CN113363542B - Proton exchange membrane, preparation method thereof and fuel cell - Google Patents
Proton exchange membrane, preparation method thereof and fuel cell Download PDFInfo
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Abstract
The invention discloses a preparation method of a proton exchange membrane, which comprises the following steps of firstly, adding an initiator into a mixed solution of diene amine, vinyl sulfonate and a water solvent at a reaction temperature of 65-80 ℃ under the condition of nitrogen to initiate free radical polymerization reaction of the diene amine and the vinyl sulfonate to obtain a linear prepolymer solution; then, carrying out mixing reaction on the linear prepolymer solution, the perfluorinated sulfonic acid resin dispersion liquid and the mixed polyol according to a preset proportion to obtain polymer slurry; finally, coating the polymer slurry to form a film, and drying, curing and forming the film to obtain the proton exchange membrane with the cross-linked interpenetrating network structure; the invention takes a high-stability cross-linked polymer network as a framework, realizes an interpenetrating network with perfluorinated sulfonic acid polymer molecules, and realizes the suppression of the swelling degree of a proton exchange membrane in a macroscopic view and a microscopic view.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a proton exchange membrane, a preparation method thereof and a fuel cell.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are an important branch of the fuel cell field, and proton exchange membranes (pemcs) are one of the core components of the PEM fuel cells, and provide a passage for the migration and transport of protons, and simultaneously, have a barrier effect on anode hydrogen fuel and cathode oxide in the PEM fuel cells.
In the starting-running-stopping process of the proton exchange membrane fuel cell, the proton exchange membrane is in the changes of drying, wetting, drying, low temperature, high temperature and low temperature, namely the proton exchange membrane is in the environment changes of dry-wet cycle and cold-hot cycle for a long time, so that the proton exchange membrane is repeatedly swelled and shrunk and deformed. Because the proton exchange membrane is a polymer polyelectrolyte, the proton exchange membrane can creep and even permanently deform under repeated deformation, so that cracks and defects occur between a catalyst layer and the proton exchange membrane of the proton exchange membrane fuel cell. In addition, under the environmental change of dry-wet cycle, the proton exchange membrane is easily affected by the stress change caused by repeated swelling-shrinking deformation, and the phenomena of fine lines, thinning, wrinkles and the like can occur, thus seriously affecting the mechanical service life of the proton exchange membrane.
The structure of the proton exchange membrane has great influence on the performance of the proton exchange membrane fuel cell, and the swelling degree of the proton exchange membrane is an important factor influencing the service mechanical life of the proton exchange membrane. The higher the swelling degree of the proton exchange membrane is, the higher the deformation degree of the proton exchange membrane in the environment change of dry-wet cycle and cold-hot cycle, and the more obvious the stress change caused by the high deformation degree is, the more the mechanical service life of the proton exchange membrane is seriously influenced.
In the prior art, in order to reduce the swelling degree of the proton exchange membrane, researchers add a microporous reinforcing layer, such as a microporous polytetrafluoroethylene membrane (PTFE), a microporous polyvinylidene fluoride membrane (PVDF), etc., into the proton exchange membrane, which has high thermal stability and mechanical strength, and can macroscopically ensure that the proton exchange membrane has a low swelling degree (< 5%) under wet and high temperature conditions. However, this method cannot microscopically suppress the swelling degree of the proton exchange membrane, and since the above-mentioned added microporous reinforcing layer has a planar structure, the swelling effect cannot be controlled in the proton permeation direction, and thus the swelling degree of the proton exchange membrane tends to be too high in the proton permeation direction.
Disclosure of Invention
Based on this, it is necessary to provide a proton exchange membrane capable of suppressing the swelling degree of the proton exchange membrane from macroscopic and microscopic view, a method for preparing the same, and a fuel cell.
In order to achieve the above purpose, the invention provides a preparation method of a proton exchange membrane, which comprises the following steps:
preparing a linear prepolymer solution; the linear prepolymer solution is obtained by adding an initiator into a mixed solution of a binary olefin amine, a vinyl sulfonate and a water solvent at a reaction temperature of 65-80 ℃ under the condition of nitrogen, and then initiating the free radical polymerization reaction of the binary olefin amine and the vinyl sulfonate in the mixed solution;
mixing the linear prepolymer solution, perfluorinated sulfonic acid resin dispersion liquid and mixed polyol according to a preset proportion to obtain polymer slurry;
and coating the polymer slurry to form a film, and drying, curing and forming the film to obtain the proton exchange membrane with the cross-linked interpenetrating network structure.
