CN111952616A - Fuel cell with good alkali resistance and high strength - Google Patents
Fuel cell with good alkali resistance and high strength Download PDFInfo
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- CN111952616A CN111952616A CN202010845940.6A CN202010845940A CN111952616A CN 111952616 A CN111952616 A CN 111952616A CN 202010845940 A CN202010845940 A CN 202010845940A CN 111952616 A CN111952616 A CN 111952616A
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a fuel cell with good alkali resistance and high strength, and a preparation method of a fuel cell diaphragm comprises the following steps: step S1, preparing poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide, step S2, preparing glucoside modified poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide, step S3, crosslinking, curing and film forming, and step S4, and performing ion exchange. The fuel cell disclosed by the invention has the advantages of good diaphragm comprehensive performance, high ionic conductivity, excellent alkali resistance, excellent chemical stability and excellent mechanical property.
Description
The invention relates to a Chinese patent 'a fuel cell diaphragm and a preparation method thereof', wherein the application date is 2019, 10 and 24 months, and the application number is 201911014743.3.
Technical Field
The invention belongs to the technical field of fuel cells, relates to a fuel cell, and particularly relates to a fuel cell with good alkali resistance and high strength.
Background
In recent years, with the increasing shortage of non-renewable resources such as oil gas and the like and the continuous deep understanding of human on problems such as environmental pollution, energy crisis and the like, people pay more and more attention to the development of renewable clean energy sources in order to meet the requirements of development modes of low-carbon economy and energy conservation and emission reduction. As a common clean energy device, fuel cells attract a lot of attention. The fuel cell is a device for directly converting chemical energy in fuel into electric energy, is considered to be the most promising clean energy due to the advantages of high energy conversion efficiency, low noise emission, fast load response, high operation quality and the like, has wide market demand and good application value in the fields of vehicle power energy, portable electronic products, distributed power stations and the like, has greater development potential, and is a new favorite in the new energy device market at present and in some future.
A common fuel cell mainly comprises an electrode, a membrane and an external circuit, wherein the membrane is one of the key components of a fuel cell represented by a polyelectrolyte fuel cell, and plays dual roles of flame retarding fuel and ion conduction in the fuel cell, and the performance of the membrane directly influences the performance and the cycle service life of the fuel cell. The development of fuel cell membranes with excellent performance is a precondition for ensuring high energy conversion efficiency, safety and normal working stability of fuel cells.
At present, a common fuel cell membrane is a perfluorosulfonic acid membrane represented by a Nafion membrane produced by dupont, which has high proton conductivity and excellent chemical stability, but is mainly imported and expensive, and the application range of the membrane is usually below 80 ℃, so that the membrane is easy to dehydrate in a high-temperature environment, dehydration leads to increase of membrane resistance, and the proton conductivity of the membrane is rapidly reduced, so that the energy conversion efficiency of the cell is reduced. The polymer anion exchange membrane developed in recent years can be used at high temperature, but the process of chloromethylation is required when ion exchange groups are introduced, and chloromethyl ether which is a highly toxic carcinogenic substance is required to be used in the chloromethylation process, which has great harm to environmental protection and human health, and the heat stability, chemical stability and strong base resistance of the anion exchange membrane fuel cell membrane in the prior art need to be further improved.
The Chinese patent with application number 201610462433.8 discloses a preparation method of a diaphragm for a fuel cell, which introduces adamantyl triazine ion exchange groups by adopting a radiation-initiated free radical polymerization mode, and is favorable for improving the alkali resistance and chemical stability of triazine ionic liquid by utilizing adamantane as an electron supply group; double-bond modified titanium dioxide is used as a cross-linking agent, so that the alkali resistance, the mechanical property, the water absorption of the membrane, the methanol permeation resistance and the chemical stability of the membrane are improved on the premise of ensuring higher ionic conductivity; however, the diaphragm has low product yield and high price of preparation raw materials due to the large steric hindrance effect of adamantane and triazine, and the prepared film has insufficient toughness and is not suitable for industrial production.
