CN112701339A - Fuel cell proton exchange membrane suitable for intermediate temperature and preparation method thereof - Google Patents
Fuel cell proton exchange membrane suitable for intermediate temperature and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of fuel cells, and provides a proton exchange membrane suitable for a medium-temperature fuel cell and a preparation method thereof, wherein the proton exchange membrane is prepared by mixing gel powder and nafion solution, coating, rolling, drying, washing and drying; the gel powder is prepared by adding modified bentonite into a dopamine aqueous solution under an alkaline condition, then adding acrylamide, acrylic acid, polyethylene glycol diacrylate, N' N-methylene bisacrylamide and ammonium persulfate, mixing to obtain a gel precursor solution, and performing ultraviolet irradiation and centrifugal separation; the proton exchange membrane provided by the invention has excellent stability at medium temperature (80-100 ℃), good mechanical property and durability and simple process, and can effectively improve the working temperature of a fuel cell.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a fuel cell proton exchange membrane suitable for medium temperature and a preparation method thereof.
Background
A fuel cell is a chemical device that directly converts chemical energy of fuel into electrical energy, and is also called an electrochemical generator. It is a fourth power generation technology following hydroelectric power generation, thermal power generation and atomic power generation. The fuel cell converts the Gibbs free energy in the chemical energy of the fuel into electric energy through electrochemical reaction, and is not limited by the Carnot cycle effect, so the efficiency is high; in addition, fuel cells use fuel and oxygen as raw materials; meanwhile, no mechanical transmission part is arranged, so that no noise pollution is caused, and the discharged harmful gas is less. It follows that fuel cells are the most promising power generation technology from the viewpoint of energy conservation and ecological environment conservation.
The fuel cell is a powerful competitor of the next generation new energy automobile power source due to the characteristics of environmental protection, energy conservation and hopeful solution of mileage anxiety of the lithium battery. The core of the membrane electrode assembly is a membrane electrode assembly formed by compounding a proton exchange membrane, a catalyst and a gas diffusion layer. The proton exchange membrane is a core component of the proton exchange membrane fuel cell and plays a key role in the performance of the cell. Not only has the function of blocking, but also has the function of conducting protons. The performance of the proton exchange membrane largely determines the performance of the fuel cell.
At present, the proton exchange membrane of the fuel cell mainly uses a fluorosulfonic acid type proton exchange membrane, a nafion recast membrane, a non-fluorine polymer proton exchange membrane, a novel composite proton exchange membrane and the like. The traditional nafion perfluorosulfonic acid proton exchange membrane has the working temperature stabilized at 60-80 ℃, but water is easy to remain in a gas diffusion layer to cause flooding, and the catalyst is also easy to be poisoned by carbon monoxide. However, the loss of water at high temperature is serious, and the membrane material structure is seriously affected, the proton conductivity is sharply reduced, and the service life is seriously reduced. Therefore, the method has important significance for improving the durability of the proton exchange membrane.
Chinese patent application No. 200810160561.2 discloses a fuel cell proton exchange membrane capable of being used at medium temperature, which is a proton exchange membrane doped with sulfonated phenylphosphonic acid zirconium, and is characterized in that a membrane-making material is composed of a sulfonated high polymer material and sulfonated phenylphosphonic acid salt, wherein the sulfonation degree of the sulfonated high polymer material is selected from 20 to 85 percent, accounts for 60 to 95 percent of the mass of the membrane-making material, the sulfonation degree of the sulfonated phenylphosphonic acid salt is selected from 30 to 90 percent, and accounts for 5 to 40 percent of the mass of the membrane-making material. Porous supporting materials can be added into the membrane to improve the strength of the membrane and reduce the deformability; the membrane-making material fills the pores of the porous support material and forms a layer of membrane on the outer surface of the porous support material. Chinese invention patent application No. 201310357482.1 discloses a medium temperature proton exchange membrane material, a preparation method thereof and a fuel cell prepared by using the material, wherein the membrane material is a nitrogen-containing polyphosphonic siloxane polymer, the raw materials for preparing the nitrogen-containing polyphosphonic siloxane polymer comprise organic phosphonic acid, isocyanate siloxane and a solvent, the molar ratio of the raw materials is that the organic phosphonic acid: isocyanate siloxane = 1: 1-1: 2, mixing and reacting the raw materials to form nitrogen-containing polyphosphonic siloxane sol, and gelling and drying the nitrogen-containing polyphosphonic siloxane sol to form the intermediate-temperature proton exchange membrane material.
