CN111261915A - ePTFE reinforced proton exchange membrane forming method - Google Patents
ePTFE reinforced proton exchange membrane forming method Download PDFInfo
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- CN111261915A CN111261915A CN201811452921.6A CN201811452921A CN111261915A CN 111261915 A CN111261915 A CN 111261915A CN 201811452921 A CN201811452921 A CN 201811452921A CN 111261915 A CN111261915 A CN 111261915A
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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
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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
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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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- 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
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Abstract
The invention discloses a forming method of an ePTFE (expanded polyethylene) enhanced proton exchange membrane, and relates to the field of membrane material preparation. Preparing ePTFE reinforced membranes by adopting an electrodeposition method, and preparing the ePTFE reinforced membranes with different thicknesses by controlling current or voltage and matching with the modulation of solution components, the infiltration area of an electrode in the solution, the electrode distance and the deposition time. Overcomes the defects of the traditional ePTFE reinforced membrane preparation process and can realize high-efficiency and quick membrane formation.
Description
Technical Field
The invention relates to a preparation method of a proton exchange membrane for a fuel cell, in particular to a proton exchange membrane with a porous network material as a support structure, and relates to the field of membrane material preparation.
Background
Fuel cells are electrochemical conversion devices that convert chemical energy into electrical energy, and are one of the most competitive power generation technologies in the 21 st century. The proton exchange membrane fuel cell has the characteristics of relatively low temperature and normal pressure, has no chemical hazard to human bodies and no harm to the environment, is suitable for daily life, and is developed and applied to units such as a transportation power type unit, a field type unit, a portable unit and the like.
The application of the ultrathin proton exchange membrane reduces ohmic polarization to a certain extent, promotes the development of fuel cells, and however, the application of the ultrathin proton exchange membrane in the fuel cells is restricted by the problems of poor membrane stability, short service life, high fuel permeability and the like. At present, the ePTFE (expanded polytetrafluoroethylene) reinforced proton exchange membrane can solve the problems of the ultrathin proton exchange membrane, reduce the swelling rate of the membrane, improve the strength of the membrane and prolong the service life of the membrane. The preparation method of the ePTFE reinforced membrane comprises a laminating method, a dipping method and a spraying method.
The lamination method is to hot press the cation exchange membrane prepared by melt extrusion casting method onto the porous support layer, and then fill cation exchange resin into the ePTFE material by coating, dipping or spraying, so the process has high requirements on process conditions and film forming equipment, and is only suitable for thermoplastic cationic polymers. The spraying method needs to repeatedly spray cation exchange resin solution on two sides of the ePTFE material for many times, so that the film forming efficiency is low; the dipping method is influenced by gravity, the perfluorosulfonic acid solution is accumulated at the low point of the membrane, the prepared composite membrane usually has the problem of uneven thickness, and repeated dipping is needed to obtain the ideal thickness.
Disclosure of Invention
The invention aims to overcome the defects of the traditional ePTFE reinforced membrane preparation process, an ePTFE reinforced membrane is prepared by adopting an electrodeposition method, and ePTFE reinforced membranes with different thicknesses are prepared by controlling current or voltage and matching with the modulation of solution components, the infiltration area of an electrode in the solution, the electrode distance and the deposition time.
A method for forming an ePTFE reinforced proton exchange membrane,
1) preparing a cation exchange resin solution;
2) wrapping the opposite surfaces of the plate-shaped working electrode and the plate-shaped counter electrode by using an ePTFE membrane;
3) and vertically placing the working electrode and the counter electrode into a cation exchange resin solution, placing the plate surfaces in parallel and opposite or opposite to each other, and carrying out electrodeposition to obtain the ePTFE (expanded polytetrafluoroethylene) enhanced proton exchange membrane containing a small amount of solvent on the surface of the plate-shaped working electrode. The method can realize in-situ film formation on the surface of an electrode soaked in a cation exchange resin solution;
4) and stripping the obtained ePTFE enhanced proton exchange membrane from the working electrode and drying. . The method only needs to evaporate a small amount of solvent to obtain a dry film, and compared with a solution casting film forming process, an impregnation process and a spraying process, the recovery cost of the volatile solvent is greatly reduced;
5) soaking the membrane obtained by stripping in the step 4) in 0.01-2M acid solution for more than 24 hours, soaking with water and performing ultrasonic treatment for more than 1 hour, and repeating the acid and water treatment process for 2-5 times; and drying the treated membrane to obtain the ePTFE reinforced proton exchange membrane.