Therefore, the fuel cell diaphragm with good comprehensive performance, good chemical stability, excellent alkali resistance, excellent toughness and dimensional stability and high ionic conductivity is developed, meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the fuel cell industry.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the fuel cell diaphragm and the preparation method thereof, and the preparation method has the advantages of simple process, convenient implementation, low energy consumption in the preparation process, high preparation efficiency and high qualified rate of finished products; the prepared fuel cell diaphragm has the advantages of good comprehensive performance, high ionic conductivity, excellent alkali resistance, excellent chemical stability and excellent mechanical property.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a method for preparing a fuel cell membrane, comprising the steps of:
step S1, preparation of poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 2, 5-piperidinedicarboxylic acid, 4-diaminodiphenyl sulfide and a catalyst into a high-boiling point solvent, stirring for 40-60 minutes to obtain a mixed material, transferring the mixed material into a high-pressure reaction kettle, replacing air in the kettle with nitrogen or inert gas, keeping the temperature in the high-pressure reaction kettle at 250 ℃ and the pressure at 1-2MPa, stirring for reaction for 3-5 hours, slowly exhausting gas within 1-2 hours and reducing the pressure to 0.5-0.8MPa, simultaneously heating the temperature in the high-pressure reaction kettle to 270 ℃ and 290 ℃, stirring for reaction for 0.5-1 hour, finally controlling the temperature between 225 ℃ and 235 ℃ under a vacuum condition, stirring for reaction for 8-12 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, finally taking out and placing in a forced air drying oven to dry to constant weight at the temperature of 80-90 ℃ to obtain poly 2, 5-piperidine dicarboxylic acid 4, 4-diaminodiphenyl sulfide amide;
step S2, preparation of glucoside modified poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding poly (2, 5-piperidinedicarboxylic acid) 4, 4-diaminodiphenyl sulfide amide, methyl 6-chloro-6-deoxy-alpha-D-glucopyranoside and an alkaline catalyst into N-methylpyrrolidone, stirring and reacting at 40-60 ℃ for 4-6 hours, then precipitating in water, washing the precipitated polymer with ethanol for 3-7 times, finally taking out and placing in a blast drying oven at 85-95 ℃ for drying to constant weight to obtain glucoside modified poly (2, 5-piperidinedicarboxylic acid) 4, 4-diaminodiphenyl sulfide amide;
step S3, crosslinking, curing and film forming: dissolving the glucoside modified poly-2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide and 1, 4-dichlorocyclohexane obtained in the step S2 in N, N-dimethylformamide to obtain a solution, then pouring the solution on a polytetrafluoroethylene plate, and drying the polytetrafluoroethylene plate at the temperature of 80-90 ℃ to constant weight to obtain a base membrane;
step S4, ion exchange: and (4) soaking the base membrane prepared in the step S3 in 0.5-1.0mol/L sodium hydroxide aqueous solution at 55-65 ℃ for 30-48 hours for ion exchange, taking out and soaking in deionized water until the deionized water is neutral, taking out the product, filtering out surface moisture, and drying in a vacuum drying oven at 65-75 ℃ to constant weight.
Further, the mass ratio of the 2, 5-piperidinedicarboxylic acid, the 4, 4-diaminodiphenyl sulfide, the catalyst and the high boiling point solvent in the step S1 is 1:1.24 (0.4-0.6) to (6-10).
Preferably, the catalyst is at least one of thiophosphonate, phosphorous acid and thiophosphoramide; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide; the inert gas is one of helium, neon and argon.
Further, in step S2, the mass ratio of the poly (2, 5-piperidinedicarboxylic acid-4, 4-diaminodiphenyl sulfide amide), the methyl 6-chloro-6-deoxy-alpha-D-glucopyranoside, the basic catalyst and the N-methylpyrrolidone is 1.1:1 (0.6-1) to (7-10).
Preferably, the alkaline catalyst is at least one of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
Further, in step S3, the mass ratio of the glucoside modified poly-2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide to the 1, 4-dichlorocyclohexane to the N, N-dimethylformamide is 1:0.19 (20-40).
Another object of the present invention is to provide a fuel cell separator prepared according to the method for preparing a fuel cell separator.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the fuel cell diaphragm provided by the invention is simple and feasible, the process is easy to control, the operation is convenient, the dependence on equipment is small, the preparation method is suitable for continuous industrial production, the preparation efficiency and the qualification rate of finished products are high, and the economic value, the social value and the ecological value are higher.