In order to improve the durability of the proton exchange membrane of the fuel cell at the intermediate temperature and effectively improve the working temperature of the fuel cell, a novel proton exchange membrane is necessary to be provided, and further, the development of the proton exchange membrane of the fuel cell and the development of the fuel cell are promoted.
Disclosure of Invention
Aiming at the problem that the existing fuel cell proton exchange membrane has poor durability at the medium temperature, the invention provides the fuel cell proton exchange membrane suitable for the medium temperature and the preparation method thereof, thereby improving the temperature tolerance of the proton exchange membrane and promoting the development of the fuel cell.
In order to achieve the purpose, the invention adopts the following technical scheme:
a proton exchange membrane suitable for a medium-temperature fuel cell is prepared by mixing gel powder and nafion solution, coating, rolling, drying, washing and drying; the gel powder is prepared by adding modified bentonite into an aqueous solution of dopamine under an alkaline condition, then adding acrylamide, acrylic acid, polyethylene glycol diacrylate, N' N-methylene bisacrylamide and ammonium persulfate, mixing and performing ultrasonic treatment to obtain a gel precursor solution, and then performing ultraviolet irradiation and centrifugal separation; the modified bentonite is prepared by adding a dilute hydrochloric acid solution of titanium tetrachloride into a suspension of bentonite powder, aging to obtain a modified bentonite slurry, mixing and stirring with an aluminum chloride aqueous solution and activated carbon powder, coating the mixture on the surface of a glass substrate, and calcining.
Preferably, the mass concentration of the nafion solution is 5-15%.
Preferably, the bentonite powder is sodium bentonite powder.
Preferably, the molar concentration of the dilute hydrochloric acid solution is 0.1-0.2 mol/L.
Preferably, the mass concentration of the aluminum chloride aqueous solution is 2-3%.
The invention also provides a preparation method of the proton exchange membrane suitable for the intermediate temperature fuel cell, which comprises the following steps:
(1) adding bentonite powder into deionized water to prepare a suspension, slowly adding a dilute hydrochloric acid solution of titanium tetrachloride into the suspension, standing and aging for 2-4h, and filtering to remove redundant solvent to obtain modified bentonite slurry;
(2) mixing the modified bentonite slurry with an aluminum chloride aqueous solution and activated carbon powder, stirring at the rotation speed of 400-500rpm for 30-40min, filtering, coating on the surface of a glass substrate, and calcining at high temperature to obtain modified bentonite powder;
(3) mixing dopamine and deionized water to prepare a solution, then adjusting the pH value to 10-11 by using sodium hydroxide, then adding modified bentonite powder, uniformly mixing to obtain a dopamine-modified bentonite dispersion solution, then adding acrylamide, acrylic acid, polyethylene glycol diacrylate, N' N-methylene bisacrylamide and ammonium persulfate, and then carrying out ultrasonic treatment for 10-30min at the frequency of 30-50kHz to obtain a gel precursor solution;
(4) and irradiating the obtained gel precursor solution under ultraviolet light, then performing centrifugal separation to obtain gel powder, mixing the gel powder with nafion solution, and then performing coating, rolling, drying, washing and drying to obtain the fuel cell proton exchange membrane suitable for medium temperature.
Preferably, in the preparation of the modified bentonite slurry in the step (1), the mass ratio of the bentonite powder, the deionized water, the titanium tetrachloride and the dilute hydrochloric acid solution is 10-20: 30-50: 0.5-1: 20-50.
Preferably, the coating mode in the step (2) is knife coating.
Preferably, the temperature of the high-temperature calcination in the step (2) is controlled at 400-500 ℃, and the calcination is carried out for 4-5 h.
Preferably, in the preparation of the modified bentonite powder in the step (2), the mass ratio of the modified bentonite slurry, the aluminum chloride aqueous solution and the activated carbon powder is 40-50: 30-50: 4-5.
Preferably, in the preparation of the gel precursor solution in the step (3), the mass ratio of dopamine, deionized water, modified bentonite powder, acrylamide, acrylic acid, polyethylene glycol diacrylate, N' N-methylene bisacrylamide and ammonium persulfate is 5-10: 50-100: 30-50: 200-210: 40-60: 0.1-0.5: 0.1-0.5: 2-5.
Preferably, the light intensity of the irradiation in the step (4) is controlled to be 1700-1800W, the wavelength range is 200-450nm with 365nm as the center, and the irradiation is performed for 10-60 min.
