CN111048811B - Composite proton exchange membrane, preparation method and proton exchange membrane fuel cell - Google Patents

Composite proton exchange membrane, preparation method and proton exchange membrane fuel cell Download PDF

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CN111048811B
CN111048811B CN201910083608.8A CN201910083608A CN111048811B CN 111048811 B CN111048811 B CN 111048811B CN 201910083608 A CN201910083608 A CN 201910083608A CN 111048811 B CN111048811 B CN 111048811B
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exchange membrane
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CN111048811A (en
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陈莉
王洁
胡斌
孟宪涛
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Nanjing Panfeng Saiao Energy Technology Co ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • 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
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • 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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Abstract

The invention relates to a composite proton exchange membrane, a preparation method and a proton exchange membrane fuel cell, belonging to the technical field of proton exchange membrane fuel cells. The composite proton exchange membrane is prepared by using a polytetrafluoroethylene porous membrane as a base material, filling titanium oxide particles in micropores of the base material, and coating Nafion resin on the micropores and the surface of the base material. The composite proton exchange membrane provided by the invention utilizes TiO2The water retention property of the Nafion proton exchange membrane is beneficial to improving the operation stability of the Nafion proton exchange membrane under the high temperature condition; meanwhile, the invention adopts the polytetrafluoroethylene substrate, which is beneficial to improving the physical strength of the proton exchange membrane.

Description

Composite proton exchange membrane, preparation method and proton exchange membrane fuel cell
Technical Field
The invention relates to a composite proton exchange membrane, a preparation method and a proton exchange membrane fuel cell, belonging to the technical field of proton exchange membrane fuel cells.
Background
With the increasingly prominent global energy and environmental problems, proton exchange membrane fuel cells are receiving more and more attention from researchers due to the advantages of high energy conversion rate, zero pollution and the like. Proton exchange membrane fuel cells have high requirements on membranes, and the proton exchange membranes have the functions of conducting protons and blocking reaction gases, so that high proton conducting capacity, low reaction gas permeability, certain mechanical strength, good chemical and electrochemical stability and the like are required. Nowadays, in the membrane electrode material of proton exchange membrane fuel cells, the perfluorinated sulfonic acid type proton exchange membrane has always occupied a leading position, and internationally, Dupont company realizes the commercial production of the perfluorinated sulfonic acid type proton exchange membrane for large-scale fuel cells, and the product is a Nafion membrane. However, such a film is expensive, and has disadvantages such as poor dimensional properties and poor strength, and therefore, it has become a hot spot of recent research to compound Nafion resin with various reinforcing substrates by a compounding method.
Meanwhile, when the Nafion membrane works at high temperature, a large amount of water is evaporated inside the Nafion membrane, so that the proton conductivity of the Nafion membrane is reduced rapidly, and further development of the Nafion membrane is limited. However, this method has certain disadvantages, on one hand, because the loading amount of the titanium dioxide nanoparticles in the film is limited, the excessive loading of the titanium dioxide nanoparticles can cause the strength of the film to be reduced; on the other hand, the surface of the titanium dioxide has higher hydrophilicity, the Nafion membrane has higher hydrophobicity, the Nafion membrane and the titanium dioxide cannot be effectively fused, and the agglomeration and the loss of titanium dioxide particles are waited during long-term operation, so that the performance of the membrane is reduced.
Disclosure of Invention
The invention aims to solve the technical problems that the Nafion membrane is not high in strength on one hand, and the operation effect is reduced due to the fact that titanium dioxide particles are filled in the Nafion membrane on the other hand.
A composite proton exchange membrane is prepared from porous teflon membrane as substrate, titanium oxide particles filled in the pores of substrate, and Nafion resin coated on the pores and surface of substrate.
In one embodiment, a pH sensitive gel is also distributed within the micropores of the substrate.