(2) The fuel cell diaphragm provided by the invention overcomes the defects that the thermal stability, the chemical stability and the strong base resistance of an anion exchange membrane fuel cell diaphragm in the prior art need to be further improved and the preparation process is not environment-friendly, and has the advantages of good comprehensive performance, high ionic conductivity, excellent alkali resistance, excellent chemical stability and excellent mechanical property.
(3) The fuel cell diaphragm provided by the invention takes methyl 6-chloro-6-deoxy-alpha-D-glucopyranoside modified poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide as a base membrane, introduces an electron donating group of a glucoside structure, and improves the chemical stability of an ion conducting group, particularly the alkali resistance, through an electronic effect and a steric effect; the introduction of a diphenyl sulfide structure and a polyamide structure on a molecular main chain can endow the membrane with excellent comprehensive performance.
(4) According to the fuel cell diaphragm provided by the invention, 1, 4-dichlorocyclohexane ionizes amino at the stage of membrane forming, so that ion conduction groups are introduced; on the other hand, the 1, 4-dichlorocyclohexane can also play a role of a cross-linking agent, so that a three-dimensional network structure is formed in the membrane structure, and the comprehensive performance of the membrane can be effectively improved.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The raw materials involved in the following examples of the present invention were all purchased commercially.
Example 1
A method for preparing a fuel cell membrane, comprising the steps of:
step S1, preparation of poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 10g of 2, 5-piperidinedicarboxylic acid, 12.4g of 4, 4-diaminodiphenyl sulfide and 4g of thiophosphonate into 60g of dimethyl sulfoxide, stirring for 40 minutes to obtain a mixed material, transferring the mixed material into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, keeping the temperature and the pressure in the high-pressure reaction kettle at 230 ℃ and the pressure at 1MPa, stirring for reaction for 3 hours, slowly exhausting and reducing the pressure to 0.5MPa within 1 hour, simultaneously heating the temperature in the high-pressure reaction kettle to 270 ℃, stirring for reaction for 0.5 hour, finally controlling the temperature to 225 ℃ under a vacuum condition, stirring for reaction for 8 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 3 times with ethanol, finally taking out and drying in a blast drying oven at 80 ℃ to constant weight to obtain poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide;
step S2, preparation of glucoside modified poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 11g of poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide), 10g of methyl 6-chloro-6-deoxy-alpha-D-glucopyranoside and 6g of sodium carbonate into 70g of N-methylpyrrolidone, stirring for reacting for 4 hours at 40 ℃, then precipitating in water, washing the precipitated polymer with ethanol for 3 times, finally taking out and placing in a forced air drying oven for drying at 85 ℃ to constant weight to obtain glucoside modified poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide);
step S3, crosslinking, curing and film forming: dissolving 10g of glucoside modified poly (2, 5-piperidinedicarboxylic acid) 4, 4-diaminodiphenyl sulfide amide and 1.9g of 1, 4-dichlorocyclohexane prepared in step S2 in 200g of N, N-dimethylformamide to obtain a solution, pouring the solution on a polytetrafluoroethylene plate, and drying at 80 ℃ to constant weight to obtain a base film;
step S4, ion exchange: and (4) soaking the base membrane prepared in the step S3 in 0.5mol/L sodium hydroxide aqueous solution at 55 ℃ for 30 hours for ion exchange, taking out and soaking in deionized water until the deionized water is neutral, taking out the product, filtering out surface moisture, and drying in a vacuum drying oven at 65 ℃ to constant weight.
A fuel cell separator produced according to the method for producing a fuel cell separator.