Preferably, in the preparation of the proton exchange membrane in the step (4), the mass ratio of the gel powder to the nafion solution is 1: 5-20.
It is known that when a proton exchange membrane of a fuel cell works at a low temperature, moisture is easy to remain in a gas diffusion layer to cause flooding, and a catalyst is also easy to be poisoned by carbon monoxide, although the problems can be avoided under a medium-temperature condition, water loss is serious at a high temperature, and meanwhile, a membrane material structure is seriously influenced, proton conductivity is sharply reduced, and the service life is seriously reduced. In the prior art, in the modification technology of the proton exchange membrane, the water retention capacity of the proton exchange membrane can be improved by adding hydrogel, but the existing hydrogel material has poor stability under the condition of temperature change, the hydrogel is easy to freeze-dry at low temperature, and the hydrogel can lose water to cause water loss at high temperature, so that the temperature tolerance of the proton exchange membrane can be effectively improved by adding the hydrogel with excellent composite temperature tolerance into the proton exchange membrane. The invention creatively loads hydrogel with excellent temperature resistance and water retention performance in the pillared bentonite, and finally coats and forms a film through the nafion solution, thereby effectively solving the problems.
The invention selects sodium bentonite as raw material, the sodium bentonite has low water absorption speed, but large water absorption and expansion times, high cation exchange capacity and good dispersibility in water medium; the colloidal suspension liquid has good thixotropy and thermal stability; has high plasticity and high adhesion. Adding sodium bentonite into deionized water to prepare a suspension, adding a dilute hydrochloric acid solution of titanium tetrachloride, standing for aging, and filtering to remove redundant solvent to obtain the modified bentonite slurry. The whole process enables titanium ions to react with bentonite to form titanium pillared bentonite, and the titanium pillared bentonite has larger pore passages compared with other propping-swelling compounds.
Furthermore, the modified bentonite slurry, an aluminum chloride aqueous solution and activated carbon powder are mixed and coated on the surface of a glass substrate, and the mixture is calcined to obtain modified bentonite powder, so that the porosity and the water resistance of the bentonite can be improved, and the mechanical property of the proton exchange membrane can be improved.
Further, mixing dopamine and deionized water to prepare a solution, adding modified bentonite under an alkaline condition to obtain a dopamine-modified bentonite dispersion solution, then adding acrylamide, acrylic acid, polyethylene glycol diacrylate, N' N-methylene bisacrylamide and ammonium persulfate, and performing ultrasonic treatment to obtain a gel precursor solution. The method comprises the steps of controlling the dosage ratio of dopamine and modified bentonite, enabling the dopamine and modified bentonite to be oxidized and polymerized under an alkaline condition to form polydopamine-modified titanium pillared bentonite, enabling polydopamine and a copolymer of acrylic acid and acrylamide to have strong non-covalent interaction, and enabling the titanium pillared bentonite to form gel precursor liquid in the bentonite after adsorbing the gel precursor liquid.
And finally, irradiating the gel precursor solution under ultraviolet rays, initiating copolymerization of acrylic acid and acrylamide through ultraviolet rays and ammonium persulfate to enable the modified bentonite to load copolymer gel of the acrylic acid and the acrylamide, adsorbing deionized water through the gel to form a hydrogel system, and finally forming a film with nafion solution to obtain the proton exchange membrane with excellent water resistance and mechanical properties. According to the invention, the mechanical strength of the membrane material is improved by adding the modified bentonite, dopamine and gel precursor liquid form a bentonite/dopamine/gel composite material through adsorption and ultraviolet polymerization, and the bentonite/dopamine/gel composite material is compounded with water through a hydrogen bond, so that the storage capacity of the water at the medium temperature is improved, and the water loss cracking of the membrane material at the medium temperature is inhibited.