The cation exchange resin is one or more of perfluorinated sulfonic acid resin, perfluorinated sulfonimide sulfonic acid resin, partial fluorine-containing sulfonimide sulfonic acid resin, sulfonated polyaryletherketone, sulfonated polyarylethersulfone, sulfonated polyimide, sulfonated polystyrene and sulfonated polyphenyl ether, and the mass solid content of the cation exchange resin solution is 1-25% (preferably 5-15%). The invention can recycle the Nafion series membrane with high cost, firstly dissolve the Nafion series membrane, and then form the membrane by an electrodeposition method, thereby reducing the cost.
The cation exchange resin solution preferably has a mass solid content of 5 to 15%.
The solvent adopted by the cation exchange resin solution is one or more than two of methanol, ethanol, N-propanol, isopropanol, glycol, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and sulfolane.
The plate-shaped working electrode and the plate-shaped counter electrode are one or two of metal plates, conductive glass, graphite plates and carbon paper with smooth surfaces and uniform thickness.
One or both surfaces of the working electrode are coated with an ePTFE membrane impregnated with the above cation exchange resin solution.
The distance between the working electrode and the counter electrode is 0.1-10 cm;
adopting a constant voltage mode, setting the voltage to be 0.1-30.0V, and setting the electrodeposition time to be 10 seconds-1 hour;
adopting constant current mode, setting current density at 0.01-10mA/cm2And the electrodeposition time is 10 seconds to 1 hour.Under the same other conditions, the thickness of the film prepared by the electrodeposition film forming process is positively correlated with the deposition time, the film with the thickness of tens of microns can be prepared only in hundreds of seconds, and the film forming efficiency is high compared with other processes.
Adopting a constant voltage mode, wherein the voltage is preferably 0.2-10V, and the electrodeposition time is preferably 1-20 minutes;
the current density is preferably 0.1-5mA/cm in constant current mode2The electrodeposition time is preferably 1 to 20 minutes.
The acid is one or more of sulfuric acid, hydrochloric acid, acetic acid, nitric acid and phosphoric acid, and the preferable concentration of the acid is 0.5-1M.
The dry film thickness of the ePTFE reinforced proton exchange membrane prepared by the method is 5-30 mu m.
The invention has the following advantages:
1) the resin is precipitated in situ in the solution to the pores and the surface of ePTFE, and the prepared film has a compact structure;
2) overcomes the problem of low efficiency in the traditional process, and can realize high-efficiency and rapid film formation.
Drawings
FIG. 1 example 2 electrodeposition method for preparing a cross-sectional structure of a reinforced membrane (PFSA/ePTFE with a thickness of 14 μm),
FIG. 2 example 6 impregnation method for preparing reinforced membrane (PFSA/ePTFE with thickness of 14 μm) cross-sectional structure
Detailed Description
Example 1
Preparing perfluorosulfonic acid solution with mass solid content of 5.0% of cation exchange resin solution, wherein the solvent is ethanol, and the solute is domestic perfluorosulfonic acid resin (PFSA). Copper plates were used as the working electrode and the counter electrode, respectively, and the working electrode was wrapped with an ePTFE membrane impregnated with the above solution.
Vertically placing the working electrode and the counter electrode in the solution, and parallelly placing the working electrode and the counter electrode in opposite directions (one surface of the working electrode wrapping the ePTFE membrane is parallelly placed in opposite directions), wherein the vertical distance between the working electrode and the ePTFE membrane is 0.5cm, and the infiltration area of the working electrode in the solution is 100cm2. In constant voltage mode, voltage is set to1.0V, and the electrodeposition time was set to 400 s.