Example 2
A method for preparing a fuel cell membrane, comprising the steps of:
step S1, preparation of poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 10g of 2, 5-piperidinedicarboxylic acid, 12.4g of 4, 4-diaminodiphenyl sulfide and 4.5g of phosphorous acid into 75g of N, N-dimethylformamide, stirring for 45 minutes to obtain a mixed material, transferring the mixed material into a high-pressure reaction kettle, replacing air in the kettle with helium, keeping the temperature in the high-pressure reaction kettle at 235 ℃ and the pressure at 1.2MPa, stirring for reaction for 3.5 hours, slowly exhausting and reducing the pressure to 0.6MPa within 1.2 hours, simultaneously heating the temperature in the high-pressure reaction kettle to 275 ℃, stirring for reaction for 0.6 hour, finally controlling the temperature to 227 ℃ under a vacuum condition, stirring for reaction for 9 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 4 times with ethanol, finally taking out and drying in a forced air drying oven at 83 ℃ to obtain poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide;
step S2, preparation of glucoside modified poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 11g of poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide), 10g of methyl 6-chloro-6-deoxy-alpha-D-glucopyranoside and 7.5g of potassium carbonate into 80g of N-methylpyrrolidone, stirring and reacting for 4.5 hours at 45 ℃, precipitating in water, washing the precipitated polymer for 4 times by using ethanol, finally taking out and placing in a blast drying oven to dry at 87 ℃ to constant weight to obtain glucoside modified poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide;
step S3, crosslinking, curing and film forming: dissolving 10g of glucoside modified poly (2, 5-piperidinedicarboxylic acid) 4, 4-diaminodiphenyl sulfide amide and 1.9g of 1, 4-dichlorocyclohexane prepared in step S2 in 250g of N, N-dimethylformamide to obtain a solution, pouring the solution on a polytetrafluoroethylene plate, and drying at 82 ℃ to constant weight to obtain a base film;
step S4, ion exchange: and (4) soaking the base membrane prepared in the step S3 in 0.6mol/L sodium hydroxide aqueous solution at 57 ℃ for 33 hours for ion exchange, taking out and soaking in deionized water until the deionized water is neutral, taking out the product, filtering out surface moisture, and drying in a 67 ℃ vacuum drying oven to constant weight.
A fuel cell separator produced according to the method for producing a fuel cell separator.
Example 3
A method for preparing a fuel cell membrane, comprising the steps of:
step S1, preparation of poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 10g of 2, 5-piperidinedicarboxylic acid, 12.4g of 4, 4-diaminodiphenyl sulfide and 5g of thiophosphoramide into 80g of N, N-dimethylacetamide, stirring for 50 minutes to obtain a mixed material, transferring the mixed material into a high-pressure reaction kettle, replacing air in the kettle with neon, keeping the temperature in the high-pressure reaction kettle at 240 ℃ and the pressure at 1.5MPa, stirring for reacting for 4 hours, slowly exhausting and reducing the pressure to 0.65MPa within 1.5 hours, simultaneously heating the temperature in the high-pressure reaction kettle to 280 ℃, stirring for reacting for 0.8 hour, finally controlling the temperature to 230 ℃ under a vacuum condition, stirring for reacting for 10 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 5 times, finally taking out and placing in a blast drying oven to 85 ℃ to constant weight to obtain poly (2, 5-piperidinedicarboxylic acid 4), 4-diaminodiphenyl sulfide amide;
step S2, preparation of glucoside modified poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 11g of poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide), 10g of methyl 6-chloro-6-deoxy-alpha-D-glucopyranoside and 8g of sodium hydroxide into 85g of N-methylpyrrolidone, stirring and reacting for 5 hours at 50 ℃, then precipitating in water, washing the precipitated polymer for 5 times by using ethanol, finally taking out and placing in a blast drying oven for drying at 90 ℃ to constant weight to obtain glucoside modified poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide);
step S3, crosslinking, curing and film forming: dissolving 10g of glucoside modified poly (2, 5-piperidinedicarboxylic acid) 4, 4-diaminodiphenyl sulfide amide and 1.9g of 1, 4-dichlorocyclohexane prepared in step S2 in 300g of N, N-dimethylformamide to obtain a solution, pouring the solution on a polytetrafluoroethylene plate, and drying at 85 ℃ to constant weight to obtain a base film;
step S4, ion exchange: and (4) soaking the base film prepared in the step S3 in 0.8mol/L sodium hydroxide aqueous solution at 60 ℃ for 40 hours for ion exchange, taking out and soaking in deionized water until the deionized water is neutral, taking out the product, filtering out surface moisture, and drying in a vacuum drying oven at 70 ℃ to constant weight.
A fuel cell separator produced according to the method for producing a fuel cell separator.
