CN110783612A - Low-yellowness index composite proton exchange membrane and preparation method thereof - Google Patents
Low-yellowness index composite proton exchange membrane and preparation method thereof Download PDFInfo
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- CN110783612A CN110783612A CN201911024087.5A CN201911024087A CN110783612A CN 110783612 A CN110783612 A CN 110783612A CN 201911024087 A CN201911024087 A CN 201911024087A CN 110783612 A CN110783612 A CN 110783612A
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- 239000012528 membrane Substances 0.000 title claims abstract description 145
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002952 polymeric resin Substances 0.000 claims abstract description 73
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 73
- 238000001035 drying Methods 0.000 claims abstract description 43
- 239000002033 PVDF binder Substances 0.000 claims abstract description 31
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 150000003460 sulfonic acids Chemical class 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- -1 transition metal salt Chemical class 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 5
- 230000008961 swelling Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920003934 Aciplex® Polymers 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- 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
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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
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Abstract
The invention relates to the technical field of proton exchange membranes, in particular to a low-yellowness index composite proton exchange membrane and a preparation method thereof. The composite proton exchange membrane with the low yellowness index comprises a three-layer composite structure of a middle layer of a PVDF porous membrane and modified polymer resin layers on two sides of the middle layer, wherein modified polymer resin is filled in membrane pores of the PVDF porous membrane; the composite proton exchange membrane is prepared by coating modified polymer resin on the upper surface and the lower surface of a PVDF porous membrane and humidifying and drying; the modified polymer resin layer is prepared by modifying polymer resin by adopting an additive containing a transition metal element. The low-yellowness index composite proton exchange membrane has a compact structure, low air permeability and low yellowness index, prolongs the service life of the proton exchange membrane, reduces the swelling degree of the proton exchange membrane, and improves the appearance of the proton exchange membrane; the invention also provides a preparation method of the composition.
Description
Technical Field
The invention relates to the technical field of proton exchange membranes, in particular to a low-yellowness index composite proton exchange membrane and a preparation method thereof.
Background
Proton exchange membrane fuel cell technology relies on the development of two key materials, proton exchange membrane and electrocatalyst. The proton exchange membrane mainly plays the roles of electronic isolation of an anode and a cathode and isolation of reaction gas, and simultaneously provides the proton conduction function of the electrolyte. The proton exchange membrane is located at the middle position of the membrane electrode in the fuel cell, and is increasingly becoming a vital role in the research of the fuel cell.
The perfluorinated sulfonic acid proton exchange membrane is a proton exchange membrane which is most applied in the development of the proton exchange membrane fuel cell at present, and has excellent conductivity and a series of other advantages. Although the price is high, the comprehensive performance of the film is incomparable with other film materials at present. In addition to the Nafion membrane of dupont, similar products have been developed by companies such as Dow membrane of Dow Chemical company, usa, Aciplex membrane of Asahi Chemical company, japan, and Flemion membrane of Asahi Glass company.
The perfluorinated sulfonic acid proton exchange membrane is a solid polymer electrolyte, has excellent heat resistance, mechanical property, electrochemical property and chemical stability, and can be used under severe conditions of strong acid, strong base, strong oxidant medium and the like; however, perfluorosulfonic acid proton exchange membranes still have some disadvantages when used in fuel cells: high cost, low ion exchange capacity, low conductivity, low gas permeability, high methanol permeability, poor thermal stability, and the like.
Currently, commercially available Nafion membranes and Gore composite proton exchange membranes (Gore-Select membranes) are widely used, but these membranes have different appearance colors, gas permeability and lifetime. Therefore, modifying the existing proton exchange membrane to improve the comprehensive performance thereof becomes the key content of the extensive research of people.
