CN113185736A - Polyelectrolyte material for new energy automobile fuel cell and preparation method thereof - Google Patents
Polyelectrolyte material for new energy automobile fuel cell and preparation method thereof Download PDFInfo
- Publication number
- CN113185736A CN113185736A CN202110419327.2A CN202110419327A CN113185736A CN 113185736 A CN113185736 A CN 113185736A CN 202110419327 A CN202110419327 A CN 202110419327A CN 113185736 A CN113185736 A CN 113185736A
- Authority
- CN
- China
- Prior art keywords
- fuel cell
- new energy
- energy automobile
- automobile fuel
- polyelectrolyte material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—After-treatment
- C08J5/2293—After-treatment of fluorine-containing membranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
- C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
-
- 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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Development (AREA)
- Electrochemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Conductive Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a polyelectrolyte material for a new energy automobile fuel cell, which is characterized by comprising the following steps: step S1, preparing a polymerizable cyclohexyl imidazole salt; step S2, carrying out copolymerization on polymerizable imidazole salt based on cyclohexyl, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tri (2-acryloxyethyl) isocyanurate and 5-vinyl bicyclo [2.2.1] hept-2-ene, and casting to obtain a copolymer film; and step S3, ion exchange. The invention also discloses the polyelectrolyte material for the new energy automobile fuel cell, which is prepared by the preparation method of the polyelectrolyte material for the new energy automobile fuel cell. The polyelectrolyte material for the new energy automobile fuel cell disclosed by the invention is good in comprehensive performance and performance stability, high in ionic conductivity and mechanical strength, good in alkali resistance and oxidation resistance, long in service life, safe and environment-friendly to use.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a new energy automobile fuel cell component, and specifically relates to a polyelectrolyte material for a new energy automobile fuel cell and a preparation method thereof.
Background
Along with the rapid development of social economy, energy sources are widely applied and required as the most basic power sources. The fuel cell has the advantages of long cycle life, high energy efficiency, low initial investment cost, low operation and maintenance cost, environmental friendliness, short response time, long duration and the like, becomes a hotspot of novel power technology research, and is widely applied to the fields of military affairs, space, power generation, motor vehicles, mobile equipment, resident families and the like.
The new energy automobile is a common application field of the fuel cell, the fuel cell serves as a power source in the new energy automobile, and higher requirements are provided for the fuel cell of the new energy automobile in order to guarantee the normal working stability of the new energy automobile and the safety of a driver. And the development of new energy automobile fuel cells depends on the development of cell materials. The polyelectrolyte material is used as an important indispensable component in the fuel cell of a new energy automobile, and plays roles in isolating fuel and transferring ions in the fuel cell. The performance of the electrolyte material, which is a critical component of the battery system, determines the operating efficiency of the fuel cell. How to improve the ionic conductivity and performance stability of the electrolyte material, reduce the fuel permeability and obtain the polyelectrolyte material with excellent comprehensive performance for the new energy automobile fuel cell is always the research focus of the scholars.
At present, polyelectrolyte materials for fuel cells on the market have the defects of insufficient mechanical property, thermal stability and chemical stability, poor oxidation resistance, environment-friendly preparation process and further improved alkali resistance. For example, chinese patent application No. 201910016166.5 discloses a method for preparing a polyelectrolyte membrane for a new energy automobile fuel cell, comprising the steps of: preparing 1-adamantyl hydroxyl substituted methyl-2-fluoroimidazole, (II) preparing polymerized cyclobutyl substituted imidazole salt, (III) preparing polyelectrolyte membrane material, and (IV) ion exchange. The invention also discloses the polyelectrolyte membrane for the new energy automobile fuel cell prepared by the preparation method. The polyelectrolyte membrane for the new energy automobile fuel cell disclosed by the invention has the advantages of good mechanical property, weather resistance, alkali resistance, excellent chemical stability and high ionic conductivity. However, in the preparation process of the polyelectrolyte membrane material, the product uses monomers with relatively high price and relatively low polymerization activity, so that the prepared polyelectrolyte membrane material has high cost, and the comprehensive performance and the performance stability are required to be further improved.
