprises the following steps: s1, dissolving polybenzimidazole in an organic solvent for purification treatment to obtain a polybenzimidazole solution; s2, coating the polybenzimidazole solution on a flat plate to form a film, and drying; s3, carrying out acidic modification in a phosphoric acid steam atmosphere; and S4, curing at high temperature in vacuum to obtain the phosphoric acid modified polybenzimidazole proton exchange membrane. Compared with the traditional proton exchange membrane, the preparation method has the advantages of simplified process, moderate conditions, no need of nitrogen protection, low cost and more contribution to commercial large-scale application; compared with the phosphoric acid treatment technology in the prior art, the method reduces the loss of phosphoric acid micromolecules from a proton exchange membrane, thereby having good proton conduction stability; the obtained proton exchange membrane has good mechanical capacity.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a preparation method of a phosphoric acid modified polybenzimidazole proton exchange membrane.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are used as clean energy power generation technologies, have the advantages of simple Cell structure, high energy specific power, fast start-up speed, proper working temperature, high conversion efficiency, no noise, and the like, and are known as the best power source options for vehicles, portable power sources, and the like. In order to break through the technical bottleneck of high cost of the existing fuel cell, it is urgent to develop a proton exchange membrane material for a fuel cell with a low-cost material system. The controllable construction and chemical stability of high-flux transport channels in fuel cell ionic conductors are key issues in the development process. The hydrogen storage tank and the proton exchange membrane are two major core technologies recognized in the field of hydrogen fuel automobiles.
Proton Exchange Membranes (PEM) are the core components of Proton Exchange Membrane fuel cells, play a key role in fuel cell performance, and have not only a barrier function but also a Proton conduction function. Among proton exchange membranes, perfluorosulfonic acid proton exchange membranes are widely used.
The normal working temperature of the traditional perfluorosulfonic acid membrane (such as Nafion membrane series of DuPont) electrolyte is maintained at 60-80 ℃ because the proton conductivity of the membrane material is strongly dependent on the water content of the exchange membrane. The temperature is too low, the electrochemical reaction rate is low, and the battery power is low. If the temperature is too high and the battery is close to 100 ℃, the wettability of the proton exchange membrane is sharply reduced, so that the internal resistance of the proton exchange membrane is sharply increased, the performance of the fuel cell is sharply reduced, and the service life of the proton exchange membrane is sharply reduced while the output power is reduced. Therefore, the proton exchange membrane represented by the conventional perfluorosulfonic acid proton exchange membrane has the characteristics of strong correlation between the proton conductivity and the water content and temperature, and limits the working temperature of the cell, so that the working temperature of the conventional proton exchange membrane fuel cell is limited to the range of 60 ℃ to 80 ℃.
The limitation of the operating temperature of the conventional pem fuel cell to 60 to 80 ℃ poses a number 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. Secondly, the rate of electrochemical reaction at 80 ℃ is not high enough, the electrochemical polarization of the cathode is serious, and the performance of the battery catalyst is influenced. And thirdly, the difference between the working temperature of the battery from 60 ℃ to 80 ℃ and the ambient temperature is not large, so that the heat dissipation of a battery system is not facilitated, the requirement of the battery on a cooling system is increased, and the volume power density of the battery can be reduced due to the existence of a complex cooling system.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a phosphoric acid modified polybenzimidazole proton exchange membrane with a simple process and the prepared phosphoric acid modified polybenzimidazole proton exchange membrane.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the phosphoric acid modified polybenzimidazole proton exchange membrane comprises the following steps:
s1, dissolving polybenzimidazole in an organic solvent for purification treatment to obtain a polybenzimidazole solution;
s2, coating the polybenzimidazole solution on a flat plate to form a film, and drying;
s3, carrying out acidic modification in a phosphoric acid steam atmosphere;
and S4, curing at high temperature in vacuum to obtain the phosphoric acid modified polybenzimidazole proton exchange membrane.