The working current density is from-0.53 mA/cm2Reduced to-0.18 mA/cm2Taking out the working electrode, taking the membrane off the working electrode, putting the membrane into an oven 120, drying for 2 hours, soaking for more than 24 hours by using 0.1M sulfuric acid, soaking for 2 hours by using deionized water and carrying out ultrasonic treatment, repeating for 3 times, and putting the membrane into the oven 120, drying for 2 hours to obtain the ePTFE reinforced perfluorinated sulfonic acid proton exchange membrane (PFSA/ePTFE) with the average thickness of 17 microns. The film has uniform structure and high transmittance.
Example 2
Preparing a perfluorosulfonic acid solution with the mass solid content of 5.0% of a cation exchange resin solution, wherein a solvent is a mixed solution of ethanol and DMSO (the volume ratio of the ethanol to the DMSO is 6:4), and a solute is domestic PFSA. Stainless steel plates were used as the working electrode and the counter electrode, respectively, and the working electrode was wrapped with an ePTFE membrane impregnated with the above solution.
Vertically placing the working electrode and the counter electrode in the solution, and parallelly placing the working electrode and the counter electrode in opposite directions (one surface of the working electrode wrapping the ePTFE membrane is parallelly placed in opposite directions), wherein the vertical distance between the working electrode and the ePTFE membrane is 0.5cm, and the infiltration area of the working electrode in the solution is 100cm2. In the constant voltage mode, the voltage was set to 1.0V and the electrodeposition time was set to 400 s.
The working current density is from-0.63 mA/cm2Reduced to-0.23 mA/cm2Taking out the working electrode, taking the membrane off the working electrode, putting the membrane into an oven 120, drying for 2 hours, soaking for more than 24 hours by using 0.1M sulfuric acid, soaking for 2 hours by using deionized water and carrying out ultrasonic treatment, repeating for 3 times, and putting the membrane into the oven 120, drying for 2 hours to obtain the ePTFE reinforced perfluorinated sulfonic acid proton exchange membrane (PFSA/ePTFE) with the average thickness of 14 microns. The film has uniform structure and high transmittance.
Example 3
Preparing a perfluorosulfonic acid solution with the mass solid content of 5.0% of a cation exchange resin solution, wherein a solvent is a mixed solution of ethanol and DMSO (the volume ratio of the ethanol to the DMSO is 6:4), and a solute is domestic PFSA. Copper plates were used as the working electrode and the counter electrode, respectively, and the working electrode was wrapped with an ePTFE membrane impregnated with the above solution.
The working electrode and the counter electrode are vertically placed in the solution and are oppositely placed in parallel (the working electrode is wrapped on one side of the ePTFE membrane and is oppositely placed in parallel with the counter electrode). The wetting area of the working electrode in the solution is 100cm2And the distance from the counter electrode was 0.5 cm. The constant current mode is adopted, and the current density is set to-0.25 mA/cm2The electrodeposition time was set to 400 s.
Increasing the working voltage from 0.27V to 0.90V, taking out the working electrode, taking the membrane off the working electrode, putting the membrane into an oven 120 for drying for 2 hours, soaking and treating for more than 24 hours by using 0.1M sulfuric acid, soaking and ultrasonically treating for 2 hours by using deionized water, repeating for 3 times, and putting the membrane into the oven 120 for drying for 2 hours to obtain the ePTFE reinforced perfluorosulfonic acid proton exchange membrane (PFSA/ePTFE) with the average thickness of 14 μ M. The film has uniform structure and high transmittance.
Example 4
Preparing sulfonated polyaryletherketone with the mass solid content of 10% in a cation exchange resin solution, wherein a solvent is a mixed solution of ethanol and DMSO (the volume ratio of the ethanol to the DMSO is 6:4), and a solute is domestic PFSA (sulfonated polyaryletherketone) (SPEEEK). Stainless steel plates were used as the working and counter electrodes, respectively, and the working electrode was wrapped with an ePTFE membrane impregnated with the above solution.