Preferably, the step of preparing the linear prepolymer solution comprises:
mixing a first preset amount of dyadic alkene amine and a second preset amount of vinyl sulfonate to obtain a premix, dissolving the premix in a third preset amount of water solvent, and uniformly stirring to obtain a mixed solution;
and adding an initiator into the mixed solution at the reaction temperature of 65-80 ℃ and under the nitrogen condition to initiate free radical polymerization reaction between the dialkene amine and the vinyl sulfonate in the mixed solution to obtain the linear prepolymer solution.
Preferably, the step of mixing and reacting the linear prepolymer solution with the perfluorosulfonic acid resin dispersion and the polyol mixture according to a preset ratio to obtain the polymer slurry further comprises:
and (3) carrying out acidification treatment on the linear prepolymer solution.
Preferably, the step of coating the polymer slurry into a membrane, and drying, curing and molding the coated membrane to obtain the proton exchange membrane with the cross-linked interpenetrating network structure comprises:
coating the polymer slurry into a film, and drying the coated film at a reaction temperature of 65-80 ℃;
carrying out cross-linking curing treatment on the dried membrane;
carrying out heat treatment on the film subjected to crosslinking and curing treatment at the reaction temperature of 160-180 ℃;
and activating the membrane after heat treatment to obtain the proton exchange membrane with a cross-linked interpenetrating network structure.
Preferably, the step of activating the heat-treated film includes:
placing the heat-treated film in H 2 O 2 And H 2 SO 4 And carrying out an activation reaction in the solution, and drying the membrane subjected to the activation treatment after the activation reaction.
Preferably, the dialkene amine is an organic amine having a diene bond.
Preferably, the vinyl sulfonate is a sulfonate having a double bond.
Preferably, the initiator consists of a persulfate and a sulfite or a persulfate and a bisulfite.
The invention also provides a proton exchange membrane prepared by any one of the preparation methods.
The invention also provides a fuel cell, which comprises the proton exchange membrane prepared by the preparation method.
The technical scheme of the invention has the beneficial effects that:
1. the preparation method of the proton exchange membrane provided by the invention comprises the steps of adding an initiator into a mixed solution obtained by mixing and dissolving the dialkene amine and the vinyl sulfonate into a water solvent to initiate the radical polymerization reaction of the dialkene amine and the vinyl sulfonate in the mixed solution, thereby obtaining a linear prepolymer solution with a linear structure; then, interpenetrating polymer networks are carried out on the linear prepolymer solution and the perfluorinated sulfonic acid resin dispersion liquid, and then the proton exchange membrane with the cross-linked interpenetrating polymer networks is obtained after drying, curing and forming. The invention takes the high-stability cross-linked polymer network in the linear prepolymer solution as a framework to realize interpenetrating network with the perfluorosulfonic acid polymer molecules in the perfluorosulfonic acid resin dispersion liquid, thereby ensuring that the prepared proton exchange membrane has higher mechanical strength and dimensional stability, and macroscopically and microscopically realizing the inhibition of the swelling degree of the proton exchange membrane, namely macroscopically and microscopically realizing the inhibition of the repeated swelling-shrinking deformation of the proton exchange membrane caused by the long-term dry-wet cycle and cold-hot cycle environmental change of the proton exchange membrane.
2. The dyadic alkene amine has a certain amount of amido (-NH-), and the vinyl sulfonate has a certain amount of sulfonic acid group (-SO-) 3 H) SO that the cross-linked interpenetrating network in the proton exchange membrane prepared by the preparation method has sulfonic acid groups (-SO) on the side chain 3 H) And a chain segment of amino (-NH-), i.e. contains a large amount of amino (-NH-), sulfonic acid groups (-SO) 3 H) The hydrophilic group, the amino (-NH-) can be reacted with the sulfonic acid group (-SO) 3 H) An acid-base pair is formed, so that the proton jumping between the sulfonic acid group and the amino group is facilitated, and the high proton conductivity and the water retention capacity of the proton exchange membrane can be realized through the acid-base pair.