Preferably, step S1 includes the steps of:
s1.1, dissolving polybenzimidazole in a first organic solvent to prepare a polybenzimidazole solution with the molar concentration of 0.1-0.4 mol/L, keeping the polybenzimidazole solution at a constant temperature for 2-4 hours, and removing the first organic solvent to obtain a solid benzimidazole polymer;
s1.2, dropwise adding a second organic solvent into the benzimidazole polymer, and keeping the temperature for 2-4 hours to obtain a polybenzimidazole solution with the molar concentration of 0.1-0.4 mol/L.
Preferably, the first organic solvent is a 30% dilute sulfuric acid solution, dimethyl sulfoxide, N-dimethylacetamide, or N, N-dimethylformamide;
the second organic solvent is a dilute sulfuric acid solution with a concentration of 30%, dimethyl sulfoxide, N-dimethylacetamide, or N, N-dimethylformamide, and is different from the first organic solvent.
Preferably, in step S1.1, the temperature of the first organic solvent is 30 ℃ to 50 ℃;
in step S1.2, the temperature of the second organic solvent is 40-50 ℃.
Preferably, step S1 further includes the steps of:
s1.3, adding a second organic solvent into the polybenzimidazole solution obtained in the step S1.2, controlling the molar concentration of the second organic solvent to be 0.1-0.3 mol/L, removing water in vacuum, and keeping the temperature constant for 2-4 hours.
Preferably, in step S1.3, the vacuum is between 0.65KPa and 0.68 KPa.
Preferably, in step S2, the surface temperature of the flat plate is 40 ℃ to 60 ℃ during coating; controlling the film forming speed to be 10 cm/min-25 cm/min; the drying temperature is 60-80 ℃.
Preferably, in step S3, the saturated vapor pressure of the phosphoric acid vapor atmosphere is 0.65KPa-0.68 KPa.
Preferably, in step S4, curing is carried out for 4-8 h at a temperature of 100-120 ℃ and a vacuum degree of-0.1 MPa.
The invention also provides a phosphoric acid modified polybenzimidazole proton exchange membrane prepared by the preparation method of the phosphoric acid modified polybenzimidazole proton exchange membrane.
The invention has the beneficial effects that: 1. compared with the traditional proton exchange membrane, the preparation method has the advantages of simplified process, moderate conditions, no need of nitrogen protection, low cost and more contribution to commercial large-scale application; 2. compared with the phosphoric acid treatment technology in the prior art, the method reduces the loss of phosphoric acid micromolecules from the 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. because the raw materials are purified, the structure of the membrane is uniform, and the obtained proton exchange membrane has good mechanical capacity (the tensile strength reaches 38-55 MPa); the proton conductivity reaches 0.02-0.04S/cm when tested under the national standard.
The invention realizes the low-cost high-efficiency 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 of the membrane electrode enterprise.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a flow chart of a preparation method of a phosphoric acid modified polybenzimidazole proton exchange membrane of the invention.
Detailed Description
For a more clear understanding of the technical features, objects and effects of the present invention, embodiments of the present invention will now be described in detail with reference to the accompanying drawings.
Referring to fig. 1, the preparation method of the phosphoric acid modified polybenzimidazole proton exchange membrane of the present invention may include the following steps:
s1, dissolving the polybenzimidazole in an organic solvent for purification treatment to obtain the polybenzimidazole solution.
Step S1 further includes the steps of:
s1.1, dissolving polybenzimidazole in a first organic solvent at the temperature of 30-50 ℃ to prepare a polybenzimidazole solution with the molar concentration of 0.1-0.4 mol/L, keeping the polybenzimidazole solution at a constant temperature for 2-4 hours, and removing the first organic solvent to obtain a solid benzimidazole polymer.
The first organic solvent is a dilute sulfuric acid solution with the concentration of 30%, dimethyl sulfoxide, N-dimethylacetamide or N, N-dimethylformamide.