The preparation method of the composite proton exchange membrane comprises the following steps:
step 1, preparation of a base film: uniformly mixing 100 parts of polytetrafluoroethylene, 1-2 parts of surfactant, 10-12 parts of pore-forming agent and 90-130 parts of organic solvent according to parts by weight, removing the organic solvent under reduced pressure, raising the temperature to 120-140 ℃, pressing into a tablet, stretching into a film at 120-130 ℃, and then raising the temperature under reduced pressure to remove the pore-forming agent to obtain a porous polytetrafluoroethylene-based film;
step 2, preparing a pH sensitive monomer reaction solution: uniformly mixing 40-50 parts by weight of N, N '-dimethylaminoethyl methacrylate, 25-30 parts by weight of N, N' -dimethylacrylamide and 70-100 parts by weight of dimethylformamide, adding 5-10 parts by weight of a cross-linking agent, 2-4 parts by weight of an initiator and 10-12 parts by weight of polyethylene glycol, uniformly mixing, and degassing to obtain a pH sensitive monomer reaction solution;
step 3, dip-coating monomer reaction solution on the base film: soaking the base membrane in a pH sensitive monomer reaction solution, and vacuumizing to enable the reaction solution to enter the micropores;
step 4, polymerization: heating the obtained base membrane to 65-75 ℃ in a nitrogen atmosphere, reacting for 2-4h, soaking the reaction product in deionized water to remove unreacted raw materials, taking out, and drying under reduced pressure to obtain a base membrane modified by the pH sensitive polymer;
step 5, preparing titanium oxide sol: dissolving 3-5 parts by weight of n-butyl titanate in 25-35 parts by weight of absolute ethyl alcohol, dripping the absolute ethyl alcohol into 30-40 parts by weight of deionized water, heating to 60-70 ℃, reacting for 0.5-1h, adjusting the pH to 4-5 by using dilute nitric acid with the pH of 1, keeping the temperature at 60-65 ℃ for 3-5h, cooling to room temperature, and aging for 10-20h to obtain titanium oxide sol;
step 6, loading of the titanium oxide sol on the base material: adjusting the pH value of the titanium oxide sol to 3-4 by using dilute nitric acid, and then performing pressure filtration on a base membrane modified by a pH sensitive polymer to deposit titanium oxide nano particles in membrane pores of the base membrane until the flow of a filter solution is reduced to 2/3 of the initial value; taking out the base membrane, soaking the base membrane in a dilute NaOH solution with the pH of 8-9 to swell the gel, soaking the base membrane in a dilute HCl solution with the pH of 5-6 to shrink the gel, taking out the base membrane, and drying the base membrane to obtain a titanium oxide loaded base material;
and 7, preparing coating liquid: mixing 100 parts by weight of Nafion solution, 80-120 parts by weight of dimethylformamide and 1-3 parts by weight of non-ionic surfactant, and heating to 90-100 ℃ to uniformly mix to obtain Nafion coating liquid;
step 8, loading of Nafion resin: soaking a titanium oxide-loaded substrate in a Nafion coating solution, vacuumizing, taking out the substrate, and placing the substrate in a vacuum drying oven at 60-80 ℃ for vacuum drying to remove a solvent to obtain a proton exchange membrane;
step 9, post-treatment: and (3) treating the proton exchange membrane obtained in the step (8) in isopropanol, 1mol/L dilute sulfuric acid solution at 70-80 ℃ and deionized water at 90-100 ℃ in sequence to obtain the composite proton exchange membrane.
In one embodiment, the surfactant in step 1 is an anionic fluorocarbon surfactant; the pore-forming agent is liquid paraffin; the organic solvent is absolute ethyl alcohol.
In one embodiment, said crosslinking agent in step 2 is N, N' -methylenebisacrylamide; the initiator is azobisisobutyronitrile; the molecular weight of the polyethylene glycol is 400-2000.
In one embodiment, the mass concentration of the Nafion resin in the Nafion solution in step 7 is 5%, and the nonionic surfactant is polyethylene glycol octyl phenyl ether.
In one embodiment, step 8 is repeated 2-4 times.
The fuel cell comprises the composite proton exchange membrane.
Advantageous effects
The composite proton exchange membrane provided by the invention utilizes TiO2The water retention property of the Nafion proton exchange membrane is beneficial to improving the operation stability of the Nafion proton exchange membrane under the high temperature condition.
Meanwhile, the invention adopts the polytetrafluoroethylene substrate, which is beneficial to improving the physical strength of the proton exchange membrane.
In the preparation method, firstly, the gel with pH sensitivity is prepared and distributed in the film pores of the base material, and when the pH is reduced, the gel shrinks and can be dissolved by titanium oxideThe glue penetrates into the pore channel more, and the gel swells after the pH value is raised, so that titanium oxide particles and Nafion solution are fully distributed in the pore channel, the physical property of the proton exchange membrane and TiO are improved2Stability of (2).