Therefore, the search for a more effective method to prepare the polyelectrolyte material for the new energy automobile fuel cell, which has good comprehensive performance and performance stability, high ionic conductivity and mechanical strength, good alkali resistance and oxidation resistance, long service life, and safe and environment-friendly use, is a difficult problem to be solved by researchers in the industry at present.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the polyelectrolyte material for the new energy automobile fuel cell, which has the advantages of good comprehensive performance and performance stability, high ionic conductivity and mechanical strength, good alkali resistance and oxidation resistance, long service life, and safe and environment-friendly use. Meanwhile, the invention also provides a preparation method of the polyelectrolyte material for the new energy automobile fuel cell, and the preparation method is simple in process, convenient to construct, low in requirement on equipment and suitable for industrial continuous production.
In order to achieve the aim, the invention relates to a preparation method of a polyelectrolyte material for a new energy automobile fuel cell, which is characterized by comprising the following steps:
step S1, preparation of polymerizable cyclohexyl imidazole salt: adding 1, 3-dicyclohexylimidazole hydrochloride, 1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane and a basic catalyst into an organic solvent, carrying out reflux stirring reaction at 35-50 ℃ for 4-6 hours, filtering to remove insoluble substances, and carrying out rotary evaporation to remove the solvent to obtain a polymerizable cyclohexyl-based imidazole salt;
step S2, preparation of copolymer film: adding the polymerizable cyclohexyl imidazole salt prepared in the step S1, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tris (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene and an initiator into a high boiling point solvent, and carrying out primary polymerization for 1-2 hours at 65-75 ℃ in an inert gas atmosphere to form a prepolymer; then pouring the prepolymer into a mold, placing the mold in a blast drying oven, drying at 90-98 ℃ to constant weight, and then uncovering the film to obtain a copolymer film;
step S3, ion exchange: and (3) soaking the copolymer membrane prepared in the step S2 in a sodium hydroxide solution with the mass fraction of 3-5% at 50-60 ℃ for 24-72 hours, and then washing the membrane with deionized water until the eluent is neutral to obtain the polyelectrolyte material for the new energy automobile fuel cell.
Preferably, the molar ratio of the 1, 3-dicyclohexylimidazole hydrochloride, the 1,1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane, the basic catalyst and the organic solvent in the step S1 is 1:2 (2-3): 15-25.
Preferably, the basic catalyst is at least one of sodium carbonate and potassium carbonate.
Preferably, the organic solvent is any one of diethyl ether, acetone, dichloromethane and ethyl acetate.
Preferably, the polymerizable type in the step S2 is based on cyclohexyl imidazole salt, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tri (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene, initiator and high boiling point solvent, and the mass ratio of the polymerizable type to the cyclohexyl imidazole salt to the N- (4-cyano-3-trifluoromethylphenyl) methacrylamide to the high boiling point solvent is 1 (0.5-0.7) (0.1-0.2):0.3 (0.02-0.03): 6-10).
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the inert gas is any one of nitrogen, helium, neon and argon.
The invention also aims to provide the polyelectrolyte material for the new energy automobile fuel cell, which is prepared according to the preparation method of the polyelectrolyte material for the new energy automobile fuel cell.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the polyelectrolyte material for the new energy automobile fuel cell provided by the invention has the advantages of simple process, convenience in construction, low requirement on equipment and suitability for industrial continuous production; the method can be realized by adopting a common polymerization production line without special equipment such as ultraviolet light, a radiation source and the like, the capital investment is low, the environmental influence in the preparation process is small, and the environmental protection performance is better.
(2) The polyelectrolyte material for the new energy automobile fuel cell provided by the invention has the advantages that all raw materials are synergistic, and under the multiple actions of an electronic effect, a steric effect and a conjugated effect, the prepared polyelectrolyte material is good in comprehensive performance and performance stability, high in ionic conductivity and mechanical strength, good in alkali resistance and oxidation resistance, safe and environment-friendly to use and long in service life.
(3) According to the polyelectrolyte material for the new energy automobile fuel cell, the polymerizable cyclohexyl imidazole salt is introduced, due to the introduction of a dication structure, the prepared material is high in ion conduction capability, cyclohexyl and cyclobutane substituents are arranged around a cation group, and the alkali resistance and the chemical resistance of the prepared material are remarkably improved under the multiple actions of an electronic effect, a steric hindrance effect and a conjugation effect.