The existing proton exchange membrane has the problem of poor durability at medium temperature, and the application of the proton exchange membrane is limited. In view of the above, the invention provides a proton exchange membrane suitable for a medium-temperature fuel cell and a preparation method thereof, bentonite powder is added with deionized water to prepare a suspension, then a dilute hydrochloric acid solution of titanium tetrachloride is slowly added into the solution, standing and aging are carried out, and redundant solvent is removed by filtration to obtain modified bentonite slurry; mixing the slurry with an aluminum chloride aqueous solution and activated carbon powder, stirring, filtering, coating on the surface of a glass substrate, and calcining to obtain modified bentonite powder; mixing dopamine and deionized water to prepare a solution, adjusting the solution to be alkaline by using sodium hydroxide, uniformly mixing, and adding the obtained modified bentonite to obtain the dopamine-modified bentonite dispersion liquid. Then adding acrylamide, acrylic acid, polyethylene glycol diacrylate, N' N-methylene bisacrylamide and ammonium persulfate, and carrying out ultrasonic treatment to obtain gel precursor liquid; irradiating the obtained gel precursor solution under ultraviolet light, and performing centrifugal separation to obtain gel powder; mixing the gel powder with the nafion solution, and obtaining the needed proton exchange membrane through coating, rolling, drying, washing and drying. The proton exchange membrane provided by the invention has excellent stability at medium temperature (80-100 ℃), good mechanical property and durability and simple process, and can effectively improve the working temperature of a fuel cell.
Compared with the prior art, the invention provides a proton exchange membrane suitable for a medium-temperature fuel cell and a preparation method thereof, and the outstanding characteristics and excellent effects are as follows:
1. the proton exchange membrane prepared by the invention has excellent stability at a medium temperature (80-100 ℃), can be directly improved according to the existing nafion-based proton exchange membrane, effectively improves the working temperature of a fuel cell, and promotes the development of the proton exchange membrane and even the fuel cell.
2. According to the invention, the bentonite is used for loading copolymer gel of acrylic acid and acrylamide, deionized water is adsorbed by the gel to form a hydrogel system, and finally the hydrogel system and nafion solution are formed into a film. The mechanical strength of the membrane material is improved by adding the modified bentonite, dopamine and gel precursor liquid form a bentonite/dopamine/gel composite material through adsorption and ultraviolet polymerization, and the bentonite/dopamine/gel composite material is compounded with water through a hydrogen bond, so that the storage capacity of the water at the medium temperature is improved, and the water loss cracking of the membrane material at the medium temperature is inhibited.
Drawings
FIG. 1: photos before and after testing of the proton exchange membrane sample of example 1;
FIG. 2: photos before and after testing of the proton exchange membrane sample of comparative example 1;
FIG. 3: photographs before and after testing of the proton exchange membrane sample of comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Adding 15kg of sodium bentonite powder into 40kg of deionized water to prepare a suspension, then slowly adding 0.8kg of titanium tetrachloride and 35kg of dilute hydrochloric acid solution with the molar concentration of 0.15mol/L into the suspension, standing and aging for 3 hours, and filtering to remove redundant solvent to obtain modified bentonite slurry;
(2) mixing 45kg of modified bentonite slurry, 40kg of aluminum chloride aqueous solution with the mass concentration of 2.5% and 4.5kg of activated carbon powder, stirring at the rotating speed of 450rpm for 35min, then blade-coating the mixture on the surface of a glass substrate after filtering, and calcining at the temperature of 450 ℃ for 4.5h to obtain modified bentonite powder;
(3) mixing 8kg of dopamine with 75kg of deionized water to prepare a solution, then adjusting the pH value to 10.5 by using sodium hydroxide, then adding 40kg of modified bentonite powder, uniformly mixing to obtain a dopamine-modified bentonite dispersion solution, then adding 205kg of acrylamide, 50kg of acrylic acid, 0.3kg of polyethylene glycol diacrylate, 0.3kg of N' N-methylene bisacrylamide and 3.5kg of ammonium persulfate, and then carrying out ultrasonic treatment at the frequency of 40kHz for 20min to obtain a gel precursor solution;
(4) irradiating the obtained gel precursor solution under ultraviolet light, controlling the irradiation light intensity at 1750W, irradiating for 35min, then performing centrifugal separation to obtain gel powder, then mixing 1kg of the gel powder with 12kg of nafion solution with the mass concentration of 10%, and then performing coating, rolling, drying, washing and drying to obtain the fuel cell proton exchange membrane suitable for the intermediate temperature.