Drawings
FIG. 1 is a SEM photograph of the surface of a proton exchange membrane supporting silica sol in example 3.
FIG. 2 is a SEM photograph of the surface of the proton exchange membrane loaded with silica sol after the sol is gelled in example 3.
Figure 3 is a graph comparing water content performance of proton exchange membranes.
Figure 4 is a graph comparing proton exchange membrane swelling ratio performance.
Figure 5 is a graph comparing tensile strength performance of proton exchange membranes.
Figure 6 is a proton exchange membrane fuel cell operational stability test output voltage curve.
Detailed Description
EXAMPLE 1 preparation of composite proton exchange membranes
Step 1, preparation of a base film: uniformly mixing 100 parts of polytetrafluoroethylene, 1 part of anionic fluorocarbon surfactant, 10 parts of liquid paraffin and 90 parts of absolute ethyl alcohol according to parts by weight, decompressing and removing an organic solvent, raising the temperature to 120 ℃, pressing into a sheet, stretching into a thin film at 120 ℃, decompressing and heating to remove a pore-forming agent, and obtaining a porous polytetrafluoroethylene-based film;
step 2, preparing a pH sensitive monomer reaction solution: uniformly mixing 40 parts by weight of N, N ' -dimethylaminoethyl methacrylate, 25 parts by weight of N, N ' -dimethylacrylamide and 70 parts by weight of dimethylformamide, adding 5 parts by weight of crosslinking agent N, N ' -methylenebisacrylamide, 2 parts by weight of initiator azobisisobutyronitrile and 200010 parts by weight of polyethylene glycol, uniformly mixing, and degassing to obtain a pH sensitive monomer reaction solution;
step 3, dip-coating monomer reaction solution on the base film: soaking the base membrane in a pH sensitive monomer reaction solution, and vacuumizing to enable the reaction solution to enter the micropores;
step 4, polymerization: heating the obtained base membrane to 65 ℃ in a nitrogen atmosphere for reaction for 2 hours, soaking the reaction product in deionized water to remove unreacted raw materials, taking out the raw materials, and drying the raw materials under reduced pressure to obtain a base membrane modified by the pH sensitive polymer;
step 5, preparing titanium oxide sol: dissolving 3 parts by weight of n-butyl titanate in 25 parts by weight of absolute ethyl alcohol, dripping the absolute ethyl alcohol solution into 30 parts by weight of deionized water, heating to 60 ℃, reacting for 0.5h, adjusting the pH to 4-5 by using dilute nitric acid with the pH of 1, keeping the temperature at 60 ℃ for 3h, cooling to room temperature, and aging for 10h to obtain titanium oxide sol;
step 6, loading of the titanium oxide sol on the base material: adjusting the pH value of the titanium oxide sol to 3-4 by using dilute nitric acid, and then performing pressure filtration on a base membrane modified by a pH sensitive polymer to deposit titanium oxide nano particles in membrane pores of the base membrane until the flow of a filter solution is reduced to 2/3 of the initial value; taking out the base membrane, soaking the base membrane in a dilute NaOH solution with the pH of 8-9 to swell the gel, soaking the base membrane in a dilute HCl solution with the pH of 5-6 to shrink the gel, taking out the base membrane, and drying the base membrane to obtain a titanium oxide loaded base material;
and 7, preparing coating liquid: mixing 100 parts by weight of 5wt% Nafion solution, 80 parts by weight of dimethylformamide and 1 part by weight of polyethylene glycol octyl phenyl ether, and heating to 90 ℃ to uniformly mix to obtain Nafion coating liquid;
step 8, loading of Nafion resin: soaking a titanium oxide-loaded substrate in a Nafion coating solution, vacuumizing, taking out the substrate, and placing the substrate in a vacuum drying oven at 60 ℃ for vacuum drying to remove a solvent to obtain a proton exchange membrane; and repeat step 3 times;
step 9, post-treatment: and (3) treating the proton exchange membrane obtained in the step (8) in isopropanol, 1mol/L dilute sulfuric acid solution at 70 ℃ and deionized water at 90 ℃ in sequence to obtain the composite proton exchange membrane.