(4) The polyelectrolyte material for the new energy automobile fuel cell is a silicon-free copolymer formed by copolymerization of polymerizable cyclohexyl imidazole salt, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tri (2-acryloyloxyethyl) isocyanurate and 5-vinyl bicyclo [2.2.1] hept-2-ene, and due to the fact that substituent groups on vinyl bonds of comonomers are few and copolymerization activity is high, a cyano-group, trifluoromethylphenyl, isocyanurate and bicyclo [2.2.1] hept-2-ene structure is introduced through the comonomers and synergistic effect is achieved, the prepared polyelectrolyte material is good in comprehensive performance and performance stability, and excellent in mechanical property, alkali resistance and oxidation resistance; the polymerizable cyclohexyl imidazole salt and tris (2-acryloyloxyethyl) isocyanurate contain multiple unsaturated functional groups, so that a three-dimensional network structure can be formed, and the comprehensive performance and the performance stability of the material are effectively improved.
(5) The polyelectrolyte material for the new energy automobile fuel cell provided by the invention adopts the processes of solution prepolymerization and film casting, so that the defect that a cross-linked structure formed after complete polymerization is insoluble and infusible and is difficult to process and form is avoided, the defect that the material durability is poor and the mechanical property of the polymer is influenced by the unreacted monomer in the polymer due to poor compatibility among monomers and uneven dispersion of the monomers in a bulk polymerization in-situ forming mode is also avoided, the surface of the formed material is smooth, the defects are few, and the fuel isolation performance of the formed material is good.
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 and are not intended to limit the scope of the invention, the raw materials used are commercially available.
Example 1
A preparation method of a polyelectrolyte material for a new energy automobile fuel cell is characterized by comprising the following steps:
step S1, preparation of polymerizable cyclohexyl imidazole salt: adding 1, 3-dicyclohexylimidazole hydrochloride, 1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane and a basic catalyst into an organic solvent, carrying out reflux stirring reaction for 4 hours at 35 ℃, filtering to remove insoluble substances, and carrying out rotary evaporation to remove the solvent to obtain a polymerizable cyclohexyl-based imidazole salt;
step S2, preparation of copolymer film: adding the polymerizable cyclohexyl imidazole salt prepared in the step S1, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tris (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene and an initiator into a high boiling point solvent, and carrying out primary polymerization for 1 hour at 65 ℃ in an inert gas atmosphere to form a prepolymer; then pouring the prepolymer into a mold, placing the mold in a blast drying oven, drying at 90 ℃ to constant weight, and then uncovering the film to obtain a copolymer film;
step S3, ion exchange: and (3) soaking the copolymer membrane prepared in the step S2 in a sodium hydroxide solution with the mass fraction of 3% at 50 ℃ for 24 hours, and then washing the membrane with deionized water until an eluent is neutral to obtain the polyelectrolyte material for the new energy automobile fuel cell.
The molar ratio of the 1, 3-dicyclohexylimidazole hydrochloride, the 1,1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane, the basic catalyst and the organic solvent in the step S1 is 1:2:2: 15; the alkaline catalyst is sodium carbonate; the organic solvent is diethyl ether.
The mass ratio of the polymerizable type based on cyclohexyl imidazole salt, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tri (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene, initiator and high boiling point solvent in the step S2 is 1:0.5:0.1:0.3:0.02: 6; the initiator is azobisisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen.
The polyelectrolyte material for the new energy automobile fuel cell is prepared by the preparation method of the polyelectrolyte material for the new energy automobile fuel cell.
Example 2
A preparation method of a polyelectrolyte material for a new energy automobile fuel cell is characterized by comprising the following steps:
step S1, preparation of polymerizable cyclohexyl imidazole salt: adding 1, 3-dicyclohexylimidazole hydrochloride, 1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane and a basic catalyst into an organic solvent, carrying out reflux stirring reaction at 38 ℃ for 4.5 hours, filtering to remove insoluble substances, and carrying out rotary evaporation to remove the solvent to obtain a polymerizable cyclohexyl-based imidazole salt;
step S2, preparation of copolymer film: adding the polymerizable cyclohexyl imidazole salt prepared in the step S1, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tris (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene and an initiator into a high boiling point solvent, and carrying out primary polymerization for 1.2 hours at 68 ℃ in an inert gas atmosphere to form a prepolymer; then pouring the prepolymer into a mold, placing the mold in a blast drying oven, drying at 92 ℃ to constant weight, and then uncovering the film to obtain a copolymer film;
step S3, ion exchange: and (3) soaking the copolymer membrane prepared in the step S2 in a sodium hydroxide solution with the mass fraction of 3.5% at 52 ℃ for 32 hours, and then washing the membrane with deionized water until an eluent is neutral to obtain the polyelectrolyte material for the new energy automobile fuel cell.