The patent CN201910220927.9 discloses a proton exchange membrane and a preparation method thereof, wherein the proton exchange membrane consists of three layers of membranes, the middle layer comprises 3.125-16.25 wt% of transition metal sulfide, 6.25-62.5 wt% of vinyl polymer, 21.25-90.625 wt% of perfluorinated sulfonic acid, and the rest two layers comprise perfluorinated sulfonic acid and polyvinylidene fluoride copolymer; the coating is prepared by a layer-by-layer coating and drying method. The prepared proton exchange membrane has good heat resistance, greatly improved water retention capacity, long service life and high open circuit voltage of the battery.
Patent CN200510018912.2 discloses a method for preparing a composite proton exchange membrane from alkali metal ion type perfluorosulfonic acid resin, which comprises treating perfluorosulfonic acid resin solution with solution containing alkali metal ions to convert sulfonic acid functional group of the resin into M type with alkali metal ions, then compounding M type perfluorosulfonic acid resin into a porous polytetrafluoroethylene membrane, and performing vacuum drying treatment to form the porous polymer reinforced proton exchange membrane for fuel cells. The prepared membrane has good air tightness, high strength and proton conductivity, and has good application effect in proton exchange membrane fuel cells.
Patent CN200910231452.X discloses a perfluorosulfonic acid composite proton exchange membrane for fuel cells, which consists of perfluorosulfonic acid resin, M-type perfluorosulfonic acid resin and porous polymer reinforced material, wherein the M-type perfluorosulfonic acid resin is cerium or/and manganese metal ion type perfluorosulfonic acid resin formed by completely exchanging cerium or/and manganese ions with sulfonic acid groups or sulfonyl fluoride groups in the perfluorosulfonic acid resin. Cerium or/and manganese ions can be uniformly distributed in a membrane body, so that the thermal stability is high, the heat treatment temperature of the composite membrane is increased, the combination of a porous polymer reinforced material and perfluorinated sulfonic acid resin is facilitated, and the prepared composite proton exchange membrane has good mechanical strength and proton conductivity and is favorable for improving the performance of a fuel cell.
Although the above patent discloses cerium and/or manganese metal ion type perfluorosulfonic acid resin, manganese ions can be uniformly distributed in the membrane body, and the composite membrane has high thermal stability and increases the heat treatment temperature, while the thermal recombination temperature of the membrane is increased, the color of the membrane is changed, i.e. the yellowness index is increased, and the appearance of the membrane is affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-yellowness index composite proton exchange membrane which has a compact structure, low air permeability and low yellowness index, prolongs the service life of the proton exchange membrane, reduces the swelling degree of the proton exchange membrane and improves the appearance of the proton exchange membrane; the invention also provides a preparation method of the composition.
The composite proton exchange membrane with the low yellowness index comprises a three-layer composite structure of a middle layer of a PVDF porous membrane and modified polymer resin layers on two sides of the middle layer, wherein modified polymer resin is filled in membrane pores of the PVDF porous membrane; the composite proton exchange membrane is prepared by coating modified polymer resin on the upper surface and the lower surface of a PVDF porous membrane and humidifying and drying;
the modified polymer resin layer is prepared by modifying polymer resin by adopting an additive containing a transition metal element.
The polymer resin is perfluorosulfonic acid resin with equivalent weight range of 700-1400 g/mmol.
The PVDF porous membrane has a thickness of 10 to 25 μm and a pore diameter of 0.1 to 0.9. mu.m.
The modified polymer resin layers are uniformly coated on the upper and lower surfaces of the PVDF porous membrane.
The thickness of the composite proton exchange membrane is 20-100 μm.
The additive containing transition metal element is one of transition metal simple substance, transition metal alloy, transition metal oxide and transition metal salt. Preferably MnO
2、Mn
2O
3、MnO、MnSO
4、NiF
2、NiSO
4One kind of (1).
In the modified polymer resin, the sulfonated high molecular polymer and the additive can form a complex compound to prevent iron nickel ions and hydrogen peroxide from generating free radicals, so that the free radicals in the membrane are prevented from attacking the membrane, and the service life and the durability of the proton exchange membrane can be better improved.