EXAMPLE 2 preparation of composite proton exchange membranes
Step 1, preparation of a base film: uniformly mixing 100 parts of polytetrafluoroethylene, 2 parts of anionic fluorocarbon surfactant, 12 parts of liquid paraffin and 130 parts of absolute ethyl alcohol according to parts by weight, decompressing and removing organic solvent, raising the temperature to 140 ℃, pressing into a sheet, stretching into a film at 130 ℃, decompressing and heating to remove pore-forming agent, and obtaining a porous polytetrafluoroethylene-based film;
step 2, preparing a pH sensitive monomer reaction solution: according to the weight portion, 50 portions of N, N ' -dimethylaminoethyl methacrylate, 30 portions of N, N ' -dimethylacrylamide and 100 portions of dimethylformamide are uniformly mixed, 10 portions of cross-linking agent N, N ' -methylene bisacrylamide, 4 portions of initiator azobisisobutyronitrile and 200012 portions of polyethylene glycol are added, and degassing is carried out after uniform mixing to obtain pH sensitive monomer reaction solution;
step 3, dip-coating monomer reaction solution on the base film: soaking the base membrane in a pH sensitive monomer reaction solution, and vacuumizing to enable the reaction solution to enter the micropores;
step 4, polymerization: heating the obtained base membrane to 75 ℃ in a nitrogen atmosphere for reacting for 4h, soaking the reaction product in deionized water to remove unreacted raw materials, taking out the raw materials, and drying the raw materials under reduced pressure to obtain a base membrane modified by the pH sensitive polymer;
step 5, preparing titanium oxide sol: dissolving 5 parts by weight of n-butyl titanate in 35 parts by weight of absolute ethyl alcohol, dripping the absolute ethyl alcohol into 40 parts by weight of deionized water, heating to 70 ℃ for reaction for 1h, adjusting the pH to 4-5 by using dilute nitric acid with the pH of 1, keeping the pH at 65 ℃ for 5h, cooling to room temperature, and aging for 20h to obtain titanium oxide sol;
step 6, loading of the titanium oxide sol on the base material: adjusting the pH value of the titanium oxide sol to 3-4 by using dilute nitric acid, and then performing pressure filtration on a base membrane modified by a pH sensitive polymer to deposit titanium oxide nano particles in membrane pores of the base membrane until the flow of a filter solution is reduced to 2/3 of the initial value; taking out the base membrane, soaking the base membrane in a dilute NaOH solution with the pH of 8-9 to swell the gel, soaking the base membrane in a dilute HCl solution with the pH of 5-6 to shrink the gel, taking out the base membrane, and drying the base membrane to obtain a titanium oxide loaded base material;
and 7, preparing coating liquid: mixing 100 parts by weight of 5wt% Nafion solution, 120 parts by weight of dimethylformamide and 3 parts by weight of polyethylene glycol octyl phenyl ether, and heating to 100 ℃ to uniformly mix to obtain Nafion coating liquid;
step 8, loading of Nafion resin: soaking a titanium oxide-loaded substrate in a Nafion coating solution, vacuumizing, taking out the substrate, and placing the substrate in a vacuum drying oven at 80 ℃ for vacuum drying to remove a solvent to obtain a proton exchange membrane; and repeat step 3 times;
step 9, post-treatment: and (3) treating the proton exchange membrane obtained in the step (8) in isopropanol, 1mol/L dilute sulfuric acid solution at 80 ℃ and deionized water at 100 ℃ in sequence to obtain the composite proton exchange membrane.