The molar ratio of the 1, 3-dicyclohexylimidazole hydrochloride, the 1,1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane, the basic catalyst and the organic solvent in the step S1 is 1:2:2.2: 17; the alkaline catalyst is potassium carbonate; the organic solvent is acetone.
The mass ratio of the polymerizable type based on cyclohexyl imidazole salt, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tri (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene, initiator and high boiling point solvent in the step S2 is 1:0.55:0.12:0.3:0.023: 7; the initiator is azobisisoheptonitrile; the high boiling point solvent is N, N-dimethylformamide; the inert gas is helium.
The polyelectrolyte material for the new energy automobile fuel cell is prepared by the preparation method of the polyelectrolyte material for the new energy automobile fuel cell.
Example 3
A preparation method of a polyelectrolyte material for a new energy automobile fuel cell is characterized by comprising the following steps:
step S1, preparation of polymerizable cyclohexyl imidazole salt: adding 1, 3-dicyclohexylimidazole hydrochloride, 1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane and a basic catalyst into an organic solvent, carrying out reflux stirring reaction at 43 ℃ for 5 hours, filtering to remove insoluble substances, and carrying out rotary evaporation to remove the solvent to obtain a polymerizable cyclohexyl-based imidazole salt;
step S2, preparation of copolymer film: adding the polymerizable cyclohexyl imidazole salt prepared in the step S1, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tris (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene and an initiator into a high boiling point solvent, and carrying out primary polymerization for 1.5 hours at 70 ℃ in an inert gas atmosphere to form a prepolymer; then pouring the prepolymer into a mold, placing the mold in a blast drying oven, drying at 95 ℃ to constant weight, and then uncovering the film to obtain a copolymer film;
step S3, ion exchange: and (4) soaking the copolymer membrane prepared in the step S2 in a sodium hydroxide solution with the mass fraction of 4% at the temperature of 55 ℃ for 52 hours, and then washing the membrane with deionized water until an eluent is neutral to obtain the polyelectrolyte material for the new energy automobile fuel cell.
The molar ratio of the 1, 3-dicyclohexylimidazole hydrochloride, the 1,1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane, the basic catalyst and the organic solvent in the step S1 is 1:2:2.5: 20; the alkaline catalyst is formed by mixing sodium carbonate and potassium carbonate according to the mass ratio of 3: 5; the organic solvent is dichloromethane.
The mass ratio of the polymerizable type based on cyclohexyl imidazole salt, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tri (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene, initiator and high boiling point solvent in the step S2 is 1:0.6:0.15:0.3:0.025: 8; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5; the high boiling point solvent is N, N-dimethylacetamide; the inert gas is neon.
The polyelectrolyte material for the new energy automobile fuel cell is prepared by the preparation method of the polyelectrolyte material for the new energy automobile fuel cell.
Example 4
A preparation method of a polyelectrolyte material for a new energy automobile fuel cell is characterized by comprising the following steps:
step S1, preparation of polymerizable cyclohexyl imidazole salt: adding 1, 3-dicyclohexylimidazole hydrochloride, 1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane and a basic catalyst into an organic solvent, carrying out reflux stirring reaction at 48 ℃ for 5.5 hours, filtering to remove insoluble substances, and carrying out rotary evaporation to remove the solvent to obtain a polymerizable cyclohexyl-based imidazole salt;
step S2, preparation of copolymer film: adding the polymerizable cyclohexyl imidazole salt prepared in the step S1, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tris (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene and an initiator into a high boiling point solvent, and carrying out primary polymerization for 1.8 hours at 73 ℃ in an inert gas atmosphere to form a prepolymer; then pouring the prepolymer into a mold, placing the mold in a forced air drying oven, drying at 96 ℃ to constant weight, and then uncovering the film to obtain a copolymer film;
step S3, ion exchange: and (4) soaking the copolymer membrane prepared in the step S2 in a sodium hydroxide solution with the mass fraction of 4.5% at 58 ℃ for 68 hours, and then washing the membrane with deionized water until an eluent is neutral to obtain the polyelectrolyte material for the new energy automobile fuel cell.