3. The cross-linked interpenetrating network in the proton exchange membrane prepared by the preparation method can obviously improve the gas permeability of the proton exchange membrane, and is beneficial to prolonging the chemical-mechanical mixing life of the proton exchange membrane; meanwhile, the stress change caused by swelling-shrinkage due to dry-wet and temperature change can be reduced, and the mechanical life of the proton exchange membrane is finally prolonged.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic flow chart of a method for preparing a proton exchange membrane according to the present invention;
FIG. 2 is a schematic flow chart illustrating the specific steps of step S100 in the method for preparing a proton exchange membrane according to the present invention;
FIG. 3 is a schematic flow chart of step S300 in the method for preparing a proton exchange membrane according to the present invention.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, a method for preparing a proton exchange membrane according to a preferred embodiment of the present invention includes the following steps:
step S100: preparing a linear prepolymer solution; the linear prepolymer solution is obtained by adding an initiator into a mixed solution of a dialkene amine, a vinyl sulfonate and a water solvent at the reaction temperature of 65-80 ℃ under the condition of nitrogen, and then initiating the radical polymerization reaction of the dialkene amine and the vinyl sulfonate in the mixed solution;
the reaction formula for synthesizing the above linear prepolymer solution is shown in the following formula (1):
specifically, in the above formula (1)
Refers to a dialkene amine;
refers to vinyl sulfonate;
refers to the polymer molecules of the resulting linear prepolymer solution prepared; k 2 S 2 O 8 Is an initiator.
The step S100 specifically includes the following steps:
step S110: mixing a first preset amount of dyadic alkene amine and a second preset amount of vinyl sulfonate to obtain a premix, dissolving the premix in a third preset amount of water solvent, and uniformly stirring to obtain a mixed solution;
step S120: and adding an initiator into the mixed solution at a reaction temperature of 65-80 ℃ under the condition of nitrogen to initiate free radical polymerization reaction between the binary alkylene amine and the vinyl sulfonate in the mixed solution so as to obtain a linear prepolymer solution.
Step S200: and (3) carrying out mixing reaction on the linear prepolymer solution, the perfluorinated sulfonic acid resin dispersion liquid and the mixed polyol according to a preset proportion to obtain the polymer slurry.
Step S300: and coating the polymer slurry to form a film, and drying, curing and forming the film to obtain the proton exchange membrane with the cross-linked interpenetrating network structure.
In this embodiment, an initiator is added to a mixed solution obtained by mixing and dissolving a dialkene amine and a vinyl sulfonate in an aqueous solvent to initiate a radical polymerization reaction between the dialkene amine and the vinyl sulfonate in the mixed solution, thereby obtaining a linear prepolymer solution having a linear structure; then, interpenetrating networks are carried out on the linear prepolymer solution and the perfluorinated sulfonic acid resin dispersion liquid, and the proton exchange membrane with the cross-linked interpenetrating networks is finally obtained after drying, curing and forming. The invention takes the high-stability cross-linked polymer network in the linear prepolymer solution as a framework to realize interpenetrating network with the perfluorosulfonic acid polymer molecules in the perfluorosulfonic acid resin dispersion liquid, thereby ensuring that the prepared proton exchange membrane has higher mechanical strength and dimensional stability, and macroscopically and microscopically realizing the inhibition of the swelling degree of the proton exchange membrane, namely macroscopically and microscopically realizing the inhibition of the repeated swelling-shrinking deformation of the proton exchange membrane caused by the long-term dry-wet cycle and cold-hot cycle environmental change of the proton exchange membrane.
Specifically, in this embodiment, the swelling degree of the proton exchange membrane refers to the ratio of the volume after swelling to the volume before non-swelling when the polymer molecules in the proton exchange membrane adsorb the solvent molecules and reach the swelling equilibrium. More specifically, the degree of swelling of the proton exchange membrane is an important factor affecting the mechanical lifetime of the proton exchange membrane. The higher the swelling degree of the proton exchange membrane is, the higher the deformation degree of the proton exchange membrane in the environment change of dry-wet cycle and cold-hot cycle, and the more remarkable the stress change caused by the high deformation degree, thereby seriously affecting the mechanical service life of the proton exchange membrane. In addition, the dimensional stability of a proton exchange membrane refers to the property of the proton exchange membrane that the outer dimensions of the proton exchange membrane are not changed under the action of mechanical force, heat or other external conditions.