The preparation method of the low-yellowness index composite proton exchange membrane comprises the following steps:
(1) adding polymer resin into a solvent to prepare a polymer resin solution with the solid content of 15-18 wt%, and adding an additive containing a transition metal element into the polymer resin solution to uniformly disperse the additive in a perfluorinated sulfonic acid resin solution for complete reaction;
(2) firstly, uniformly coating a modified polymer resin on a base material, then placing a PVDF porous membrane on the modified polymer resin coating, then coating a layer of modified polymer resin on the PVDF porous membrane, and obtaining a wet membrane after leveling by a scraper;
(3) and (3) carrying out stage heating, humidifying and drying on the wet membrane to obtain the low-yellowness-index composite proton exchange membrane.
In the step (1), the solvent is a mixture of one or more of propanol, ethanol and acetonitrile and water.
In the step (1), the addition amount of the additive containing the transition metal element is 0.3-1% of the mass of the polymer resin.
The substrate in the step (2) is a glass plate. The wet membrane is separated from the composite proton exchange membrane after being dried and is reused.
And (4) in the step (3), the temperature rise, humidification and drying are carried out by adopting an oven or a constant temperature and humidity test box with a humidification function. The stage heating, humidifying and drying is divided into three stages, the first two stages adopt humidifying and drying, and the third stage does not carry out humidifying.
The heating, humidifying and drying conditions in the step (3) are as follows: the first stage is as follows: drying at 50-70 deg.C and 50-80 RH% for 0.5-2 hr; and a second stage: drying at 80-100 deg.C and 50-99 RH% for 0.5-2 hr; and a third stage: drying at the temperature of 110 ℃ and 160 ℃ for 0.5-2h under the condition of no humidity.
When the wet film is dried and solidified, a unique stage heating, humidifying and drying process is adopted, humidity is respectively given during the first two stages of heating during drying gradient heating, the volatilization speed of the solvent is controlled, the dry cracking is prevented, and finally the aging temperature is increased for aging.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the polymer resin is modified by adopting the additive containing the transition metal element, and the polymer resin layer is modified by the transition metal ionic compound to form a complex compound, so that the free radicals in the membrane can be prevented from attacking the membrane, and the service life and the durability of the proton exchange membrane are further improved;
(2) the composite proton exchange membrane has a three-layer composite structure of a PVDF porous membrane middle layer and modified polymer resin layers on two sides of the middle layer, and the PVDF porous membrane has higher mechanical strength and has a reinforcing effect on the proton exchange membrane;
(3) the invention adopts a method of heating, humidifying and drying in stages to carry out heat treatment on the composite proton exchange membrane, can control the humidity in the drying process, further control the volatilization speed of the solvent in the modified polymer resin layer, prevent the modified polymer resin layer from cracking in the film forming process and greatly improve the yield.
Drawings
FIG. 1 is a schematic structural view of a low yellowness index composite proton exchange membrane according to the present invention;
1. a modified polymer resin; 2. a PVDF porous membrane; 3. PVDF porous membrane pores.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto, and modifications of the technical solutions of the present invention by those skilled in the art should be within the scope of the present invention.
Example 1
The low yellowness index composite proton exchange membrane is prepared by the following method:
(1) uniformly mixing propanol, ethanol, acetonitrile and water according to the mass ratio of 4:2:2:1, then adding perfluorinated sulfonic acid resin powder in batches, stirring to completely dissolve the perfluorinated sulfonic acid resin powder to prepare a polymer resin solution with the solid content of 15 wt%, and adding Mn (OH) into the polymer resin solution
2The adding amount of the catalyst is 0.3 percent of the mass of the polymer resin, and the catalyst is uniformly stirred to be uniformly dispersed in the perfluorinated sulfonic acid resin solution for complete reaction;
(2) uniformly coating modified polymer resin on a glass plate, placing a PVDF porous membrane with the thickness of 20 mu m and the pore diameter of 0.7 mu m on the modified polymer resin coating, then coating a layer of modified polymer resin on the PVDF porous membrane, and obtaining a wet membrane after leveling by a scraper;
(3) the wet film is put into a constant temperature and humidity box for stage heating, humidifying and drying, and the setting conditions of the constant temperature and humidity box are as follows: the first stage is as follows: drying at 50 deg.C and humidity of 60 RH% for 1 h; and a second stage: drying at 80 deg.C and 90 RH% for 1 h; and a third stage: drying at 150 deg.C for 1h without humidity; the low-yellowness index composite proton exchange membrane is prepared.
