CN113736390B - Adhesive for membrane electrode and membrane electrode - Google Patents
Adhesive for membrane electrode and membrane electrode Download PDFInfo
- Publication number
- CN113736390B CN113736390B CN202111033899.3A CN202111033899A CN113736390B CN 113736390 B CN113736390 B CN 113736390B CN 202111033899 A CN202111033899 A CN 202111033899A CN 113736390 B CN113736390 B CN 113736390B
- Authority
- CN
- China
- Prior art keywords
- adhesive
- membrane electrode
- film
- curing
- beaker
- 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.)
- Active
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 249
- 239000000853 adhesive Substances 0.000 title claims abstract description 243
- 239000012528 membrane Substances 0.000 title claims abstract description 95
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 41
- 238000000016 photochemical curing Methods 0.000 claims abstract description 35
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 19
- BTVVNGIPFPKDHO-UHFFFAOYSA-K cerium(3+);octadecanoate Chemical compound [Ce+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O BTVVNGIPFPKDHO-UHFFFAOYSA-K 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- 238000009792 diffusion process Methods 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- -1 cerium ion Chemical class 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 38
- 238000000034 method Methods 0.000 abstract description 33
- 150000003254 radicals Chemical class 0.000 abstract description 22
- 239000000654 additive Substances 0.000 abstract description 21
- 239000000446 fuel Substances 0.000 abstract description 17
- 239000002516 radical scavenger Substances 0.000 abstract description 16
- 229940123457 Free radical scavenger Drugs 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000004026 adhesive bonding Methods 0.000 abstract description 3
- 239000002313 adhesive film Substances 0.000 description 93
- 230000000052 comparative effect Effects 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 30
- 230000004580 weight loss Effects 0.000 description 25
- 238000011010 flushing procedure Methods 0.000 description 24
- 239000000126 substance Substances 0.000 description 24
- 229910021642 ultra pure water Inorganic materials 0.000 description 23
- 239000012498 ultrapure water Substances 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 230000001678 irradiating effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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 relates to the field of fuel cells, in particular to an adhesive for a membrane electrode and the membrane electrode, wherein the photo-curing adhesive for the membrane electrode comprises a photo-curing adhesive body and an organic photosensitizer, wherein the organic photosensitizer is one or more mixtures of metal phthalocyanine complexes containing metal ions and/or one or more mixtures of stearates containing metal ions, and the organic photosensitizer added into the adhesive can promote the crosslinking and curing of the adhesive, improve the curing efficiency of the adhesive and can also be used as a free radical scavenger to kill free radicals generated in the operation process of the fuel cell so as to slow down the degradation of the adhesive and avoid the influence of a plurality of additives with single functions on the adhesive bonding performance.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to an adhesive for a membrane electrode and the membrane electrode.
Background
The fuel cell is a combination of tens to hundreds of membrane electrodes, the membrane electrodes are hearts of a fuel cell stack, the performance and the service life of the membrane electrodes determine the service condition and the service life of the fuel cell, and the whole cell cannot work as long as any membrane electrode is damaged and air leakage occurs in the operation process of the cell. The membrane electrode is used as a core component of the fuel cell and mainly comprises an anode gas diffusion layer, an anode catalyst layer, a proton exchange membrane, a cathode catalyst layer and a cathode gas diffusion layer. The current mainstream packaging method of the membrane electrode is a double-side frame packaging method, firstly, anode catalyst layers and cathode catalyst layers are respectively coated on two sides of a proton exchange membrane to prepare a catalyst coating membrane with a three-layer structure, then, the edges of the catalyst coating membrane and the edges of two frames are bonded and sealed through an adhesive to form a five-layer assembly, and finally, the two gas diffusion layers are respectively bonded with the frames through the adhesive to form a seven-layer membrane electrode. In the prior art, a membrane electrode adopting a single-side frame packaging technology is also available, but an adhesive is needed to be used for preparing the membrane electrode with a double-side frame structure or a membrane electrode with a single-side frame structure. The adhesive has the functions of adhesion and fixation in the membrane electrode and sealing, and can prevent the catalyst coating film from damaging and air leakage during the operation of the fuel cell, so that the adhesion and stability of the adhesive have great influence on the performance and service life of the membrane electrode.
The adhesive is typically a high molecular weight polymer. In the operation process of the fuel cell, hydrogen and oxygen generate hydrogen peroxide under the action of a platinum catalyst, and the hydrogen peroxide reacts with metal ion impurities in the membrane electrode to generate free radicals, so that a macromolecular chain of the adhesive is attacked, the adhesive is degraded to fail, the air tightness of the membrane electrode is reduced, and an intermediate or a product generated by the degradation of the adhesive may poison the fuel cell catalyst and degrade a proton exchange membrane, thereby influencing the performance and the service life of the membrane electrode.
There are techniques currently developed for using additives in the active area of the layers of the membrane electrode that scavenge hydrogen peroxide and free radicals generated during the reaction. However, since the active region and the adhesive region of the membrane electrode are different in environments, the manner in which these additives are present is different, and the diffusion rate and the loss rate of the additive added to the active region are high, it is difficult to protect the membrane electrode for a long period of time, and it is difficult to greatly improve the life of the fuel cell. The Chinese patent 'an adhesive for a membrane electrode and a membrane electrode' (publication No. CN112375529A, publication No. 2021.02.19) discloses an adhesive, wherein a free radical scavenger is added into the adhesive, so that the membrane electrode is not easy to degrade and lose efficacy, and the service life of the membrane electrode is prolonged. However, such a radical scavenger only has a single function of eliminating radicals, and if other properties of the adhesive are to be optimized, other additives are required to be added, however, when the types or the amounts of the additives are too large, the cost of the membrane electrode is increased, and the adhesive properties of the adhesive are also affected.