Further, in this embodiment, the dieneamine itself has a certain number of amine groups (-NH-), and the vinylsulfonate itself has a certain number of sulfonic acid groups (-SO-) 3 H) SO that the cross-linked interpenetrating network in the proton exchange membrane prepared by the preparation method has sulfonic acid groups (-SO) on the side chain 3 H) And a chain segment of amino (-NH-), i.e. contains a large amount of amino (-NH-), sulfonic acid groups (-SO) 3 H) The hydrophilic group, the amino (-NH-) can be reacted with the sulfonic acid group (-SO) 3 H) Acid-base pairs are formed, so that protons can jump between sulfonic acid groups and amino groups, and the acid-base pairs can realizeThe proton exchange membrane has high proton conductivity and water retention capacity.
Further, in this embodiment, the cross-linked interpenetrating network inside the proton exchange membrane prepared by the above preparation method can significantly improve the gas permeability of the proton exchange membrane, which is beneficial to improving the chemical-mechanical mixing life of the proton exchange membrane; meanwhile, the stress change caused by swelling-shrinkage due to dry-wet and temperature change can be reduced, and the mechanical life of the proton exchange membrane is finally prolonged. Further, in the present embodiment, step S110: the first predetermined amount of the dialkene amine is mixed with the second predetermined amount of the vinyl sulfonate to obtain a premix, and the premix is mixed under the oxygen-free condition. Specifically, in this embodiment, the oxygen-free condition in step S110 and the nitrogen condition in step S120 are to provide an oxygen-free environment for the preparation of the linear prepolymer solution, because oxygen is a polymerization inhibitor in the radical polymerization reaction, the reaction rate and the monomer conversion rate of the radical polymerization can be improved in the oxygen-free environment.
Further, in this embodiment, the mixed polyol is added in the mixing reaction in the step S200 to dissolve and disperse the perfluorosulfonic acid resin, so as to facilitate the interpenetrating network of the linear prepolymer solution and the perfluorosulfonic acid polymer molecules in the perfluorosulfonic acid resin dispersion.
In one embodiment, the dialkene amine is an organic amine having a diene bond. Specifically, the dialkylene amine is any one of diallylamine, diallylacetamide, diallylchloroacetamide, and diallyldimethylammonium chloride. In other embodiments, the diolefinic amines also include other diolefinic-bonded organic amines.
In one embodiment, the vinyl sulfonate is a sulfonate having a double bond. Specifically, the vinylsulfonate is any one of styrene sulfonate, ortho-vinyl salt, vinylsulfonate and allylsulfonate. In other embodiments, the vinyl sulfonate salts also include other sulfonate salts having a double bond.
In one embodiment, the initiator is composed of a persulfate and a sulfite or a persulfate and a bisulfite. Further, in this example, the initiator was prepared as follows: and mixing a fourth preset amount of persulfate and a fifth preset amount of sulfite or bisulfite, dissolving in a water solvent, and uniformly stirring to obtain the initiator.
In this embodiment, the initiator is a redox system initiator, the persulfate in the initiator has oxidation property, the sulfite or bisulfite has reduction property, and the persulfate and the sulfite or bisulfite generate free radicals through redox reaction, so as to initiate free radical polymerization reaction between the alkyleneamine and the vinylsulfonate in the mixed solution.
Specifically, in this embodiment, the initiator is composed of sodium persulfate and sodium sulfite, or composed of ammonium persulfate and potassium sulfite, or composed of potassium persulfate and sodium bisulfite, or composed of sodium persulfate and sodium bisulfite, or composed of ammonium persulfate and potassium bisulfite. In other embodiments, the initiator also includes other redox system initiators.
Further, in the present embodiment, the mixed polyol may be, but is not limited to, an ethanol-isopropanol mixed solution.
In an embodiment, step S200 further includes the following steps:
step S210: the linear prepolymer solution is acidified.
The vinyl sulfonate in the linear prepolymer solution is converted into sulfonic acid groups by carrying out acidification treatment on the linear prepolymer solution, so that the proton conduction capability of the polymer is improved, and the film forming is facilitated.
Specifically, adding a sixth preset amount of acid solution into the linear prepolymer solution obtained in step S100 and treating the solution with a dialysis bag with a cut-off molecular weight of 8000-14000 to achieve acidification of the linear prepolymer solution, so as to obtain an acidified linear prepolymer solution; and then mixing the prepolymer solution after the acidification treatment with perfluorosulfonic acid resin dispersion liquid (PFSA dispersion liquid) and mixed polyol according to a preset proportion to obtain polymer slurry. More specifically, the above-mentioned acidic solution may be, but is not limited to, a sulfuric acid solution.