EXAMPLE 3 preparation of composite proton exchange membranes
Step 1, preparation of a base film: uniformly mixing 100 parts of polytetrafluoroethylene, 1 part of anionic fluorocarbon surfactant, 11 parts of liquid paraffin and 110 parts of absolute ethyl alcohol according to parts by weight, decompressing and removing an organic solvent, raising the temperature to 130 ℃, pressing into a tablet, stretching into a film at 125 ℃, decompressing and heating to remove a pore-forming agent to obtain a porous polytetrafluoroethylene-based film;
step 2, preparing a pH sensitive monomer reaction solution: uniformly mixing 45 parts by weight of N, N ' -dimethylaminoethyl methacrylate, 280 parts by weight of N, N ' -dimethylacrylamide and 90 parts by weight of dimethylformamide, adding 6 parts by weight of crosslinking agent N, N ' -methylenebisacrylamide, 3 parts by weight of initiator azobisisobutyronitrile and 200011 parts by weight of polyethylene glycol, uniformly mixing, and degassing to obtain a pH sensitive monomer reaction solution;
step 3, dip-coating monomer reaction solution on the base film: soaking the base membrane in a pH sensitive monomer reaction solution, and vacuumizing to enable the reaction solution to enter the micropores;
step 4, polymerization: heating the obtained base membrane to 70 ℃ in a nitrogen atmosphere for reaction for 3 hours, soaking the reaction product in deionized water to remove unreacted raw materials, taking out the raw materials, and drying the raw materials under reduced pressure to obtain a base membrane modified by the pH sensitive polymer;
step 5, preparing titanium oxide sol: dissolving 4 parts by weight of n-butyl titanate in 30 parts by weight of absolute ethyl alcohol, dripping the absolute ethyl alcohol into 35 parts by weight of deionized water, heating to 65 ℃ for reaction for 1h, adjusting the pH to 4-5 by using dilute nitric acid with the pH of 1, keeping the pH at 62 ℃ for 4h, cooling to room temperature, and aging for 15h to obtain titanium oxide sol;
step 6, loading of the titanium oxide sol on the base material: adjusting the pH value of the titanium oxide sol to 3-4 by using dilute nitric acid, and then performing pressure filtration on a base membrane modified by a pH sensitive polymer to deposit titanium oxide nano particles in membrane pores of the base membrane until the flow of a filter solution is reduced to 2/3 of the initial value; taking out the base membrane, soaking the base membrane in a dilute NaOH solution with the pH of 8-9 to swell the gel, soaking the base membrane in a dilute HCl solution with the pH of 5-6 to shrink the gel, taking out the base membrane, and drying the base membrane to obtain a titanium oxide loaded base material;
and 7, preparing coating liquid: mixing 100 parts by weight of 5wt% Nafion solution, 110 parts by weight of dimethylformamide and 2 parts by weight of polyethylene glycol octyl phenyl ether, and heating to 95 ℃ to uniformly mix to obtain Nafion coating liquid;
step 8, loading of Nafion resin: soaking a titanium oxide-loaded substrate in a Nafion coating solution, vacuumizing, taking out the substrate, and placing the substrate in a vacuum drying oven at 70 ℃ for vacuum drying to remove a solvent to obtain a proton exchange membrane; and repeat step 3 times;
step 9, post-treatment: and (3) treating the proton exchange membrane obtained in the step (8) in isopropanol, 1mol/L dilute sulfuric acid solution at 75 ℃ and deionized water at 95 ℃ in sequence to obtain the composite proton exchange membrane.
Comparative example 1
The differences from example 3 are: no pH sensitive gel was used for loading on the substrate.
Step 1, preparation of a base film: uniformly mixing 100 parts of polytetrafluoroethylene, 1 part of anionic fluorocarbon surfactant, 11 parts of liquid paraffin and 110 parts of absolute ethyl alcohol according to parts by weight, decompressing and removing an organic solvent, raising the temperature to 130 ℃, pressing into a tablet, stretching into a film at 125 ℃, decompressing and heating to remove a pore-forming agent to obtain a porous polytetrafluoroethylene-based film;
step 2, preparing titanium oxide sol: dissolving 4 parts by weight of n-butyl titanate in 30 parts by weight of absolute ethyl alcohol, dripping the absolute ethyl alcohol into 35 parts by weight of deionized water, heating to 65 ℃ for reaction for 1h, adjusting the pH to 4-5 by using dilute nitric acid with the pH of 1, keeping the pH at 62 ℃ for 4h, cooling to room temperature, and aging for 15h to obtain titanium oxide sol;
step 3, loading of the titanium oxide sol on the base material: adjusting the pH value of the titanium oxide sol to 3-4 by using dilute nitric acid, and then performing pressure filtration on a porous polytetrafluoroethylene-based membrane to deposit titanium oxide nanoparticles in membrane pores of a base membrane until the flow of a filtrate is reduced to 2/3 of the initial value, thereby obtaining a titanium oxide-loaded base material;
step 4, preparing coating liquid: mixing 100 parts by weight of 5wt% Nafion solution, 110 parts by weight of dimethylformamide and 2 parts by weight of polyethylene glycol octyl phenyl ether, and heating to 95 ℃ to uniformly mix to obtain Nafion coating liquid;
step 5, loading of Nafion resin: soaking a titanium oxide-loaded substrate in a Nafion coating solution, vacuumizing, taking out the substrate, and placing the substrate in a vacuum drying oven at 70 ℃ for vacuum drying to remove a solvent to obtain a proton exchange membrane; and repeat step 3 times;
step 6, post-treatment: and (3) treating the proton exchange membrane obtained in the step (5) in isopropanol, 1mol/L dilute sulfuric acid solution at 75 ℃ and deionized water at 95 ℃ in sequence to obtain the composite proton exchange membrane.