The molar ratio of the 1, 3-dicyclohexylimidazole hydrochloride, the 1,1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane, the basic catalyst and the organic solvent in the step S1 is 1:2:2.8: 23; the alkaline catalyst is sodium carbonate; the organic solvent is ethyl acetate.
The mass ratio of the polymerizable type based on cyclohexyl imidazole salt, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tri (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene, initiator and high boiling point solvent in the step S2 is 1:0.65:0.18:0.3:0.028: 9.5; the initiator is azobisisobutyronitrile; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide according to a mass ratio of 1:3: 5; the inert gas is argon.
The polyelectrolyte material for the new energy automobile fuel cell is prepared by the preparation method of the polyelectrolyte material for the new energy automobile fuel cell.
Example 5
A preparation method of a polyelectrolyte material for a new energy automobile fuel cell is characterized by comprising the following steps:
step S1, preparation of polymerizable cyclohexyl imidazole salt: adding 1, 3-dicyclohexylimidazole hydrochloride, 1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane and a basic catalyst into an organic solvent, carrying out reflux stirring reaction at 50 ℃ for 6 hours, filtering to remove insoluble substances, and carrying out rotary evaporation to remove the solvent to obtain a polymerizable cyclohexyl-based imidazole salt;
step S2, preparation of copolymer film: adding the polymerizable cyclohexyl imidazole salt prepared in the step S1, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tris (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene and an initiator into a high boiling point solvent, and carrying out primary polymerization for 2 hours at 75 ℃ in an inert gas atmosphere to form a prepolymer; then pouring the prepolymer into a mold, placing the mold in a blast drying oven, drying at 98 ℃ to constant weight, and then uncovering the film to obtain a copolymer film;
step S3, ion exchange: and (3) soaking the copolymer membrane prepared in the step S2 in a sodium hydroxide solution with the mass fraction of 5% at 60 ℃ for 72 hours, and then washing the membrane with deionized water until an eluent is neutral to obtain the polyelectrolyte material for the new energy automobile fuel cell.
The molar ratio of the 1, 3-dicyclohexylimidazole hydrochloride, the 1,1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane, the basic catalyst and the organic solvent in the step S1 is 1:2:3: 25; the alkaline catalyst is potassium carbonate; the organic solvent is diethyl ether.
The mass ratio of the polymerizable type based on cyclohexyl imidazole salt, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tri (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene, initiator and high boiling point solvent in the step S2 is 1:0.7:0.2:0.3:0.03: 10; the initiator is azobisisoheptonitrile; the high boiling point solvent is N, N-dimethylformamide; the inert gas is nitrogen.
The polyelectrolyte material for the new energy automobile fuel cell is prepared by the preparation method of the polyelectrolyte material for the new energy automobile fuel cell.
Comparative example 1
The formula and the preparation method of the polyelectrolyte material for the new energy automobile fuel cell are basically the same as those in example 1, except that 1-allyl-3-vinyl imidazole chloride salt is used for replacing a polymerizable cyclohexyl-based imidazole salt.
Comparative example 2
A polyelectrolyte material for a new energy automobile fuel cell has a formula and a preparation method which are basically the same as those of example 1, except that N- (4-cyano-3-trifluoromethylphenyl) methacrylamide is not added.
Comparative example 3
The formula and the preparation method of the polyelectrolyte material for the new energy automobile fuel cell are basically the same as those of example 1, except that tris (2-acryloyloxyethyl) isocyanurate is not added.
Comparative example 4
The formula and the preparation method of the polyelectrolyte material for the new energy automobile fuel cell are basically the same as those in example 1, except that 5-vinyl bicyclo [2.2.1] hept-2-ene is not added.