Example 4
A method for preparing a fuel cell membrane, comprising the steps of:
step S1, preparation of poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 10g of 2, 5-piperidinedicarboxylic acid, 12.4g of 4, 4-diaminodiphenyl sulfide and 5.5g of catalyst into 90g of high-boiling-point solvent, stirring for 55 minutes to obtain a mixed material, transferring the mixed material into a high-pressure reaction kettle, replacing air in the kettle with argon, keeping the temperature in the high-pressure reaction kettle at 245 ℃ and the pressure at 1.9MPa, stirring for reacting for 4.8 hours, slowly exhausting and reducing the pressure to 0.75MPa within 1.9 hours, simultaneously heating the temperature in the high-pressure reaction kettle to 288 ℃, stirring for reacting for 0.9 hour, finally controlling the temperature to 233 ℃ under vacuum conditions, stirring for reacting for 11 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 6 times, finally taking out and placing in a blast drying oven to constant weight at 88 ℃ to obtain poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide; the catalyst is formed by mixing thiophosphonate, phosphorous acid and thiophosphoryl amide according to the mass ratio of 1:3: 2; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide according to a mass ratio of 1:2: 2;
step S2, preparation of glucoside modified poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 11g of poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide), 10g of methyl 6-chloro-6-deoxy-alpha-D-glucopyranoside and 9g of basic catalyst into 95g of N-methylpyrrolidone, stirring and reacting for 5.8 hours at 58 ℃, precipitating in water, washing the precipitated polymer for 6 times by using ethanol, finally taking out and placing in a blast drying oven to dry at 93 ℃ to constant weight to obtain glucoside modified poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide); the alkaline catalyst is formed by mixing sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide according to the mass ratio of 1:1:3: 2;
step S3, crosslinking, curing and film forming: dissolving 10g of glucoside modified poly (2, 5-piperidinedicarboxylic acid) 4, 4-diaminodiphenyl sulfide amide and 1.9g of 1, 4-dichlorocyclohexane prepared in step S2 in 350g of N, N-dimethylformamide to obtain a solution, pouring the solution on a polytetrafluoroethylene plate, and drying at 88 ℃ to constant weight to obtain a base film;
step S4, ion exchange: and (4) soaking the base membrane prepared in the step S3 in 0.9mol/L sodium hydroxide aqueous solution at 63 ℃ for 46 hours for ion exchange, taking out and soaking in deionized water until the deionized water is neutral, taking out the product, filtering out surface moisture, and drying in a vacuum drying oven at 73 ℃ to constant weight.
A fuel cell separator produced according to the method for producing a fuel cell separator.
Example 5
A method for preparing a fuel cell membrane, comprising the steps of:
step S1, preparation of poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 10g of 2, 5-piperidinedicarboxylic acid, 12.4g of 4, 4-diaminodiphenyl sulfide and 6g of phosphorous acid into 100g of N, N-dimethylacetamide, stirring for 60 minutes to obtain a mixed material, transferring the mixed material into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, keeping the temperature in the high-pressure reaction kettle at 250 ℃ and the pressure at 2MPa, stirring for 5 hours, slowly exhausting air and reducing the pressure to 0.8MPa within 2 hours, simultaneously heating the temperature in the high-pressure reaction kettle to 290 ℃, stirring for 1 hour, finally controlling the temperature at 235 ℃ under vacuum conditions, stirring for 12 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 6 times with ethanol, finally taking out and drying in a blast drying oven at 90 ℃ to constant weight to obtain poly (2, 5-piperidinedicarboxylic acid 4), 4-diaminodiphenyl sulfide amide;
step S2, preparation of glucoside modified poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 11g of poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide), 10g of methyl 6-chloro-6-deoxy-alpha-D-glucopyranoside and 10g of potassium hydroxide into 100g of N-methylpyrrolidone, stirring and reacting for 6 hours at 60 ℃, then precipitating in water, washing the precipitated polymer with ethanol for 7 times, finally taking out and placing in a blast drying oven to dry to constant weight at 95 ℃ to obtain glucoside modified poly (2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide);
step S3, crosslinking, curing and film forming: dissolving 10g of glucoside modified poly (2, 5-piperidinedicarboxylic acid) 4, 4-diaminodiphenyl sulfide amide and 1.9g of 1, 4-dichlorocyclohexane prepared in step S2 in 400g of N, N-dimethylformamide to obtain a solution, pouring the solution on a polytetrafluoroethylene plate, and drying at 90 ℃ to constant weight to obtain a base film;
step S4, ion exchange: and (4) soaking the base film prepared in the step S3 in a 1.0mol/L sodium hydroxide aqueous solution at 65 ℃ for 48 hours for ion exchange, taking out and soaking the base film in deionized water until the deionized water is neutral, taking out a product, filtering out surface moisture, and drying the product in a vacuum drying oven at 75 ℃ to constant weight.