Specifically, polybenzimidazole (the amount of the structural unit substance is 0.001mol, 0.3082g) is put into a beaker with a thermometer and stirred by a magneton, N-dimethylformamide solvent with the temperature of 20mL and 30-50 ℃ is added, and the temperature is kept for 2h to obtain the polybenzimidazole solution; slowly volatilizing to remove the N, N-dimethylformamide and obtain the solid benzimidazole polymer.
S1.2, dropwise adding a second organic solvent with the temperature of 40-50 ℃ into the benzimidazole polymer, and keeping the temperature for 2-4 hours to obtain a polybenzimidazole solution with the molar concentration of 0.1-0.4 mol/L.
The benzimidazole polymer is ground into powder before the second organic solvent is added dropwise.
The second organic solvent is a dilute sulfuric acid solution with the concentration of 30%, dimethyl sulfoxide, N-dimethylacetamide or N, N-dimethylformamide. The second organic solvent is different from the first organic solvent, i.e. different solvents are selected. The benzimidazole polymer is then re-polymerized by dissolving it in a second organic solvent to form a polymer of uniform (relatively uniform) molecular weight.
Step S1 may also include the steps of:
s1.3, adding a second organic solvent into the polybenzimidazole solution obtained in the step S1.2, controlling the molar concentration of the polybenzimidazole solution to be 0.1-0.3 mol/L, removing water in vacuum, and keeping the temperature for 2-4 hours to make the polybenzimidazole solution more uniform.
Wherein, the water (from air) is removed under the vacuum degree of 0.65kPa-0.68kPa, and the constant temperature is kept for 2-4 h after the vacuum degree is constant. The degree of vacuum is preferably 0.67 kPa.
S2, coating the polybenzimidazole solution on a flat plate to form a film, and drying.
According to the actual situation (the concentration of the polybenzimidazole solution), the polybenzimidazole solution obtained in step S1.2 can be coated on a flat plate to form a film; alternatively, the polybenzimidazole solution obtained in step 1.3 is coated on a flat plate to form a film.
When coating, the surface temperature of the flat plate is 40-60 ℃; the film forming speed is controlled to be 10 cm/min-25 cm/min.
The flat plate can be a glass flat plate, and is cleaned and dried before coating.
The thickness of the film can be controlled according to the selection of the coating bar, for example, 80 micron bar is selected, and the thickness of the film can be 9-20 micron.
After the flat plate is coated with the coating film, the flat plate is dried by an infrared lamp, the drying temperature is controlled to be 60-80 ℃, the drying time is kept for 6-10 hours, the thickness of the film is controlled to be uniform, and the temperature is kept to be uniformly dispersed.
To avoid environmental pollution, this step S2 is performed in an isolated space.
And S3, performing acidic modification in a phosphoric acid steam atmosphere.
The plate of step S2 with the film layer thereon was placed in a closed environment for phosphoric acid modification. Wherein the saturated vapor pressure of the phosphoric acid vapor atmosphere is 0.65KPa to 0.68KPa, preferably 0.67 KPa.
And S4, curing at high temperature in vacuum to obtain the phosphoric acid modified polybenzimidazole proton exchange membrane.
And (5) placing the film layer modified by the phosphoric acid in the step S3 and the flat plate into a vacuum environment for high-temperature curing treatment. Specifically, the vacuum degree is-0.1 MPa, and the temperature is 100-120 ℃; the drying and curing time is 4-8 h.
The phosphoric acid modified polybenzimidazole proton exchange membrane prepared by the preparation method has good proton conduction stability, and the linear swelling rate is less than 3%; as the raw materials are purified, the membrane has a uniform structure and good mechanical capacity (the tensile strength reaches 38-55 MPa). The proton conductivity reaches 0.02-0.04S/cm when tested under the national standard.