The samples obtained in examples 1 to 5 and comparative examples 1 to 4 were subjected to the relevant performance tests, the test results are shown in Table 1, the test methods are as follows,
(1) and (3) testing tensile strength: the tensile rate was 5mm/min, measured 3 times per sample using a universal prototype (Instron Model 3365) at 25 ℃ to obtain an average value; cutting a sample into a rectangular sample strip with the length of 40mm and the width of 10 mm;
(2) conductivity: the impedance is tested on a frequency response analyzer with a frequency sweep range of 1-106Hz, the amplitude of the alternating current signal is 50 mV; the cut material (2.5 cm × 1.5cm long × wide) was tested by the two-electrode ac impedance method, and before the test, the sample was saturated in room temperature deionized water. The ionic conductivity σ (S/cm) was calculated by the following formula:
wherein σ is the conductivity (S cm)-1) L is the distance (cm) between the two electrodes, R is the impedance of the sample being measured, and S is the cross-sectional area of the membrane。
(3) Alkali resistance: soaking the material in a KOH aqueous solution of 1mol/L at room temperature, taking out the material after a certain time interval, repeatedly washing the material with deionized water until the washing liquid is neutral, then measuring the ionic conductivity of the material, recording the change curve of the ionic conductivity along with the time, and comparing the alkali resistance stability of the material by the time that the ionic conductivity is reduced to 70% of that before soaking. The above is not relevant and is applicable to the prior art.
TABLE 1 Properties of samples of examples and comparative examples
As can be seen from Table 1, the polyelectrolyte material for the new energy automobile fuel cell disclosed by the invention has better tensile strength and alkali resistance, and higher conductivity, which is a result of synergistic effect of the raw materials.
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 (9)
1. A preparation method of a polyelectrolyte material for a new energy automobile fuel cell is characterized by comprising the following steps:
step S1, preparation of polymerizable cyclohexyl imidazole salt: adding 1, 3-dicyclohexylimidazole hydrochloride, 1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane and a basic catalyst into an organic solvent, carrying out reflux stirring reaction at 35-50 ℃ for 4-6 hours, filtering to remove insoluble substances, and carrying out rotary evaporation to remove the solvent to obtain a polymerizable cyclohexyl-based imidazole salt;
step S2, preparation of copolymer film: adding the polymerizable cyclohexyl imidazole salt prepared in the step S1, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tris (2-acryloyloxyethyl) isocyanurate, 5-vinyl bicyclo [2.2.1] hept-2-ene and an initiator into a high boiling point solvent, and carrying out primary polymerization for 1-2 hours at 65-75 ℃ in an inert gas atmosphere to form a prepolymer; then pouring the prepolymer into a mold, placing the mold in a blast drying oven, drying at 90-98 ℃ to constant weight, and then uncovering the film to obtain a copolymer film;
step S3, ion exchange: and (3) soaking the copolymer membrane prepared in the step S2 in a sodium hydroxide solution with the mass fraction of 3-5% at 50-60 ℃ for 24-72 hours, and then washing the membrane with deionized water until the eluent is neutral to obtain the polyelectrolyte material for the new energy automobile fuel cell.
2. The method as claimed in claim 1, wherein the molar ratio of 1, 3-dicyclohexylimidazole hydrochloride, 1, 2-trifluoro-2-chloro-3-methyl-3-vinylcyclobutane, basic catalyst, and organic solvent in step S1 is 1:2 (2-3): 15-25.
3. The method for preparing the polyelectrolyte material for the new energy automobile fuel cell according to claim 1, wherein the alkaline catalyst is at least one of sodium carbonate and potassium carbonate.
4. The method for preparing the polyelectrolyte material for the new energy automobile fuel cell according to claim 1, wherein the organic solvent is any one of diethyl ether, acetone, dichloromethane and ethyl acetate.
5. The method as claimed in claim 1, wherein the polymerizable polyelectrolyte material for a new energy automobile fuel cell is prepared from cyclohexyl imidazole salt, N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, tris (2-acryloyloxyethyl) isocyanurate, 5-vinylbicyclo [2.2.1] hept-2-ene, initiator and high boiling point solvent in the mass ratio of 1 (0.5-0.7) to (0.1-0.2) to 0.3 (0.02-0.03) to (6-10) in step S2.
6. The method for preparing the polyelectrolyte material for the new energy automobile fuel cell according to claim 1, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
7. The method according to claim 1, wherein the high-boiling-point solvent is at least one of dimethylsulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
8. The method for preparing the polyelectrolyte material for the new energy automobile fuel cell according to claim 1, wherein the inert gas is any one of nitrogen, helium, neon and argon.