Comparative example 2
The differences from example 3 are: when the loading of the titania sol is carried out in the 6 th step, the pH of the titania sol is not adjusted to acidity.
Step 1, preparation of a base film: uniformly mixing 100 parts of polytetrafluoroethylene, 1 part of anionic fluorocarbon surfactant, 11 parts of liquid paraffin and 110 parts of absolute ethyl alcohol according to parts by weight, decompressing and removing an organic solvent, raising the temperature to 130 ℃, pressing into a tablet, stretching into a film at 125 ℃, decompressing and heating to remove a pore-forming agent to obtain a porous polytetrafluoroethylene-based film;
step 2, preparing a pH sensitive monomer reaction solution: uniformly mixing 45 parts by weight of N, N ' -dimethylaminoethyl methacrylate, 280 parts by weight of N, N ' -dimethylacrylamide and 90 parts by weight of dimethylformamide, adding 6 parts by weight of crosslinking agent N, N ' -methylenebisacrylamide, 3 parts by weight of initiator azobisisobutyronitrile and 200011 parts by weight of polyethylene glycol, uniformly mixing, and degassing to obtain a pH sensitive monomer reaction solution;
step 3, dip-coating monomer reaction solution on the base film: soaking the base membrane in a pH sensitive monomer reaction solution, and vacuumizing to enable the reaction solution to enter the micropores;
step 4, polymerization: heating the obtained base membrane to 70 ℃ in a nitrogen atmosphere for reaction for 3 hours, soaking the reaction product in deionized water to remove unreacted raw materials, taking out the raw materials, and drying the raw materials under reduced pressure to obtain a base membrane modified by the pH sensitive polymer;
step 5, preparing titanium oxide sol: dissolving 4 parts by weight of n-butyl titanate in 30 parts by weight of absolute ethyl alcohol, dripping the absolute ethyl alcohol into 35 parts by weight of deionized water, heating to 65 ℃ for reaction for 1h, adjusting the pH to 4-5 by using dilute nitric acid with the pH of 1, keeping the pH at 62 ℃ for 4h, cooling to room temperature, and aging for 15h to obtain titanium oxide sol;
step 6, loading of the titanium oxide sol on the base material: adjusting the pH value of the titanium oxide sol to 7-8 by using NaOH solution, and then performing pressure filtration on a base membrane modified by a pH sensitive polymer to deposit titanium oxide nano particles in membrane pores of the base membrane until the flow of a filter solution is reduced to 2/3 of the initial value; taking out the base membrane, soaking the base membrane in a dilute NaOH solution with the pH of 8-9 to swell the gel, soaking the base membrane in a dilute HCl solution with the pH of 5-6 to shrink the gel, taking out the base membrane, and drying the base membrane to obtain a titanium oxide loaded base material;
and 7, preparing coating liquid: mixing 100 parts by weight of 5wt% Nafion solution, 110 parts by weight of dimethylformamide and 2 parts by weight of polyethylene glycol octyl phenyl ether, and heating to 95 ℃ to uniformly mix to obtain Nafion coating liquid;
step 8, loading of Nafion resin: soaking a titanium oxide-loaded substrate in a Nafion coating solution, vacuumizing, taking out the substrate, and placing the substrate in a vacuum drying oven at 70 ℃ for vacuum drying to remove a solvent to obtain a proton exchange membrane; and repeat step 3 times;
step 9, post-treatment: and (3) treating the proton exchange membrane obtained in the step (8) in isopropanol, 1mol/L dilute sulfuric acid solution at 75 ℃ and deionized water at 95 ℃ in sequence to obtain the composite proton exchange membrane.