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 0.001mol, 0.3082g) was dissolved in N, N-dimethylformamide solvent and N, N-dimethylacetamide organic solvent at a molar concentration of 0.1mol/L, and purification was performed twice each. The first purification is carried out in N, N-Dimethylformamide (DMF) at 30 ℃, polybenzimidazole (number average molecular weight 20000, the amount of the structural unit substance is 0.001mol, 0.3082g) is put into a beaker with a magneton stirrer and a thermometer, 20mL of N, N-dimethylformamide solvent at 50 ℃ is added, the temperature is kept for 2h, polybenzimidazole solution is obtained, the solvent is slowly volatilized, and the solvent is removed, so that the blocky benzimidazole polymer is obtained. And the second purification is to grind the benzimidazole polymer obtained by the first purification into powder with uniform granularity in N, N-dimethylacetamide (DMAc) solvent, drop-drop add the benzimidazole polymer into a dropper at 40 ℃ and 20mL of N, N-dimethylacetamide solvent, and keep the solution at constant temperature for 2h to obtain the polybenzimidazole solution with uniform molecular weight.
2) Adding N, N-dimethylacetamide (DMAc) solvent with the temperature of 40 ℃ into the polybenzimidazole solution in the step 1), and controlling the concentration to be 0.3 mol/L; removing water under vacuum condition, and keeping for 2h when the vacuum degree is constant.
3) And manually coating the polybenzimidazole solution on a glass flat plate to form a film.
Before coating, the glass plate is cleaned and then dried. The polybenzimidazole solution obtained in step 2) was manually coated in a constant temperature state while maintaining the surface temperature at 40 ℃. The commercial 80 micron specification is selected for the coating bar, and the film forming speed is controlled to be 12 cm/min.
4) And after the coating is finished, quickly drying under the action of an infrared drying lamp, controlling the temperature to be 60 ℃, and keeping for 5 hours.
5) After the film formation, the acid modification is carried out in an atmosphere of phosphoric acid vapor (pure anhydrous phosphoric acid, saturated vapor pressure of 0.67 KPa); the acidic modification must be carried out in a closed environment; phosphoric acid is an anhydrous environmental operation. After the modification is finished, the mixture is put into a vacuum oven for curing treatment at 100 ℃ for 4 h.
Through tests, the linear swelling coefficient of the proton exchange membrane prepared in the embodiment at normal temperature is 2.46%, the tensile strength is 38MPa, and the proton conductivity is 0.024S/cm according to the national standard requirements.
Example 2
1) Polybenzimidazole (number average molecular weight 30000, amount of constitutional unit substance 0.001mol, 0.3082g) was dissolved in N, N-dimethylformamide solvent and N, N-dimethylacetamide organic solvent at a molar concentration of 0.2mol/L, and purification was performed twice, respectively. The first purification is carried out in N, N-dimethylformamide solvent at 40 ℃, polybenzimidazole is put into a beaker with a thermometer and stirred by a magneton, N-dimethylformamide solvent at 35 ℃ in an amount of 20mL and kept at the constant temperature for 2 hours to obtain polybenzimidazole solution, and the polybenzimidazole solution is slowly volatilized to remove the solvent to obtain blocky benzimidazole polymer. And the second purification is to grind the benzimidazole polymer obtained by the first purification into powder with uniform granularity in an N, N-dimethylacetamide solvent, dropwise add the powder into a dropper at 40 ℃ and 20mL of the N, N-dimethylacetamide solvent, and keep the solution at constant temperature for 2 hours to obtain the polybenzimidazole solution with uniform molecular weight.
2) Adding N, N-dimethylacetamide solvent with the temperature of 50 ℃ into the polybenzimidazole solution in the step 1), and controlling the concentration to be 0.3 mol/L; and (5) putting the mixture into vacuum to remove water, and keeping the process for 2 hours when the vacuum degree is constant.
3) And manually coating the polybenzimidazole solution on a glass flat plate to form a film.
Before coating, the glass plate is cleaned and then dried. The polybenzimidazole solution obtained in step 2) was manually coated in a constant temperature state while maintaining the surface temperature at 45 ℃. The commercial 80 micron specification is selected for the coating bar, and the film forming speed is controlled to be 18 cm/min.