9. The polyelectrolyte material for the new energy automobile fuel cell, which is prepared by the method for preparing the polyelectrolyte material for the new energy automobile fuel cell according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110419327.2A CN113185736A (en) | 2021-04-19 | 2021-04-19 | Polyelectrolyte material for new energy automobile fuel cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110419327.2A CN113185736A (en) | 2021-04-19 | 2021-04-19 | Polyelectrolyte material for new energy automobile fuel cell and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113185736A true CN113185736A (en) | 2021-07-30 |
Family
ID=76977708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110419327.2A Withdrawn CN113185736A (en) | 2021-04-19 | 2021-04-19 | Polyelectrolyte material for new energy automobile fuel cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113185736A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683726A (en) * | 2021-08-25 | 2021-11-23 | 常熟三爱富中昊化工新材料有限公司 | Polymer for fuel cell proton exchange membrane and preparation method thereof |
-
2021
- 2021-04-19 CN CN202110419327.2A patent/CN113185736A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683726A (en) * | 2021-08-25 | 2021-11-23 | 常熟三爱富中昊化工新材料有限公司 | Polymer for fuel cell proton exchange membrane and preparation method thereof |
| CN113683726B (en) * | 2021-08-25 | 2022-10-14 | 常熟三爱富中昊化工新材料有限公司 | Polymer for fuel cell proton exchange membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110233288B (en) | All-solid-state polymer electrolyte with semi-interpenetrating network structure and preparation method thereof | |
| CN112185712B (en) | Imidazole polyion liquid gel electrolyte and preparation method thereof | |
| Raducha et al. | Nonaqueous H3PO4-doped gel electrolytes | |
| CN108707252B (en) | Nano composite ionic liquid gel material, preparation thereof and strain sensor based on material | |
| CN111040137A (en) | Anion exchange polymer and preparation method and application thereof | |
| KR101535062B1 (en) | Partially fluorinated anion exchange membrane and manufacturing method for thereof | |
| CN113061266B (en) | High-strength ionic gel based on multiple non-covalent crosslinking effects | |
| CN106887622A (en) | Fluorine-containing single ion conductor polymer dielectric and preparation method and application | |
| CN113185736A (en) | Polyelectrolyte material for new energy automobile fuel cell and preparation method thereof | |
| CN110071328B (en) | Cross-linked modified polyethyleneimine solid electrolyte and application thereof | |
| CN113831488A (en) | Fluorine-containing benzaldehyde-aromatic hydrocarbon polymer, electrolyte thereof, and preparation method and application of ion exchange membrane | |
| CN113871705B (en) | Self-repairing polyionic liquid-based electrolyte and preparation and application thereof | |
| Lin et al. | Phosphoric acid doped hydrophobic ionic liquid-based composite membranes for anhydrous proton exchange membrane application | |
| CN102945975A (en) | Pyridine onium salt polymer anion exchange film and preparation method thereof | |
| CN107978779B (en) | Self-repairing anion exchange membrane for fuel cell and preparation method thereof | |
| CN111063930B (en) | Solid polymer electrolyte for lithium ion battery and application thereof | |
| Li et al. | Trimethyl-ammonium alkaline anion exchange membranes with the vinylbenzyl chloride/acrylonitrile main chain | |
| CN107978769B (en) | Triazine derivative-based diaphragm for vanadium battery and preparation method thereof | |
| CN110828872B (en) | High-temperature proton exchange membrane for fuel cell and preparation method thereof | |
| CN112442153B (en) | Electrolyte polymer base material, solid electrolyte, preparation method of solid electrolyte and lithium ion battery | |
| CN112531189A (en) | Anion exchange membrane for fuel cell and preparation method thereof | |
| CN114695933A (en) | Semi-interpenetrating anion exchange membrane and preparation method and application thereof | |
| KR20010060179A (en) | Polyelectrolytic gel and process to manufacture polyelectrolytic gel | |
| CN107978778B (en) | High-temperature anhydrous proton exchange membrane and preparation method thereof | |
| CN111326797B (en) | Liquid polymer electrolyte, polymer electrolyte membrane and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210730 |