In an embodiment, the step S300 specifically includes the following steps:
step S310: coating the polymer slurry into a film, and drying the coated film at a reaction temperature of 60-80 ℃;
step S320: carrying out cross-linking curing treatment on the dried membrane;
specifically, in the present embodiment, the crosslinking curing treatment is any one of thermal curing, photo curing, and chemical curing with an external crosslinking agent. Specifically, the reaction temperature for the thermal curing is specifically 100 ℃ to 120 ℃.
Step S330: carrying out heat treatment on the film subjected to crosslinking and curing treatment at the reaction temperature of 160-180 ℃;
the film after the crosslinking and curing treatment is subjected to heat treatment, so that the mechanical property of the film can be improved, and the residual stress after the film is formed can be eliminated.
Step S340: and activating the membrane after heat treatment to obtain the proton exchange membrane with a cross-linked interpenetrating network structure.
When the film after the crosslinking curing treatment is subjected to heat treatment, a part of the sulfonic acid groups are dehydrated and condensed or converted into sulfonate, and the activating treatment is to acidify the sulfonic acid groups dehydrated and condensed or converted into sulfonate into sulfonic acid groups with high proton conductivity and is favorable for film formation.
Specifically, in the present embodiment, step S340: the activation treatment of the heat-treated film includes: placing the heat-treated film in H 2 O 2 And H 2 SO 4 And carrying out an activation reaction in the solution, and drying the membrane subjected to the activation treatment after the activation reaction.
More specifically, the reaction formula of the activation treatment of the heat-treated film is shown in the following formula (2):
specifically, in the above formula (2)
Refers to the polymer molecules within the film after heat treatment;
refers to a molecule of perfluorosulfonic acid, which is generated in an activation reaction and is subjected to dehydration condensation or salt formation;
refers to perfluorosulfonic acid molecules having sulfonic acid groups generated in an activation reaction;
refers to a proton exchange membrane with sulfonic acid groups obtained after activation treatment.
Further, in this embodiment, the control of the cross-linking density of the cross-linked interpenetrating network inside the proton exchange membrane prepared by the above preparation method can be realized by adjusting the monomer ratio between the dyadic olefin amine and the vinyl sulfonate, the amount of the initiator, the cross-linking curing conditions, and the like, so as to ensure that the prepared proton exchange membrane has sufficient strength and toughness; meanwhile, the swelling degree, the water absorption rate, the mechanical property, the gas permeability and the like of the proton exchange membrane can be controlled.
The invention also provides a proton exchange membrane which is prepared by the preparation method of any one of the above-mentioned methods.
Another preferred embodiment of the present invention also provides a fuel cell comprising the proton exchange membrane prepared by the preparation method of any one of the above.
The invention is illustrated by the following specific examples:
example 1
1) Mixing 15g of diallylamine and 5g of sodium styrene sulfonate to obtain a premix, dissolving the premix in 100mL of aqueous solvent, and uniformly stirring to obtain a mixed solution;
2) Mixing 0.5g of sodium bisulfite and 1.2g of potassium persulfate, dissolving the mixture in a water solvent, and uniformly stirring to obtain an initiator;
3) Under the condition of uniform stirring, controlling the reaction temperature to be 65-70 ℃ and keeping the reaction temperature under the condition of nitrogen, slowly dropwise adding an initiator into the mixed solution to initiate free radical polymerization reaction between the dialkene amine and the vinyl sulfonate in the mixed solution so as to obtain a linear prepolymer solution;
4) Adding 200mL of 1mol/L sulfuric acid solution into the linear prepolymer solution, and treating the linear prepolymer solution by using a dialysis bag with the molecular weight cutoff of 8000 to realize acidification treatment of the linear prepolymer solution to obtain an acidified linear prepolymer solution;
5) The linear prepolymer solution after the acidification treatment, the perfluorosulfonic acid resin dispersion (PFSA dispersion, 25 wt%), and the ethanol-isopropanol mixed solution were mixed in the following ratio of 1: mixing and reacting according to the proportion of 100 to obtain polymer slurry; the above-mentioned 25wt% means that the mass concentration of the perfluorosulfonic acid resin in the perfluorosulfonic acid resin dispersion liquid is 25%;
6) Coating the polymer slurry into a film, and drying at a reaction temperature of 60 ℃; carrying out thermal curing treatment on the dried film for 30min at the reaction temperature of 110 ℃; carrying out heat treatment on the film subjected to the heat curing treatment at the reaction temperature of 160 ℃ for 20 min; placing the heat-treated film in 3%H 2 O 2 And 1mol/LH 2 SO 4 And (3) carrying out activation treatment in the solution for 30min, and drying after the activation treatment to obtain the proton exchange membrane with the cross-linked interpenetrating network structure.