The working electrode and the counter electrode are vertically placed in the solution and are oppositely placed in parallel (the working electrode is wrapped on one side of the ePTFE membrane and is oppositely placed in parallel with the counter electrode). The wetting area of the working electrode in the solution is 100cm2And the distance from the counter electrode was 0.5 cm. The constant current mode is adopted, and the current density is set to-0.25 mA/cm2The electrodeposition time was set at 800 s.
Increasing the working voltage from 0.71V to 2.32V, taking out the working electrode, taking the membrane off the working electrode, putting the membrane into an oven 120 for drying for 2 hours, soaking and treating for more than 24 hours by using 0.1M sulfuric acid, soaking and ultrasonically treating for 2 hours by using deionized water, repeating for 3 times, and putting the membrane into the oven 120 for drying for 2 hours to obtain an ePTFE (ePTFE) reinforced sulfonated polyaryletherketone proton exchange membrane (SPEEK/ePTFE) with the average thickness of 21 mu M. The film has uniform structure and high transmittance.
Example 5
Preparing a perfluorosulfonic acid solution with the mass solid content of 5.0% of a cation exchange resin solution, wherein a solvent is a mixed solution of ethanol and DMSO (the volume ratio of the ethanol to the DMSO is 6:4), and a solute is domestic PFSA. Copper plates were used as the working electrode and the counter electrode, respectively, and the working electrode was wrapped with an ePTFE membrane impregnated with the above solution.
The working electrode and the counter electrode are vertically placed in the solution and are oppositely placed in parallel (the working electrode is wrapped on one side of the ePTFE membrane and is oppositely placed in parallel with the counter electrode). The wetting area of the working electrode in the solution is 100cm2And the distance from the counter electrode was 0.5 cm.
Standing for 30 minutes, taking out the working electrode, taking the membrane off the working electrode, and putting the membrane into an oven 120 to dry for 2 hours. The obtained composite film has a thickness of 5 μm, a non-uniform structure and low transmittance.
Other conditions are the same, and a film having a uniform thickness and a high pore filling degree cannot be obtained even for a prolonged period of time without applying any current or voltage.
Example 6
Preparing a perfluorosulfonic acid solution with the mass solid content of 25.0% of a cation exchange resin solution, wherein a solvent is a mixed solution of ethanol and DMSO (the volume ratio of the ethanol to the DMSO is 6:4), and a solute is domestic PFSA. The ePTFE membrane impregnated with the above solution was fixed on a stainless steel support and placed in an oven 120 to dry for 2 hours. The obtained composite film has the thickness of 14 +/-7 mu m, uneven structure and low transmittance.
In summary, in the perfluorosulfonic acid solution with a mass solid content of 25.0%, the composite membrane with a thickness of more than 10 μm can be prepared by the impregnation method, but the composite membrane has uneven thickness and low membrane transmittance, which may be related to low filling rate of the internal pores of ePTFE. The scanning electron microscope results of the section of fig. 2 show that the ePTFE inside the composite membrane has a low porosity.
Claims (10)
1. A forming method of an ePTFE reinforced proton exchange membrane is characterized in that:
1) preparing a cation exchange resin solution;
2) wrapping the opposite surfaces of the plate-shaped working electrode and the plate-shaped counter electrode by using an ePTFE membrane;
3) vertically placing a working electrode and a counter electrode into a cation exchange resin solution, placing the plate surfaces in parallel and opposite or opposite to each other, performing electrodeposition, and obtaining an ePTFE (expanded polytetrafluoroethylene) enhanced proton exchange membrane containing a small amount of solvent on the surface of a plate-shaped working electrode;
4) stripping the obtained ePTFE enhanced proton exchange membrane from the working electrode, and drying;
5) soaking the membrane obtained by stripping in the step 4) in 0.01-2M acid solution for more than 24 hours, soaking with water and performing ultrasonic treatment for more than 1 hour, and repeating the acid and water treatment process for 2-5 times; and drying the treated membrane to obtain the ePTFE reinforced proton exchange membrane.