Example 2
(1) Adding 12kg of sodium bentonite powder into 45kg of deionized water to prepare a suspension, slowly adding a dilute hydrochloric acid solution containing 0.6kg of titanium tetrachloride and 40kg of a dilute hydrochloric acid solution with the molar concentration of 0.12mol/L into the suspension, standing and aging for 2.5 hours, and filtering to remove redundant solvent to obtain modified bentonite slurry;
(2) mixing 42kg of modified bentonite slurry, 45kg of aluminum chloride aqueous solution with the mass concentration of 2-3% and 4.2kg of activated carbon powder, stirring at the rotating speed of 420rpm for 38min, filtering, blade-coating on the surface of a glass substrate, and calcining at the temperature of 420 ℃ for 5h to obtain modified bentonite powder;
(3) mixing 5-10kg of dopamine and 50-100kg of deionized water to prepare a solution, then adjusting the pH value to 10-11 by using sodium hydroxide, then adding 30-50kg of modified bentonite powder, uniformly mixing to obtain a dopamine-modified bentonite dispersion, then adding 200-210kg of acrylamide, 40-60kg of acrylic acid, 0.1-0.5kg of polyethylene glycol diacrylate, 0.1-0.5kg of N' -methylene bisacrylamide and 2-5kg of ammonium persulfate, and then carrying out ultrasonic treatment for 10-30min at the frequency of 30-50kHz to obtain a gel precursor solution;
(4) irradiating the obtained gel precursor solution under ultraviolet light, controlling the irradiation light intensity at 1720W, irradiating for 50min, then performing centrifugal separation to obtain gel powder, then mixing 1kg of the gel powder with 18kg of nafion solution with the mass concentration of 12%, and then performing coating, rolling, drying, washing and drying to obtain the fuel cell proton exchange membrane suitable for the intermediate temperature.
Example 3
(1) Adding 18kg of sodium bentonite powder into 35kg of deionized water to prepare a suspension, then slowly adding a dilute hydrochloric acid solution containing 0.8kg of titanium tetrachloride and 30kg of a dilute hydrochloric acid solution with the molar concentration of 0.1-0.2mol/L into the suspension, standing and aging for 3.5 hours, and filtering to remove the redundant solvent to obtain modified bentonite slurry;
(2) mixing 48kg of modified bentonite slurry with 35kg of aluminum chloride aqueous solution with the mass concentration of 2-3% and 4.8kg of activated carbon powder, stirring at 480rpm for 32min, filtering, blade-coating on the surface of a glass substrate, and calcining at 480 ℃ for 4h to obtain modified bentonite powder;
(3) mixing 9kg of dopamine with 60kg of deionized water to prepare a solution, then adjusting the pH value to 11 by using sodium hydroxide, then adding 40kg of modified bentonite powder, uniformly mixing to obtain a dopamine-modified bentonite dispersion solution, then adding 202kg of acrylamide, 55kg of acrylic acid, 0.4kg of polyethylene glycol diacrylate, 0.4kg of N' N-methylene bisacrylamide and 4kg of ammonium persulfate, and then carrying out ultrasonic treatment at the frequency of 45kHz for 15min to obtain a gel precursor solution;
(4) irradiating the obtained gel precursor solution under ultraviolet light, controlling the irradiation light intensity at 1780W, irradiating for 20min, then performing centrifugal separation to obtain gel powder, then mixing 1kg of the gel powder with 8kg of nafion solution with the mass concentration of 12%, and then performing coating, rolling, drying, washing and drying to obtain the fuel cell proton exchange membrane suitable for the intermediate temperature.
Example 4
(1) Adding 10kg of sodium bentonite powder into 50kg of deionized water to prepare a suspension, then slowly adding a dilute hydrochloric acid solution containing 0.5kg of titanium tetrachloride and having a molar concentration of 50kg of 0.2mol/L into the suspension, standing and aging for 2 hours, and filtering to remove redundant solvent to obtain modified bentonite slurry;
(2) mixing 40kg of modified bentonite slurry, 50kg of aluminum chloride aqueous solution with the mass concentration of 2-3% and 5kg of activated carbon powder, stirring at the rotating speed of 4000rpm for 40min, then blade-coating the mixture on the surface of a glass substrate after filtering, and calcining at the temperature of 400 ℃ for 5h to obtain modified bentonite powder;
(3) mixing 5kg of dopamine with 100kg of deionized water to prepare a solution, then adjusting the pH value to 10 by using sodium hydroxide, then adding 30kg of modified bentonite powder, uniformly mixing to obtain a dopamine-modified bentonite dispersion solution, then adding 210kg of acrylamide, 40kg of acrylic acid, 0.1kg of polyethylene glycol diacrylate, 0.1kg of N' N-methylene bisacrylamide and 2kg of ammonium persulfate, and then carrying out ultrasonic treatment at the frequency of 30kHz for 30min to obtain a gel precursor solution;
(4) irradiating the obtained gel precursor solution under ultraviolet light, controlling the irradiation light intensity at 1700W, irradiating for 60min, then performing centrifugal separation to obtain gel powder, then mixing 1kg of the gel powder with 20kg of nafion solution with the mass concentration of 15%, and then performing coating, rolling, drying, washing and drying to obtain the fuel cell proton exchange membrane suitable for the intermediate temperature.