Example 2
1) Mixing 12.5g of diallyl chloroacetamide with 3.6g of sodium allylsulfonate to obtain a premix, dissolving the premix in 100mL of aqueous solvent, and uniformly stirring to obtain a mixed solution;
2) Mixing 0.5g of sodium bisulfite and 1.2g of potassium persulfate, dissolving the mixture in a water solvent, and uniformly stirring to obtain an initiator;
3) Under the condition of uniform stirring, controlling the reaction temperature to be 75-80 ℃ and keeping the reaction temperature under the condition of nitrogen, slowly dropwise adding an initiator into the mixed solution to initiate free radical polymerization reaction between the dialkene amine and the vinyl sulfonate in the mixed solution so as to obtain a linear prepolymer solution;
4) Adding 200mL of 1mol/L sulfuric acid solution into the linear prepolymer solution, and treating the linear prepolymer solution by using a dialysis bag with the molecular weight cutoff of 8000-14000 to realize acidification treatment of the linear prepolymer solution to obtain the acidified linear prepolymer solution;
5) The linear prepolymer solution after the acidification treatment, the perfluorosulfonic acid resin dispersion (PFSA dispersion, 25 wt%), and the ethanol-isopropanol mixed solution were mixed in the following ratio of 2: mixing and reacting according to the proportion of 100 to obtain polymer slurry;
6) Coating the polymer slurry into a film, and drying at a reaction temperature of 60 ℃; carrying out thermal curing treatment on the dried film for 30min at the reaction temperature of 120 ℃; carrying out heat treatment on the film subjected to the heat curing treatment for 30min at the reaction temperature of 160 ℃; placing the heat-treated film in 3%H 2 O 2 And 1mol/LH 2 SO 4 And (3) carrying out activation treatment in the solution for 30min, and drying after the activation treatment to obtain the proton exchange membrane with the cross-linked interpenetrating network structure.
Example 3
1) Mixing 10g of diallyl dimethyl ammonium chloride with 5g of sodium vinyl sulfonate to obtain a premix, dissolving the premix in 100mL of water solvent, and uniformly stirring to obtain a mixed solution;
2) Mixing 0.5g of sodium bisulfite and 1.2g of potassium persulfate, dissolving the mixture in a water solvent, and uniformly stirring to obtain an initiator;
3) Under the condition of uniform stirring, controlling the reaction temperature to be 75-80 ℃ and keeping the reaction temperature under the condition of nitrogen, slowly dropwise adding an initiator into the mixed solution to initiate free radical polymerization reaction between the dialkene amine and the vinyl sulfonate in the mixed solution so as to obtain a linear prepolymer solution;
4) Adding 200mL of 1mol/L sulfuric acid solution into the linear prepolymer solution, and treating the linear prepolymer solution by using a dialysis bag with the molecular weight cutoff of 8000-14000 to realize acidification treatment of the linear prepolymer solution to obtain the acidified linear prepolymer solution;
5) The linear prepolymer solution after the acidification treatment, the perfluorosulfonic acid resin dispersion (PFSA dispersion, 25 wt%), and the ethanol-isopropanol mixed solution were mixed in the following ratio of 4: 100 (25 wt%) to obtain polymer slurry;
6) Coating the polymer slurry into a film, and drying at a reaction temperature of 60 ℃; carrying out thermal curing treatment on the dried film for 30min at the reaction temperature of 120 ℃; carrying out heat treatment on the film subjected to heat curing treatment at a reaction temperature of 160 ℃ for 30 min; placing the heat-treated film in 3%H 2 O 2 And 1mol/LH 2 SO 4 And (3) carrying out activation treatment in the solution for 30min, and drying after the activation treatment to obtain the proton exchange membrane with the cross-linked interpenetrating network structure.