A fuel cell separator produced according to the method for producing a fuel cell separator.
Comparative example
A fuel cell membrane, which is basically the same as the preparation method of the embodiment 1 of the Chinese patent with the application number of 201610462433.8.
In order to further illustrate the beneficial technical effects of the embodiments of the present invention, the specific properties of the separators prepared in the embodiments 1 to 5 and the comparative example were tested in terms of ionic conductivity, tensile properties, alkali resistance, and the like. The conductivity was measured by a two-electrode AC impedance method at an electrochemical workstation (Zahner IM6 EX), and the alkali resistance of the separator was measured by immersing the separator in a 1mol/L KOH solution at 80 ℃ for 60 days and calculating the rate of change of conductivity. The tensile properties of the membranes were measured at 25 ℃ using a universal prototype (Instron Model 3365) at a tensile rate of 5 mm/min. Each test was carried out 3 times, one sample for each example, and the data are shown in Table 1.
TABLE 1
As can be seen from table 1, compared with the comparative example in the prior art, the fuel cell separator prepared in the embodiment of the present invention has improved performance indexes in terms of ionic conductivity, tensile property, alkali resistance, etc., which is a result of synergistic effect of each component and structure.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The fuel cell with good alkali resistance and high strength is characterized in that the preparation method of the fuel cell diaphragm comprises the following steps:
step S1, preparation of poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding 2, 5-piperidinedicarboxylic acid, 4-diaminodiphenyl sulfide and a catalyst into a high-boiling point solvent, stirring for 40-60 minutes to obtain a mixed solution, transferring the mixed material into a high-pressure reaction kettle, replacing air in the kettle with nitrogen or inert gas, keeping the temperature in the high-pressure reaction kettle at 250 ℃ and the pressure at 1-2MPa, stirring for reaction for 3-5 hours, slowly exhausting gas and reducing the pressure to 0.5-0.8MPa within 1-2 hours, simultaneously heating the temperature in the high-pressure reaction kettle to 270 ℃ and 290 ℃, stirring for reaction for 0.5-1 hour, finally controlling the temperature between 225 ℃ and 235 ℃ under a vacuum condition, stirring for reaction for 8-12 hours, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, finally taking out and placing in a forced air drying oven to dry to constant weight at the temperature of 80-90 ℃ to obtain poly 2, 5-piperidine dicarboxylic acid 4, 4-diaminodiphenyl sulfide amide;
step S2, preparation of glucoside modified poly 2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide: adding poly (2, 5-piperidinedicarboxylic acid) 4, 4-diaminodiphenyl sulfide amide, methyl 6-chloro-6-deoxy-alpha-D-glucopyranoside and an alkaline catalyst into N-methylpyrrolidone, stirring and reacting at 40-60 ℃ for 4-6 hours, then precipitating in water, washing the precipitated polymer with ethanol for 3-7 times, finally taking out and placing in a blast drying oven at 85-95 ℃ for drying to constant weight to obtain glucoside modified poly (2, 5-piperidinedicarboxylic acid) 4, 4-diaminodiphenyl sulfide amide;
step S3, crosslinking, curing and film forming: dissolving the glucoside modified poly-2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide and 1, 4-dichlorocyclohexane obtained in the step S2 in N, N-dimethylformamide to obtain a solution, then pouring the solution on a polytetrafluoroethylene plate, and drying the polytetrafluoroethylene plate at the temperature of 80-90 ℃ to constant weight to obtain a base membrane;
step S4, ion exchange: and (4) soaking the base membrane prepared in the step S3 in 0.5-1.0mol/L sodium hydroxide aqueous solution at 55-65 ℃ for 30-48 hours for ion exchange, taking out and soaking in deionized water until the deionized water is neutral, taking out the product, filtering out surface moisture, and drying in a vacuum drying oven at 65-75 ℃ to constant weight.