Example 5
(1) Adding 20kg of sodium bentonite powder into 30kg of deionized water to prepare a suspension, slowly adding a dilute hydrochloric acid solution containing 1kg of titanium tetrachloride and having a molar concentration of 50kg of 0.2mol/L into the suspension, standing and aging for 4 hours, and filtering to remove redundant solvent to obtain modified bentonite slurry;
(2) mixing 50kg of modified bentonite slurry, 30kg of aluminum chloride aqueous solution with the mass concentration of 2-3% and 4kg of activated carbon powder, stirring at the rotating speed of 500rpm for 30min, then blade-coating the mixture on the surface of a glass substrate after filtering, and calcining at the temperature of 500 ℃ for 4h to obtain modified bentonite powder;
(3) mixing 10kg of dopamine with 50kg of deionized water to prepare a solution, then adjusting the pH value to 11 by using sodium hydroxide, then adding 50kg of modified bentonite powder, uniformly mixing to obtain a dopamine-modified bentonite dispersion solution, then adding 200kg of acrylamide, 60kg of acrylic acid, 0.5kg of polyethylene glycol diacrylate, 0.5kg of N' N-methylene bisacrylamide and 5kg of ammonium persulfate, and then carrying out ultrasonic treatment at the frequency of 50kHz for 10min to obtain a gel precursor solution;
(4) irradiating the obtained gel precursor solution under ultraviolet light, controlling the irradiation light intensity at 1800W, irradiating for 10min, then performing centrifugal separation to obtain gel powder, then mixing 1kg of the gel powder with 5kg of nafion solution with the mass concentration of 5%, and then performing coating, rolling, drying, washing and drying to obtain the fuel cell proton exchange membrane suitable for the intermediate temperature.
Comparative example 1
(1) Adding 15kg of sodium bentonite powder into 40kg of deionized water to prepare a suspension, then slowly adding 0.8kg of titanium tetrachloride and 35kg of dilute hydrochloric acid solution with the molar concentration of 0.15mol/L into the suspension, standing and aging for 3 hours, and filtering to remove redundant solvent to obtain modified bentonite slurry;
(2) mixing 45kg of modified bentonite slurry, 40kg of aluminum chloride aqueous solution with the mass concentration of 2.5% and 4.5kg of activated carbon powder, stirring at the rotating speed of 450rpm for 35min, then blade-coating the mixture on the surface of a glass substrate after filtering, and calcining at the temperature of 450 ℃ for 4.5h to obtain modified bentonite powder;
(3) adding 75kg of deionized water into 40kg of modified bentonite powder, uniformly mixing, adding 205kg of acrylamide, 50kg of acrylic acid, 0.3kg of polyethylene glycol diacrylate, 0.3kg of N' N-methylene bisacrylamide and 3.5kg of ammonium persulfate, and carrying out ultrasonic treatment for 20min at the frequency of 40kHz to obtain a gel precursor solution;
(4) irradiating the obtained gel precursor solution under ultraviolet light, controlling the irradiation light intensity at 1750W, irradiating for 35min, then performing centrifugal separation to obtain gel powder, then mixing 1kg of the gel powder with 12kg of nafion solution with the mass concentration of 10%, and then performing coating, rolling, drying, washing and drying to obtain the fuel cell proton exchange membrane suitable for the intermediate temperature.
Comparative example 1 compared to example 1, bentonite was not modified with dopamine, and the rest was completely identical to example 1.