Comparative example
1) Dispersing a perfluorosulfonic acid resin dispersion (PFSA dispersion) into a mixed polyol to obtain a polymer slurry with a content of 10 wt%;
2) Coating the polymer slurry to form a film to obtain a composite film, wherein the thickness of the composite film is 300um;
3) Drying the composite membrane at 80 ℃ for 10min, and then carrying out heat treatment at 180 ℃ for 30min to obtain a pure PFSA membrane;
4) The resulting pure PFSA film was placed in 3%H 2 O 2 And 1mol/LH 2 SO 4 And (3) carrying out activation treatment in the solution for 30min, and drying after treatment to obtain the pure PFSA proton exchange membrane.
Referring to table 1, table 1 shows a comparison of the performance of the proton exchange membranes prepared in examples 1, 2 and 3 and the pure PFSA proton exchange membrane prepared in the comparative example.
TABLE 1
Referring to table 1, as can be seen from comparison of data of examples 1, 2 and 3 and comparative examples in table 1, the proton exchange membrane with a cross-linked interpenetrating network prepared by using a highly stable cross-linked polymer network as a framework and realizing an interpenetrating network with a perfluorosulfonic acid polymer molecule is superior to the proton exchange membrane with pure PFSA prepared by the comparative examples in terms of swelling degree, mechanical strength, proton conductivity and the like.
In conclusion, the proton exchange membrane prepared by the invention has higher mechanical strength, dimensional stability and mechanical life, and macroscopically and microscopically inhibits the repeated swelling-shrinking deformation of the proton exchange membrane caused by the long-term dry-wet cycle and cold-hot cycle environmental change of the proton exchange membrane, thereby inhibiting the swelling degree of the proton exchange membrane; meanwhile, the proton exchange membrane prepared by the method contains a large number of hydrophilic groups such as amino groups and sulfonic acid groups, the amino groups and the sulfonic acid groups can form acid-base pairs, and the high proton conductivity and water retention capacity of the proton exchange membrane can be realized through the acid-base pairs.
The above description is only an exemplary embodiment of the present invention, and is not intended to limit the scope of the present invention. Any equivalent changes and modifications that can be made by one skilled in the art without departing from the spirit and principles of the invention should fall within the protection scope of the invention. It should be noted that the components of the present invention are not limited to the above-mentioned whole application, and various technical features described in the present specification can be selected to be used alone or in combination according to actual needs, so that the present invention naturally covers other combinations and specific applications related to the invention.
Claims (8)
1. A preparation method of a proton exchange membrane is characterized by comprising the following steps:
preparing a linear prepolymer solution; the linear prepolymer solution is obtained by adding an initiator into a mixed solution of a binary olefin amine, a vinyl sulfonate and a water solvent at a reaction temperature of 65-80 ℃ under the condition of nitrogen, and then initiating the free radical polymerization reaction of the binary olefin amine and the vinyl sulfonate in the mixed solution, wherein the initiator is a redox system initiator;
mixing the linear prepolymer solution, a perfluorinated sulfonic acid resin dispersion solution and mixed polyol according to a preset proportion to react to obtain polymer slurry;
coating the polymer slurry into a film, and drying, curing and forming the film to obtain the proton exchange membrane with a cross-linked interpenetrating network structure;
the method comprises the following steps of coating the polymer slurry into a film, drying and curing the film to obtain the proton exchange membrane with the cross-linked interpenetrating network structure, wherein the steps of coating the polymer slurry into the film, and drying, curing and molding the film to obtain the proton exchange membrane with the cross-linked interpenetrating network structure comprise:
coating the polymer slurry into a film, and drying the coated film at a reaction temperature of 60-80 ℃;
carrying out cross-linking curing treatment on the dried membrane;
carrying out heat treatment on the film subjected to crosslinking and curing treatment at the reaction temperature of 160-180 ℃;
activating the membrane after heat treatment to obtain a proton exchange membrane with a cross-linked interpenetrating network structure;
wherein, the step of mixing and reacting the linear prepolymer solution, the perfluorosulfonic acid resin dispersion solution and the mixed polyol according to a preset proportion to obtain the polymer slurry further comprises the following steps:
acidifying the linear prepolymer solution;
adding a sixth preset amount of acid solution into the linear prepolymer solution, and treating the linear prepolymer solution by using a dialysis bag with the cut-off molecular weight of 8000-14000 to realize acidification treatment of the linear prepolymer solution to obtain an acidified linear prepolymer solution; and then mixing the acidified prepolymer solution, the perfluorinated sulfonic acid resin dispersion liquid and the mixed polyol according to a preset proportion to react so as to obtain the polymer slurry.