SEM characterization of substrates
In example 3, when the acidic titania solution was pressed onto the surface of the gel, the SEM of the surface thereof is shown in fig. 1, and it can be seen that the gel was contracted and contained some titania nanoparticles therein; when the gel is treated under the alkaline condition, the SEM photograph is shown in figure 2, and it can be seen that the gel swells, so that the titanium oxide nano particles are coated by the gel, and the stability of the titanium oxide nano particles is improved.
Water content and swelling ratio of composite film
Cutting the dried composite proton exchange membrane into the size of 10cm multiplied by 10cm, soaking the membrane in deionized water at room temperature for 24h, and measuring the size again, wherein the water content in the membrane and the size change of the membrane are calculated by the following formulas:
water content W = (W)2-W1)/W1×100%
In the formula, W2Is the weight of the membrane after soaking, W1Is the membrane weight before soaking;
swelling ratio Δ S = (S)2-S1)/L1×100%
In the formula, S2Is the membrane area after soaking, S1Is the membrane area before soaking;
Figure DEST_PATH_IMAGE001
as can be seen from the table, the composite proton exchange membrane prepared by the invention has better water retention performance, and as can be seen by comparing the example 3 with the comparative example 1, the pH sensitive gel used as the loading material not only can play a role of loading titanium oxide particles, but also has better water retention; as can be seen from comparison between example 3 and comparative example 2, when the titanium oxide sol is loaded on the surface of the substrate, the gel can be effectively shrunk by adjusting the pH of the titanium oxide sol, so that more titanium oxide nanoparticles can be contained in the pores of the gel, and the titanium oxide nanoparticles fill the pores through swelling, so that the water retention performance of the proton exchange membrane is improved.
Tensile strength
The measurement is carried out by using a tensile tester under the conditions of standard width of 40mm, standard distance of 50mm and stretching speed of 50 mm/min.
Figure DEST_PATH_IMAGE002
As can be seen from the above table, the composite proton exchange membrane prepared by the invention has better strength, and as can be seen from the comparison between the example 3 and the comparative example 1, the pH sensitive gel is added in the preparation process of the proton exchange membrane substrate, so that the cross-linked gel can be effectively formed in the pore channel of the substrate, and the tensile strength of the proton exchange membrane is improved.
Assembly and operation of cells
Wetting 8g of Pt/C catalyst by using 5 ml of deionized water, adding 400ml of glycerol and 1.2g of polyvinyl alcohol, uniformly stirring, adding 35g of Nafion solution, stirring for 8 hours, adding 3g of polytetrafluoroethylene, and uniformly stirring by using ultrasonic waves to obtain the slurry. The slurry was coated on both sides of the proton exchange membranes prepared in the above examples and comparative examples, and the catalyst layer had a thickness of 5 μm and a Pt loading of 0.56mg/cm 2. And assembling the single cell by adopting carbon paper, a proton exchange membrane and a bipolar plate, and carrying out performance test. The temperature of the battery is 60 ℃, the anode is 100% humidified, and the humidifying temperature is 70 ℃.
The cells were subjected to an operation stabilization test for 800 hours, during which the output voltage was as shown in fig. 6, wherein 1 curve was the cell using the proton exchange membrane of example 3, 2 curve was the cell using the proton exchange membrane of comparative example 2, and 3 curve was the cell using the proton exchange membrane of comparative example 1.
As can be seen from the figure, the output power of the proton exchange membrane in the running process is more stable, which indicates that the service life of the proton exchange membrane is better; however, for the single cells prepared from the proton exchange membranes in comparative examples 1 and 2, the output voltage is obviously reduced in the operation process, which shows that the proton exchange membranes can not effectively maintain the moisture in the Nafion resin when operated under high temperature conditions, and the performance of the membranes is deteriorated, so that the output voltage is reduced.

Claims (8)

1. A composite proton exchange membrane is characterized in that a polytetrafluoroethylene porous membrane is used as a base material, and titanium oxide particles are filled in micropores of the base material, and Nafion resin is coated on the micropores and the surface of the base material; the pH sensitive gel is also distributed in the micropores of the substrate.