Comparative example 2
(1) Adding 15kg of sodium bentonite powder into 40kg of deionized water to prepare a suspension, then slowly adding 35kg of dilute hydrochloric acid solution with the molar concentration of 0.15mol/L and containing 0.8kg of titanium tetrachloride into the suspension, standing and aging for 3 hours, and filtering to remove redundant solvent to obtain modified bentonite slurry;
(2) mixing 45kg of modified bentonite slurry, 40kg of aluminum chloride aqueous solution with the mass concentration of 2.5% and 4.5kg of activated carbon powder, stirring at the rotating speed of 450rpm for 35min, then blade-coating the mixture on the surface of a glass substrate after filtering, and calcining at the temperature of 450 ℃ for 4.5h to obtain modified bentonite powder;
(3) mixing 8kg of dopamine with 75kg of deionized water to prepare a solution, then adjusting the pH value to 10.5 by using sodium hydroxide, then adding 40kg of modified bentonite powder, and uniformly mixing to obtain a dopamine-modified bentonite dispersion solution;
(4) 3kg of dopamine modified bentonite dispersion liquid and 12kg of nafion solution with the mass concentration of 10% are mixed, and then coating, rolling, drying, washing and drying are carried out, so that the fuel cell proton exchange membrane suitable for the medium temperature can be obtained.
Comparative example 2 compared with example 1, the gel was prepared without copolymerization of acrylic acid and acrylamide, and the modified bentonite, deionized water, and nafion solution were directly mixed and coated to form a film, which was otherwise completely the same as example 1.
The test method comprises the following steps:
intermediate temperature water resistance test: placing the proton exchange membrane samples prepared in the examples 1-5 and the comparative examples 1-2 in a closed container, controlling the humidity in the container to be 80%, keeping the temperature at 90 ℃, standing for 48h, and observing the surface deformation of the samples before and after testing; as shown in table 1.
Table 1:
through tests, the sample of the embodiment of the invention has no obvious deformation before and after the test, because the modified bentonite and the gel are used as the framework, the sample has better physical properties, meanwhile, the internal gel system can effectively improve the water retention capacity, more water can be stored in a proton exchange membrane in a liquid phase, and the structure of the sample is not changed obviously.
Wherein FIG. 1 is a deformation condition of the sample of example 1 in a medium-temperature and high-humidity environment, and FIG. 1a is a photo of a proton exchange membrane before testing; FIG. 1b is a photograph of 48h treated in a medium temperature and high humidity environment, and no obvious deformation occurs, because the modified bentonite and the gel are used as frameworks, the modified bentonite and the gel have good physical properties, meanwhile, the internal gel system can effectively improve the water retention capacity, more water can be stored in a proton exchange membrane in a liquid phase, and the structure of the proton exchange membrane is not changed obviously.
Wherein FIG. 2 is a deformation condition of the sample of comparative example 1 under a medium-temperature and high-humidity environment, and FIG. 2c is a photo of the proton exchange membrane before the test; fig. 2d is a photograph of 48h treated in a medium-temperature and high-humidity environment, and the change before and after the test is obvious, because the bentonite is not modified by dopamine, the composite performance of the gel and the bentonite is poor, and the distribution of the gel phase and the framework in the proton exchange membrane is uneven.
Wherein FIG. 3 is the deformation of the sample of comparative example 2 under the condition of medium temperature and high humidity, and FIG. 3e is the photo of the proton exchange membrane before testing; FIG. 3f is a photograph of a proton exchange membrane treated for 48 hours in a medium temperature and high humidity environment, wherein the proton exchange membrane is seriously deformed due to water loss, and because no gel is added, the modified bentonite is only used for absorbing water, the interior of the proton exchange membrane lacks gel water retention, and the proton exchange membrane is seriously deformed due to water loss.
Claims (10)
1. A proton exchange membrane suitable for a medium-temperature fuel cell is characterized in that the proton exchange membrane is prepared by mixing gel powder with nafion solution, coating, rolling, drying, washing and drying; the gel powder is prepared by adding modified bentonite into an aqueous solution of dopamine under an alkaline condition, then adding acrylamide, acrylic acid, polyethylene glycol diacrylate, N' N-methylene bisacrylamide and ammonium persulfate, mixing and performing ultrasonic treatment to obtain a gel precursor solution, and then performing ultraviolet irradiation and centrifugal separation; the modified bentonite is prepared by adding a dilute hydrochloric acid solution of titanium tetrachloride into a suspension of bentonite powder, aging to obtain a modified bentonite slurry, mixing and stirring with an aluminum chloride aqueous solution and activated carbon powder, coating the mixture on the surface of a glass substrate, and calcining.
2. A fuel cell proton exchange membrane suitable for medium temperature according to claim 1,
the mass concentration of the nafion solution is 5-15%;
the bentonite powder is sodium bentonite powder;
the molar concentration of the dilute hydrochloric acid solution is 0.1-0.2 mol/L;
the mass concentration of the aluminum chloride aqueous solution is 2-3%.