Example 2
The low yellowness index composite proton exchange membrane is prepared by the following method:
(1) uniformly mixing propanol, ethanol and water according to the mass ratio of 4:3:3, adding perfluorinated sulfonic acid resin powder in batches, stirring to completely dissolve the perfluorinated sulfonic acid resin powder to prepare polymer resin solution with the solid content of 18 wt%, and adding MnO into the polymer resin solution
2The adding amount of the catalyst is 0.1 percent of the mass of the polymer resin, and the catalyst is uniformly stirred to be uniformly dispersed in the perfluorinated sulfonic acid resin solution for complete reaction;
(2) uniformly coating modified polymer resin on a glass plate, placing a PVDF porous membrane with the thickness of 15 mu m and the pore diameter of 0.9 mu m on the modified polymer resin coating, then coating a layer of modified polymer resin on the PVDF porous membrane, and obtaining a wet membrane after leveling by a scraper;
(3) the wet film is put into a constant temperature and humidity box for stage heating, humidifying and drying, and the setting conditions of the constant temperature and humidity box are as follows: the first stage is as follows: drying at 50 deg.C and 40 RH% for 1 h; and a second stage: drying at 80 deg.C and 70 RH% for 1 h; and a third stage: drying at 150 deg.C for 1h without humidity; the low-yellowness index composite proton exchange membrane is prepared.
Example 3
The low yellowness index composite proton exchange membrane is prepared by the following method:
(1) mixing propanol, ethanol and water according to a mass ratio of 4:2, uniformly mixing, adding perfluorinated sulfonic acid resin powder in batches, stirring to completely dissolve the perfluorinated sulfonic acid resin powder to prepare a polymer resin solution with the solid content of 18 wt%, and adding NiSO into the polymer resin solution
4The adding amount of the catalyst is 0.6 percent of the mass of the polymer resin, and the catalyst is uniformly stirred to be uniformly dispersed in the perfluorinated sulfonic acid resin solution for complete reaction;
(2) uniformly coating modified polymer resin on a glass plate, placing a PVDF porous membrane with the thickness of 25 mu m and the pore diameter of 0.5 mu m on the modified polymer resin coating, then coating a layer of modified polymer resin on the PVDF porous membrane, and obtaining a wet membrane after leveling by a scraper;
(3) the wet film is put into a constant temperature and humidity box for stage heating, humidifying and drying, and the setting conditions of the constant temperature and humidity box are as follows: the first stage is as follows: drying at 50 deg.C and humidity of 60 RH% for 1 h; and a second stage: drying at 80 deg.C and 90 RH% for 1 h; and a third stage: drying at 150 deg.C for 1h without humidity; the low-yellowness index composite proton exchange membrane is prepared.
Comparative example 1
Compared with example 1, the comparative example is different from example 1 only in that a conventional drying method is adopted, and the specific steps are as follows:
(1) uniformly mixing propanol, ethanol, acetonitrile and water according to the mass ratio of 4:2:2:1, then adding perfluorinated sulfonic acid resin powder in batches, stirring to completely dissolve the perfluorinated sulfonic acid resin powder to prepare a polymer resin solution with the solid content of 15 wt%, and adding Mn (OH) into the polymer resin solution
2The adding amount of the catalyst is 0.3 percent of the mass of the polymer resin, and the catalyst is uniformly stirred to be uniformly dispersed in the perfluorinated sulfonic acid resin solution for complete reaction;
(2) uniformly coating modified polymer resin on a glass plate, placing a PVDF porous membrane with the thickness of 20 mu m and the pore diameter of 0.7 mu m on the modified polymer resin coating, then coating a layer of modified polymer resin on the PVDF porous membrane, and obtaining a wet membrane after leveling by a scraper;
(3) drying the wet film in a drying oven at 50 ℃ for 1h, at 80 ℃ for 1h and at 110 ℃ for 1 h; and preparing the composite proton exchange membrane.