2. The method for preparing a composite proton exchange membrane according to claim 1, comprising the steps of:
step 1, preparation of a base film: uniformly mixing 100 parts of polytetrafluoroethylene, 1-2 parts of surfactant, 10-12 parts of pore-forming agent and 90-130 parts of organic solvent according to parts by weight, removing the organic solvent under reduced pressure, raising the temperature to 120-140 ℃, pressing into sheets, stretching into films at 120-130 ℃, and removing the pore-forming agent under reduced pressure and elevated temperature to obtain porous polytetrafluoroethylene-based films;
step 2, preparing a pH sensitive monomer reaction solution: uniformly mixing 40-50 parts by weight of N, N '-dimethylaminoethyl methacrylate, 25-30 parts by weight of N, N' -dimethylacrylamide and 70-100 parts by weight of dimethylformamide, adding 5-10 parts by weight of a cross-linking agent, 2-4 parts by weight of an initiator and 10-12 parts by weight of polyethylene glycol, uniformly mixing, and degassing to obtain a pH sensitive monomer reaction solution;
step 3, dip-coating monomer reaction solution on the base film: soaking the base membrane in a pH sensitive monomer reaction solution, and vacuumizing to enable the reaction solution to enter the micropores;
step 4, polymerization: heating the obtained base membrane to 65-75 ℃ in a nitrogen atmosphere, reacting for 2-4h, soaking the reaction product in deionized water to remove unreacted raw materials, taking out, and drying under reduced pressure to obtain a base membrane modified by the pH sensitive polymer;
step 5, preparing titanium oxide sol: dissolving 3-5 parts by weight of n-butyl titanate in 25-35 parts by weight of absolute ethyl alcohol, dripping the absolute ethyl alcohol into 30-40 parts by weight of deionized water, heating to 60-70 ℃, reacting for 0.5-1h, adjusting the pH to 4-5 by using dilute nitric acid with the pH of 1, keeping the temperature at 60-65 ℃ for 3-5h, cooling to room temperature, and aging for 10-20h to obtain titanium oxide sol;
step 6, loading of the titanium oxide sol on the base material: adjusting the pH value of the titanium oxide sol to 3-4 by using dilute nitric acid, and then performing pressure filtration on a base membrane modified by a pH sensitive polymer to deposit titanium oxide nano particles in membrane pores of the base membrane until the flow of a filter solution is reduced to 2/3 of the initial value; taking out the base membrane, soaking the base membrane in a dilute NaOH solution with the pH of 8-9 to swell the gel, soaking the base membrane in a dilute HCl solution with the pH of 5-6 to shrink the gel, taking out the base membrane, and drying the base membrane to obtain a titanium oxide loaded base material;
and 7, preparing coating liquid: mixing 100 parts by weight of Nafion solution, 80-120 parts by weight of dimethylformamide and 1-3 parts by weight of non-ionic surfactant, and heating to 90-100 ℃ to uniformly mix to obtain Nafion coating liquid;
step 8, loading of Nafion resin: soaking a titanium oxide-loaded substrate in a Nafion coating solution, vacuumizing, taking out the substrate, and placing the substrate in a vacuum drying oven at 60-80 ℃ for vacuum drying to remove a solvent to obtain a proton exchange membrane;
step 9, post-treatment: and (3) treating the proton exchange membrane obtained in the step (8) in isopropanol, 1mol/L dilute sulfuric acid solution at 70-80 ℃ and deionized water at 90-100 ℃ in sequence to obtain the composite proton exchange membrane.
3. The method for preparing a composite proton exchange membrane according to claim 2, wherein the surfactant in the step 1 is an anionic fluorocarbon surfactant; the pore-forming agent is liquid paraffin; the organic solvent is absolute ethyl alcohol.
4. The method for preparing a composite proton exchange membrane according to claim 2, wherein the cross-linking agent in the step 2 is N, N' -methylenebisacrylamide; the initiator is azobisisobutyronitrile; the molecular weight of the polyethylene glycol is 400-2000.
5. The method for preparing a composite proton exchange membrane according to claim 2, wherein the mass concentration of the Nafion resin in the Nafion solution in the step 7 is 5%, and the nonionic surfactant is polyethylene glycol octyl phenyl ether.
6. The process of claim 2 wherein step 8 is repeated 2-4 times.
7. A fuel cell device comprising the composite proton exchange membrane of claim 1.
8. Use of the composite proton exchange membrane of claim 1 in a fuel cell.
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