3. A method for preparing a proton exchange membrane suitable for a medium-temperature fuel cell according to any one of claims 1 to 2, which is characterized in that the specific preparation method comprises the following steps:
(1) adding bentonite powder into deionized water to prepare a suspension, slowly adding a dilute hydrochloric acid solution of titanium tetrachloride into the suspension, standing and aging for 2-4h, and filtering to remove redundant solvent to obtain modified bentonite slurry;
(2) mixing the modified bentonite slurry with an aluminum chloride aqueous solution and activated carbon powder, stirring at the rotation speed of 400-500rpm for 30-40min, filtering, coating on the surface of a glass substrate, and calcining at high temperature to obtain modified bentonite powder;
(3) mixing dopamine and deionized water to prepare a solution, then adjusting the pH value to 10-11 by using sodium hydroxide, then adding modified bentonite powder, uniformly mixing to obtain a dopamine-modified bentonite dispersion solution, then adding acrylamide, acrylic acid, polyethylene glycol diacrylate, N' N-methylene bisacrylamide and ammonium persulfate, and then carrying out ultrasonic treatment for 10-30min at the frequency of 30-50kHz to obtain a gel precursor solution;
(4) and irradiating the obtained gel precursor solution under ultraviolet light, then performing centrifugal separation to obtain gel powder, mixing the gel powder with nafion solution, and then performing coating, rolling, drying, washing and drying to obtain the fuel cell proton exchange membrane suitable for medium temperature.
4. The method for preparing a proton exchange membrane of a fuel cell suitable for intermediate temperature according to claim 3, wherein in the step (1), the modified bentonite slurry is prepared by mixing bentonite powder, deionized water, titanium tetrachloride and a dilute hydrochloric acid solution in a mass ratio of 10-20: 30-50: 0.5-1: 20-50.
5. The method for preparing a proton exchange membrane suitable for a medium-temperature fuel cell according to claim 3, wherein the coating in the step (2) is knife coating.
6. The method as claimed in claim 3, wherein the temperature of the high-temperature calcination in step (2) is controlled to be 400-500 ℃ for 4-5 h.
7. The method for preparing a proton exchange membrane for a fuel cell at intermediate temperature according to claim 3, wherein in the step (2), the modified bentonite powder is prepared by mixing the modified bentonite slurry, the aluminum chloride aqueous solution and the activated carbon powder in a mass ratio of 40-50: 30-50: 4-5.
8. The preparation method of the proton exchange membrane of the fuel cell suitable for the intermediate temperature according to claim 3, wherein in the preparation of the gel precursor liquid in the step (3), the mass ratio of dopamine, deionized water, modified bentonite powder, acrylamide, acrylic acid, polyethylene glycol diacrylate, N' N-methylene bisacrylamide and ammonium persulfate is 5-10: 50-100: 30-50: 200-210: 40-60: 0.1-0.5: 0.1-0.5: 2-5.
9. The method as claimed in claim 3, wherein the light intensity of the irradiation in step (4) is controlled to be 1700-1800W, the wavelength range is 200-450nm, and the irradiation time is 10-60 min.
10. The preparation method of the proton exchange membrane suitable for the intermediate temperature fuel cell according to claim 3, wherein in the preparation of the proton exchange membrane in the step (4), the mass ratio of the gel powder to the nafion solution is 1: 5-20.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672170A (en) * | 2022-04-13 | 2022-06-28 | 深圳市亚鹰科技有限公司 | Heat insulation material and lithium battery heat insulation protection pad |
| CN116111155A (en) * | 2023-04-11 | 2023-05-12 | 山东赛克赛斯氢能源有限公司 | Hydrogen fuel cell, hydrogen production proton exchange membrane by water electrolysis and preparation method thereof |
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2021
- 2021-01-27 CN CN202110108723.3A patent/CN112701339A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672170A (en) * | 2022-04-13 | 2022-06-28 | 深圳市亚鹰科技有限公司 | Heat insulation material and lithium battery heat insulation protection pad |
| CN114672170B (en) * | 2022-04-13 | 2022-12-13 | 深圳市亚鹰科技有限公司 | Heat insulation material and lithium battery heat insulation protection pad |
| CN116111155A (en) * | 2023-04-11 | 2023-05-12 | 山东赛克赛斯氢能源有限公司 | Hydrogen fuel cell, hydrogen production proton exchange membrane by water electrolysis and preparation method thereof |
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Application publication date: 20210423 |