Comparative example 2
Compared with the example 1, the comparative example is different only in that the polymer resin is modified by the additive containing the alkali metal element, and the conventional drying method is adopted, and the specific steps are as follows:
(1) uniformly mixing propanol, ethanol, acetonitrile and water according to a mass ratio of 4:2:2:1, then adding perfluorinated sulfonic acid resin powder in batches, stirring to completely dissolve the perfluorinated sulfonic acid resin powder, preparing a polymer resin solution with a solid content of 15 wt%, adding KCl into the polymer resin solution, wherein the addition amount of the KCl is 0.3% of the mass of the polymer resin, and uniformly stirring to uniformly disperse the perfluorinated sulfonic acid resin solution for complete reaction;
(2) uniformly coating modified polymer resin on a glass plate, placing a PVDF porous membrane with the thickness of 20 mu m and the pore diameter of 0.7 mu m on the modified polymer resin coating, then coating a layer of modified polymer resin on the PVDF porous membrane, and obtaining a wet membrane after leveling by a scraper;
(3) drying the wet film in a drying oven at 50 ℃ for 1h, at 80 ℃ for 1h and at 110 ℃ for 1 h; and preparing the composite proton exchange membrane.
The performance of the composite proton exchange membranes prepared in the examples and the comparative examples is tested, and the test method is as follows:
(1) thickness: testing according to GB/T6672-2001;
(2) swelling degree: testing according to GB/T20042.3-2009 section 3.5;
(3) hydrogen gas transmittance: tested according to GB/T20042.3-2009, section 7.
The test results are shown in table 1.
Table 1 results of performance test of composite proton exchange membranes prepared in examples and comparative examples
As can be seen from Table 1, the polymer resin is modified by the additive containing the transition metal element, and the composite proton exchange membrane is subjected to heat treatment by the method of heating, humidifying and drying in stages, so that the prepared composite proton exchange membrane has a low yellowness index, the service life and the durability of the proton exchange membrane are improved, and the added additive can improve the heat resistance of the membrane, thereby improving the annealing temperature. The comparative examples 1 and 2 are dried along with the composite proton exchange membrane by adopting a conventional drying method, the annealing temperature is lower than that of humidification and drying, and the structure of the proton exchange membrane can be more compact by improving the aging temperature of drying the membrane; the polymer resin of the comparative example 1 is modified, and the prepared composite proton exchange membrane has a high yellowness index, so that the appearance and the service life of the membrane are influenced; comparative example 2 although the polymer resin was modified, the composite proton exchange membrane prepared by using the alkali metal element had a higher yellowness index than that of the examples.
Claims (10)
1. A low yellowness index composite proton exchange membrane is characterized in that: the composite structure comprises a PVDF porous membrane middle layer and modified polymer resin layers on two sides of the middle layer, wherein modified polymer resin is filled in membrane pores of the PVDF porous membrane; the composite proton exchange membrane is prepared by coating modified polymer resin on the upper surface and the lower surface of a PVDF porous membrane and humidifying and drying;
the modified polymer resin layer is prepared by modifying polymer resin by adopting an additive containing a transition metal element.
2. The low yellowness index composite proton exchange membrane according to claim 1 wherein: the polymer resin is perfluorosulfonic acid resin with equivalent weight range of 700-1400 g/mmol.
3. The low yellowness index composite proton exchange membrane according to claim 1 wherein: the PVDF porous membrane has a thickness of 10 to 25 μm and a pore diameter of 0.1 to 0.9. mu.m.
4. The low yellowness index composite proton exchange membrane according to claim 1 wherein: the thickness of the composite proton exchange membrane is 20-100 μm.