2. The method of claim 1, wherein the step of preparing a linear prepolymer solution comprises:
mixing a first preset amount of dyadic alkene amine and a second preset amount of vinyl sulfonate to obtain a premix, dissolving the premix in a third preset amount of water solvent, and uniformly stirring to obtain a mixed solution;
and adding an initiator into the mixed solution at the reaction temperature of 65-80 ℃ and under the nitrogen condition to initiate free radical polymerization reaction between the dialkene amine and the vinyl sulfonate in the mixed solution to obtain the linear prepolymer solution.
3. The production method according to claim 1, wherein the step of subjecting the heat-treated film to an activation treatment comprises:
placing the heat-treated film in H 2 O 2 And H 2 SO 4 And carrying out an activation reaction in the solution, and drying the membrane subjected to the activation treatment after the activation reaction.
4. The production method according to claim 1, wherein the dialkene amine is an organic amine having a diene bond.
5. The production method according to claim 1, wherein the vinyl sulfonate is a sulfonate having a double bond.
6. The production method according to claim 1, wherein the initiator consists of a persulfate and a sulfite or a persulfate and a bisulfite.
7. A proton exchange membrane prepared by the preparation method of any one of claims 1 to 6.
8. A fuel cell comprising the proton exchange membrane of claim 7.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101510615A (en) * | 2009-03-26 | 2009-08-19 | 同济大学 | Semi-interpenetrating network type composite proton exchange film based on crosslinkable medlin and preparation method thereof |
| CN101787141A (en) * | 2009-12-25 | 2010-07-28 | 内蒙古科技大学 | Method for preparing proton exchange membrane with polyvinylidene fluoride grafted and grafting copolymerized with 2-acrylamido-2-methylpropanesulfonic acid |
| CN112079591A (en) * | 2020-08-07 | 2020-12-15 | 北京工业大学 | Method for synthesizing environment-responsive polymer by copolymerization modification of alkenyl sulfonate monomer |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001029800A (en) * | 1999-05-18 | 2001-02-06 | Sumitomo Electric Ind Ltd | Ion exchange film, ion exchange film/electrode conjugate and production of them |
| US20070020501A1 (en) * | 2005-07-21 | 2007-01-25 | Ling-Feng Li | Polyelectrolyte membranes as separator for battery and fuel cell applications |
| US10586995B2 (en) * | 2014-08-18 | 2020-03-10 | University Of Southern California | Method for the fabrication of homogenous blends of polystyrenesulfonic acid and polyvinylidene fluoride suitable for the application in direct oxidation methanol fuel cells (DMFCs) |
| CN108899566B (en) * | 2018-06-27 | 2021-03-26 | 大连理工大学 | Tertiary amino amphoteric ion exchange membrane and preparation method thereof |
| CN110128686B (en) * | 2019-04-29 | 2022-04-19 | 天津大学 | Preparation method of proton exchange membrane with chemical stability |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101510615A (en) * | 2009-03-26 | 2009-08-19 | 同济大学 | Semi-interpenetrating network type composite proton exchange film based on crosslinkable medlin and preparation method thereof |
| CN101787141A (en) * | 2009-12-25 | 2010-07-28 | 内蒙古科技大学 | Method for preparing proton exchange membrane with polyvinylidene fluoride grafted and grafting copolymerized with 2-acrylamido-2-methylpropanesulfonic acid |
| CN112079591A (en) * | 2020-08-07 | 2020-12-15 | 北京工业大学 | Method for synthesizing environment-responsive polymer by copolymerization modification of alkenyl sulfonate monomer |
Non-Patent Citations (2)
| Title |
|---|
| "Coacervation of copolymer of diallyldimethylammonium chloride and sodium styrenesulfonate aqueous solution";Yang Li，et al;《Journal of Macromolecular Science, Part A》;20171207;第2页第4-6段，附图2 * |
| "Proton exchange membranes with cross-linked interpenetrating network of sulfonated polyvinyl alcohol and poly (2-acrylamido-2-methyl-1-propanesulfonic acid): Excellent relative selectivity";Hai Qiang Li，et al;《Journal of Membrane Science》;20200201;第595卷;第2页第1-3段，附图1 * |
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