2. The fuel cell as claimed in claim 1, wherein the mass ratio of the 2, 5-piperidinedicarboxylic acid, the 4, 4-diaminodiphenyl sulfide, the catalyst and the high boiling point solvent in step S1 is 1:1.24 (0.4-0.6) to (6-10).
3. The fuel cell of claim 1, wherein the catalyst is at least one of thiophosphonate, phosphorous acid, and thiophosphoramide.
4. The fuel cell of claim 1, wherein the high boiling point solvent is at least one of dimethylsulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
5. The fuel cell membrane of claim 1 wherein said inert gas is one of helium, neon, and argon.
6. The fuel cell as claimed in claim 1, wherein the mass ratio of poly (2, 5-piperidinedicarboxylic acid-4, 4-diaminodiphenyl sulfide amide), methyl 6-chloro-6-deoxy-alpha-D-glucopyranoside, basic catalyst and N-methylpyrrolidone in step S2 is 1.1:1 (0.6-1): 7-10.
7. The fuel cell of claim 1, wherein the alkaline catalyst is at least one of sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide.
8. The fuel cell of claim 1, wherein the mass ratio of the glucoside-modified poly-2, 5-piperidinedicarboxylic acid 4, 4-diaminodiphenyl sulfide amide, 1, 4-dichlorocyclohexane and N, N-dimethylformamide in step S3 is 1:0.19 (20-40).
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| CN202010845940.6A CN111952616A (en) | 2019-10-24 | 2019-10-24 | Fuel cell with good alkali resistance and high strength |
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| CN201911014743.3A CN110600758A (en) | 2019-10-24 | 2019-10-24 | Fuel cell diaphragm and preparation method thereof |
| CN202010845940.6A CN111952616A (en) | 2019-10-24 | 2019-10-24 | Fuel cell with good alkali resistance and high strength |
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| CN202010845943.XA Withdrawn CN111952617A (en) | 2019-10-24 | 2019-10-24 | Fuel cell diaphragm with good alkali resistance and high strength |
| CN201911014743.3A Pending CN110600758A (en) | 2019-10-24 | 2019-10-24 | Fuel cell diaphragm and preparation method thereof |
| CN202010845940.6A Withdrawn CN111952616A (en) | 2019-10-24 | 2019-10-24 | Fuel cell with good alkali resistance and high strength |
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| CN201911014743.3A Pending CN110600758A (en) | 2019-10-24 | 2019-10-24 | Fuel cell diaphragm and preparation method thereof |
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| CA2473221A1 (en) * | 2002-01-11 | 2003-07-24 | Mikuni Shikiso Kabushiki Kaisha | Carbonaceous material and dispersion containing the same |
| EP2549572B1 (en) * | 2010-03-16 | 2019-03-13 | Toppan Printing Co., Ltd. | Process for production of cathode catalyst layer for fuel cell, cathode catalyst layer, and membrane electrode assembly for solid polymer fuel cell |
| JP6237805B2 (en) * | 2016-03-15 | 2017-11-29 | 日清紡ケミカル株式会社 | Porous separator for fuel cell |
| KR101951821B1 (en) * | 2016-08-12 | 2019-02-25 | 한국과학기술원 | Carbonaceous structure and method for preparing the same, electrode material and catalyst including the carbonaceous structure, and energy storage device including the electrode material |
| CN107978769B (en) * | 2017-11-19 | 2020-05-15 | 湖南辰砾新材料有限公司 | Triazine derivative-based diaphragm for vanadium battery and preparation method thereof |
| CN108649257B (en) * | 2018-04-03 | 2020-12-18 | 福建永同丰超低能耗建筑研究院有限公司 | High-temperature proton exchange membrane and preparation method thereof |
| CN108832057A (en) * | 2018-06-20 | 2018-11-16 | 湖南辰砾新材料有限公司 | A kind of septum for lithium ion battery and preparation method thereof |
| CN109449351A (en) * | 2018-11-20 | 2019-03-08 | 孙培丽 | A kind of lithium battery diaphragm and preparation method thereof |
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| CN110600758A (en) | 2019-12-20 |
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Application publication date: 20201117 |