4) And after the coating is finished, quickly drying under the action of an infrared drying lamp, controlling the temperature to be 70 ℃, and keeping for 5 hours.
5) After the film formation, the acid modification is carried out in an atmosphere of phosphoric acid vapor (pure anhydrous phosphoric acid, saturated vapor pressure of 0.67 KPa); the acidic modification must be carried out in a closed environment; phosphoric acid is an anhydrous environmental operation. After the modification is finished, the mixture is placed into a vacuum oven for curing treatment at 105 ℃ for 5 h.
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 41MPa, and the proton conductivity is 0.026S/cm according to the national standard requirement.
Example 3
1) Polybenzimidazole (number average molecular weight 40000, amount of structural unit substance 0.001mol, 0.3082g) was dissolved in N, N-dimethylformamide solvent and N, N-dimethylacetamide organic solvent at a molar concentration of 0.1mol/L, and purification was performed twice, respectively. The first purification is carried out in N, N-dimethylformamide solvent at 50 ℃, polybenzimidazole (number average molecular weight 40000, amount of structural unit substance 0.001mol, 0.3082g) is put into a beaker of a magneton stirring thermometer, 20mL of N, N-dimethylformamide solvent at 50 ℃ is added, the temperature is kept for 2h, polybenzimidazole solution is obtained, the solvent is slowly volatilized, and the blocky benzimidazole polymer is obtained after the solvent is removed. And the second purification is to grind the benzimidazole polymer obtained by the first purification into powder with uniform granularity in an N, N-dimethylacetamide solvent, dropwise add the powder into a dropper at 40 ℃ and 20mL of the N, N-dimethylacetamide solvent, and keep the solution at constant temperature for 2 hours to obtain the polybenzimidazole solution with uniform molecular weight.
2) Adding N, N-dimethylacetamide solvent with the temperature of 50 ℃ into the polybenzimidazole solution in the step 1), and controlling the concentration to be 0.3 mol/L; removing water under vacuum condition, and keeping for 3h when the vacuum degree is constant.
3) And manually coating the polybenzimidazole solution on a glass flat plate to form a film.
Before coating, the glass plate is cleaned and then dried. The polybenzimidazole solution obtained in step 2) was manually coated in a constant temperature state while maintaining the surface temperature at 60 ℃. The commercial 80 micron specification is selected for the coating bar, and the film forming speed is controlled to be 20 cm/min.
4) And after coating, quickly drying under the action of an infrared drying lamp, controlling the temperature to be 75 ℃, and keeping for 6 hours.
5) After the film formation, the acid modification is carried out in an atmosphere of phosphoric acid vapor (pure anhydrous phosphoric acid, saturated vapor pressure of 0.67 KPa); the acidic modification must be carried out in a closed environment; phosphoric acid is an anhydrous environmental operation. After the modification is finished, the mixture is put into a vacuum oven for curing treatment at 110 ℃ for 7 h.
Through tests, the linear swelling coefficient of the proton exchange membrane prepared in the embodiment at normal temperature is 2.46%, the tensile strength is 47MPa, and the proton conductivity is 0.024S/cm according to the national standard requirements.
Example 4
1) Polybenzimidazole (number average molecular weight 80000, amount of building block material 0.001mol, 0.3082g) was dissolved in N, N-dimethylformamide solvent organic solvent at a molar concentration of 0.4mol/L, and purification was performed twice each. The first purification is carried out in N, N-dimethylformamide solvent at 60 ℃, polybenzimidazole (the number average molecular weight is 25000, the amount of the structural unit substance is 0.001mol, 0.3082g) is put into a beaker of a magneton stirring thermometer, 20mL of N, N-dimethylformamide solvent at 50 ℃ is added, the temperature is kept for 2h, polybenzimidazole solution is obtained, the solvent is slowly volatilized, and the blocky benzimidazole polymer is obtained after the solvent is removed. And the second purification is to grind the benzimidazole polymer obtained by the first purification into powder with uniform granularity in an N, N-dimethylacetamide solvent, drop-by-drop add a dropper into the N, N-dimethylacetamide solvent at 40 ℃ and 20mL, and keep the constant temperature for 4 hours to obtain the polybenzimidazole solution with uniform molecular weight.