5. The low yellowness index composite proton exchange membrane according to claim 1 wherein: the additive containing transition metal element is one of transition metal simple substance, transition metal alloy, transition metal oxide and transition metal salt.
6. A method of preparing a low yellowness index composite proton exchange membrane according to claim 1, comprising the steps of:
(1) adding polymer resin into a solvent to prepare a polymer resin solution with the solid content of 15-18 wt%, and adding an additive containing a transition metal element into the polymer resin solution to uniformly disperse the additive in a perfluorinated sulfonic acid resin solution for complete reaction;
(2) firstly, uniformly coating a modified polymer resin on a base material, then placing a PVDF porous membrane on the modified polymer resin coating, then coating a layer of modified polymer resin on the PVDF porous membrane, and obtaining a wet membrane after leveling by a scraper;
(3) and (3) carrying out stage heating, humidifying and drying on the wet membrane to obtain the low-yellowness-index composite proton exchange membrane.
7. The method of preparing a low yellowness index composite proton exchange membrane according to claim 6, wherein: in the step (1), the solvent is a mixture of one or more of propanol, ethanol and acetonitrile and water.
8. The method of preparing a low yellowness index composite proton exchange membrane according to claim 6, wherein: in the step (1), the addition amount of the additive containing the transition metal element is 0.3-1% of the mass of the polymer resin.
9. The method of preparing a low yellowness index composite proton exchange membrane according to claim 6, wherein: the substrate in the step (2) is a glass plate.
10. The method of preparing a low yellowness index composite proton exchange membrane according to claim 6, wherein: the heating, humidifying and drying conditions in the step (3) are as follows: the first stage is as follows: drying at 50-70 deg.C and 50-80 RH% for 0.5-2 hr; and a second stage: drying at 80-100 deg.C and 50-99 RH% for 0.5-2 hr; and a third stage: drying at the temperature of 110 ℃ and 160 ℃ for 0.5-2h under the condition of no humidity.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940343A (en) * | 2021-04-06 | 2021-06-11 | 苏州科润新材料股份有限公司 | Enhanced perfluorinated sulfonic acid composite proton exchange membrane and production process thereof |
| CN113871673A (en) * | 2021-09-07 | 2021-12-31 | 国家电投集团氢能科技发展有限公司 | Composite proton exchange membrane and preparation method thereof |
| CN114420987A (en) * | 2022-01-24 | 2022-04-29 | 一汽解放汽车有限公司 | Composite proton exchange membrane and preparation method and application thereof |
| CN116065171A (en) * | 2022-11-30 | 2023-05-05 | 华电重工股份有限公司 | An enhanced long-life proton exchange membrane for hydrogen production by electrolysis of water and its preparation method |
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2019
- 2019-10-25 CN CN201911024087.5A patent/CN110783612A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940343A (en) * | 2021-04-06 | 2021-06-11 | 苏州科润新材料股份有限公司 | Enhanced perfluorinated sulfonic acid composite proton exchange membrane and production process thereof |
| CN112940343B (en) * | 2021-04-06 | 2022-09-02 | 苏州科润新材料股份有限公司 | Enhanced perfluorinated sulfonic acid composite proton exchange membrane and production process thereof |
| CN113871673A (en) * | 2021-09-07 | 2021-12-31 | 国家电投集团氢能科技发展有限公司 | Composite proton exchange membrane and preparation method thereof |
| CN114420987A (en) * | 2022-01-24 | 2022-04-29 | 一汽解放汽车有限公司 | Composite proton exchange membrane and preparation method and application thereof |
| CN114420987B (en) * | 2022-01-24 | 2024-03-19 | 一汽解放汽车有限公司 | Composite proton exchange membrane and preparation method and application thereof |
| CN116065171A (en) * | 2022-11-30 | 2023-05-05 | 华电重工股份有限公司 | An enhanced long-life proton exchange membrane for hydrogen production by electrolysis of water and its preparation method |
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