2. The molding method according to claim 1, wherein:
the cation exchange resin is one or more of perfluorinated sulfonic acid resin, perfluorinated sulfonimide sulfonic acid resin, partial fluorine-containing sulfonimide sulfonic acid resin, sulfonated polyaryletherketone, sulfonated polyarylethersulfone, sulfonated polyimide, sulfonated polystyrene and sulfonated polyphenyl ether, and the mass solid content of the cation exchange resin solution is 1-25% (preferably 5-15%).
3. The molding method according to claim 2, wherein:
the cation exchange resin solution preferably has a mass solid content of 5 to 15%.
4. The molding method according to claim 1, wherein: the solvent adopted by the cation exchange resin solution is one or more than two of methanol, ethanol, N-propanol, isopropanol, glycol, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and sulfolane.
5. The molding method according to claim 1, wherein: the plate-shaped working electrode and the plate-shaped counter electrode are one or two of metal plates, conductive glass, graphite plates and carbon paper with smooth surfaces and uniform thickness.
6. The molding method according to claim 1, wherein: one or both surfaces of the working electrode are coated with an ePTFE membrane impregnated with the above cation exchange resin solution.
7. The molding method according to claim 1, wherein:
the distance between the working electrode and the counter electrode is 0.1-10 cm;
adopting a constant voltage mode, setting the voltage to be 0.1-30.0V, and setting the electrodeposition time to be 10 seconds-1 hour;
the constant current mode is adopted, the current density is set to be 0.01-10mA/cm2, and the electrodeposition time is 10 seconds-1 hour.
8. The molding method according to claim 1, wherein:
adopting a constant voltage mode, wherein the voltage is preferably 0.2-10V, and the electrodeposition time is preferably 1-20 minutes;
the constant current mode is adopted, the current density is preferably 0.1-5mA/cm2, and the electrodeposition time is preferably 1-20 minutes.
9. The molding method according to claim 1, wherein:
the acid is one or more of sulfuric acid, hydrochloric acid, acetic acid, nitric acid and phosphoric acid, and the preferable concentration of the acid is 0.5-1M.
10. An ePTFE-reinforced proton exchange membrane made according to the process of any of claims 1 to 9, characterized in that: the resulting membrane is an ePTFE reinforced membrane with a dry membrane thickness of 5-30 μm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000078850A1 (en) * | 1999-04-21 | 2000-12-28 | Dsm N.V. | Process for the production of a composite membrane |
| CN101071873A (en) * | 2007-06-06 | 2007-11-14 | 武汉理工大学 | Polymer supershort fiber reinforced fuel cell proton exchange membrane and its preparing method |
| CN101692487A (en) * | 2009-09-28 | 2010-04-07 | 新源动力股份有限公司 | Method for preparing low-permeability proton exchange membrane for fuel cell |
| CN102941026A (en) * | 2012-11-30 | 2013-02-27 | 河北工业大学 | Ion exchange composite film with selectivity on single cation |
| CN103123974A (en) * | 2011-11-18 | 2013-05-29 | 中国科学院大连化学物理研究所 | Conducting polymer/metal/proton exchange composite membrane and preparation and application thereof |
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- 2018-11-30 CN CN201811452921.6A patent/CN111261915A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000078850A1 (en) * | 1999-04-21 | 2000-12-28 | Dsm N.V. | Process for the production of a composite membrane |
| CN101071873A (en) * | 2007-06-06 | 2007-11-14 | 武汉理工大学 | Polymer supershort fiber reinforced fuel cell proton exchange membrane and its preparing method |
| CN101692487A (en) * | 2009-09-28 | 2010-04-07 | 新源动力股份有限公司 | Method for preparing low-permeability proton exchange membrane for fuel cell |
| CN103123974A (en) * | 2011-11-18 | 2013-05-29 | 中国科学院大连化学物理研究所 | Conducting polymer/metal/proton exchange composite membrane and preparation and application thereof |
| CN102941026A (en) * | 2012-11-30 | 2013-02-27 | 河北工业大学 | Ion exchange composite film with selectivity on single cation |
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