2) Adding N, N-dimethylacetamide (DMAc) solvent with the temperature of 50 ℃ into the polybenzimidazole solution in the step 1), and controlling the concentration to be 0.4 mol/L; removing water under vacuum condition, and keeping for 3h when the vacuum degree is constant.
3) And manually coating the polybenzimidazole solution on a glass flat plate to form a film.
Before coating, the glass plate is cleaned and then dried. The polybenzimidazole solution obtained in step 2) was manually coated in a constant temperature state while maintaining the surface temperature at 40 ℃. The commercial 80 micron specification is selected for the coating bar, and the film forming speed is controlled to be 25 cm/min.
4) And after the coating is finished, quickly drying under the action of an infrared drying lamp, controlling the temperature to be 80 ℃, and keeping for 10 hours.
5) After the film formation, the acid modification is carried out in an atmosphere of phosphoric acid vapor (pure anhydrous phosphoric acid, saturated vapor pressure of 0.67 KPa); the acidic modification must be carried out in a closed environment; phosphoric acid is an anhydrous environmental operation. After the modification is finished, the mixture is put into a vacuum oven for curing treatment at 120 ℃ for 8 h.
Through tests, the linear swelling coefficient of the proton exchange membrane prepared in the embodiment at normal temperature is 2.4%, the tensile strength is 55MPa, and the proton conductivity is 0.04S/cm according to the national standard requirements.
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 performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of a phosphoric acid modified polybenzimidazole proton exchange membrane is characterized by comprising the following steps:
s1, dissolving polybenzimidazole in an organic solvent for purification treatment to obtain a polybenzimidazole solution;
s2, coating the polybenzimidazole solution on a flat plate to form a film, and drying;
s3, carrying out acidic modification in a phosphoric acid steam atmosphere;
and S4, curing at high temperature in vacuum to obtain the phosphoric acid modified polybenzimidazole proton exchange membrane.
2. The method for preparing a phosphoric acid modified polybenzimidazole proton exchange membrane according to claim 1, wherein the step S1 comprises the following steps:
s1.1, dissolving polybenzimidazole in a first organic solvent to prepare a polybenzimidazole solution with the molar concentration of 0.1-0.4 mol/L, keeping the polybenzimidazole solution at a constant temperature for 2-4 hours, and removing the first organic solvent to obtain a solid benzimidazole polymer;
s1.2, dropwise adding a second organic solvent into the benzimidazole polymer, and keeping the temperature for 2-4 hours to obtain a polybenzimidazole solution with the molar concentration of 0.1-0.4 mol/L.
3. The method for preparing a phosphoric acid modified polybenzimidazole proton exchange membrane according to claim 2, wherein the first organic solvent is a 30% dilute sulfuric acid solution, dimethyl sulfoxide, N-dimethylacetamide, or N, N-dimethylformamide;
the second organic solvent is a dilute sulfuric acid solution with a concentration of 30%, dimethyl sulfoxide, N-dimethylacetamide, or N, N-dimethylformamide, and is different from the first organic solvent.
4. The method for preparing a phosphoric acid modified polybenzimidazole proton exchange membrane according to claim 2, wherein in step S1.1, the temperature of the first organic solvent is 30 ℃ to 50 ℃;
in step S1.2, the temperature of the second organic solvent is 40-50 ℃.
5. The method for preparing a phosphoric acid modified polybenzimidazole proton exchange membrane according to claim 2, wherein the step S1 further comprises the following steps:
s1.3, adding a second organic solvent into the polybenzimidazole solution obtained in the step S1.2, controlling the molar concentration of the second organic solvent to be 0.1-0.3 mol/L, removing water in vacuum, and keeping the temperature constant for 2-4 hours.
6. The method for preparing a phosphoric acid modified polybenzimidazole proton exchange membrane according to claim 5, wherein in the step S1.3, the vacuum degree is 0.65KPa to 0.68 KPa.
7. The method for preparing a phosphoric acid modified polybenzimidazole proton exchange membrane according to claim 1, wherein in step S2, the surface temperature of the flat plate is 40 ℃ to 60 ℃ during coating; controlling the film forming speed to be 10 cm/min-25 cm/min;
the drying temperature is 60-80 ℃.
8. The method of claim 1, wherein in step S3, the saturated vapor pressure of the phosphoric acid vapor atmosphere is 0.65KPa to 0.68 KPa.
9. The preparation method of the phosphoric acid modified polybenzimidazole proton exchange membrane according to claim 1, wherein in the step S4, the membrane is cured for 4-8 hours at a temperature of 100-120 ℃ and a vacuum degree of-0.1 MPa.
10. A phosphoric acid modified polybenzimidazole proton exchange membrane, which is characterized by being prepared by the preparation method of the phosphoric acid modified polybenzimidazole proton exchange membrane of any one of claims 1 to 9.
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| CN112259771A (en) * | 2020-09-16 | 2021-01-22 | 深圳大学 | Proton exchange membrane with wide operating temperature, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070193885A1 (en) * | 2006-01-30 | 2007-08-23 | H2 Pump Llc | Apparatus and methods for electrochemical hydrogen manipulation |
| WO2010022963A2 (en) * | 2008-08-29 | 2010-03-04 | Ewe-Forschungszentrum Für Energietechnologie E.V. | Proton exchange membrane for use in proton exchange membrane fuel cells |
| CN105601968A (en) * | 2015-11-19 | 2016-05-25 | 黄河科技学院 | Preparation method of polybenzimidazole multi-layer composite membrane for high-temperature fuel cell |
| CN209522795U (en) * | 2019-02-13 | 2019-10-22 | 深圳市化讯半导体材料有限公司 | A kind of high molecular polymer purification devices |
-
2019
- 2019-12-11 CN CN201911265652.7A patent/CN111129557B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070193885A1 (en) * | 2006-01-30 | 2007-08-23 | H2 Pump Llc | Apparatus and methods for electrochemical hydrogen manipulation |
| WO2010022963A2 (en) * | 2008-08-29 | 2010-03-04 | Ewe-Forschungszentrum Für Energietechnologie E.V. | Proton exchange membrane for use in proton exchange membrane fuel cells |
| CN105601968A (en) * | 2015-11-19 | 2016-05-25 | 黄河科技学院 | Preparation method of polybenzimidazole multi-layer composite membrane for high-temperature fuel cell |
| CN209522795U (en) * | 2019-02-13 | 2019-10-22 | 深圳市化讯半导体材料有限公司 | A kind of high molecular polymer purification devices |
Non-Patent Citations (2)
| Title |
|---|
| 李进等: ""高温浸渍法PBI/H3PO4复合膜特性及电池性能研究"", 《电源技术》 * |
| 甘文君等主编: "《高分子化学实验原理与技术》", 31 July 2012 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112018418A (en) * | 2020-07-28 | 2020-12-01 | 深圳欧陆通电子股份有限公司 | High-temperature modified polybenzimidazole proton exchange membrane and preparation method thereof |
| CN112018418B (en) * | 2020-07-28 | 2022-03-22 | 深圳欧陆通电子股份有限公司 | High-temperature modified polybenzimidazole proton exchange membrane and preparation method thereof |
| CN112259771A (en) * | 2020-09-16 | 2021-01-22 | 深圳大学 | Proton exchange membrane with wide operating temperature, and preparation method and application thereof |
| CN112259771B (en) * | 2020-09-16 | 2022-02-18 | 深圳大学 | Proton exchange membrane with wide operating temperature, and preparation method and application thereof |
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| CN111129557B (en) | 2022-09-09 |
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