Disclosure of Invention
The invention aims to overcome at least one defect (deficiency) of the prior art, and provides an adhesive for a membrane electrode and a membrane electrode, wherein an organic photosensitizer added in the adhesive can promote crosslinking and curing of the adhesive, improve the curing efficiency of the adhesive, and can also be used as a free radical scavenger to eliminate free radicals generated in the operation process of a fuel cell so as to slow down the degradation of the adhesive, and can avoid the influence of the addition of a plurality of additives with single functions on the bonding performance of the adhesive.
The technical scheme adopted by the invention is that the adhesive for the membrane electrode is provided, and the photocuring adhesive for the membrane electrode is characterized by comprising a photocuring adhesive body and an organic photosensitizer, wherein the organic photosensitizer is one or more mixtures of metal phthalocyanine complexes containing metal ions and/or one or more mixtures of stearates containing metal ions.
In the operation process of the fuel cell, hydrogen and oxygen generate hydrogen peroxide under the action of a platinum catalyst of the catalyst layer, the hydrogen peroxide reacts with metal ion impurities in the membrane electrode to generate free radicals (as shown in formula 1), and the free radicals attack a macromolecular chain of the adhesive to degrade and lose efficacy, so that the air tightness of the membrane electrode is reduced, and an intermediate or a product generated by degradation may poison the catalyst layer and further degrade a proton exchange membrane, so that the performance and the service life of the membrane electrode are influenced.
Formula 1:
Formation of H 2 O 2 ：
H 2 →2H·(via Pt catalyst)
H·+O 2 (diffused through PEM)→HOO·
HOO·+H·→H 2 O 2 (which can diffuse into PEM)
or
2H + +O 2 +2e→H 2 O 2
Generation of free radical：
H 2 O 2 +M 2+ (Fe 2+ ，Cu 2+ ，etc)→M 3+ +·OH+OH -
M 3+ +HO 2 - →M 2+ +HOO·
·OII+H 2 O 2 →H 2 O+HOO·
in the technical scheme, the organic photosensitizer added into the photo-curing adhesive can have the function of a free radical scavenger, can capture and eliminate free radicals generated in the operation process of the fuel cell, reduce and slow down the degradation of the adhesive when the membrane electrode is operated, and can also improve the curing efficiency of the photo-curing adhesive, and the adoption of one additive can optimize various performances of the adhesive, so that the dosage of the additive can be greatly reduced, and the bonding performance of the adhesive is ensured; in the preparation process of the membrane electrode, after the adhesive of the technical scheme is coated on the bonding part, under the irradiation of ultraviolet light, the organic photosensitizer absorbs ultraviolet light to generate active free radicals or cations, so that the high polymer of the adhesive body is promoted to generate crosslinking curing reaction, the curing speed of the adhesive is accelerated, the organic photosensitizer still remains in the adhesive for sealing after curing and still can keep activity, and the organic photosensitizer can be used as a free radical scavenger in the operation process of the fuel cell, so that the free radicals generated in an active area and diffused to the bonding part are captured and eliminated, and therefore, other metal ions are not required to be additionally introduced to capture the free radicals, and the effect that one additive has two optimization functions is realized.
Further, the metal ion is one or more of cerium ion, manganese ion or cobalt ion. The use of these metal ions can make the radical trapping effect better.
Preferably, the organic photosensitizer is one or a mixture of two of manganese phthalocyanine or cerium stearate.
Further, the addition amount of the organic photosensitizer is 0.1-10% of the mass of the adhesive body.
Preferably, the addition amount of the organic photosensitizer is 1-5% of the mass of the adhesive body.
Although the more the additive is added, the more obvious the optimizing effect is, but when the additive is added too much, the preparation cost of the membrane electrode is increased, and the bonding performance of the adhesive is also affected, so in the technical scheme, the addition of the organic photosensitizer is kept within a certain range to ensure the bonding performance of the adhesive, and meanwhile, the addition can ensure that the organic photosensitizer still has the organic photosensitizer with certain activity in the adhesive as a free radical scavenger after the photocuring of the adhesive is promoted, thereby improving the photocuring speed and stability of the adhesive, and further improving the production efficiency and the service life of the membrane electrode.
The invention also provides a membrane electrode, which comprises a frame and a membrane electrode body, wherein the frame and the membrane electrode body are bonded through an adhesive, the membrane electrode body comprises an anode gas diffusion layer, a proton exchange membrane and a cathode gas diffusion layer which are sequentially bonded and laminated through the adhesive, the proton exchange membrane is coated with an anode catalyst layer on one side where the anode gas diffusion layer is arranged, and is coated with a cathode catalyst layer on the other side, and the adhesive is the photocuring adhesive for the membrane electrode.
Compared with the prior art, the invention has the beneficial effects that:
the organic photosensitizer is added into the photo-curing adhesive body, so that photo-curing of the adhesive is promoted, the production efficiency is improved, the organic photosensitizer can still keep certain activity after photo-curing, can be used as a free radical scavenger for capturing and eliminating generated free radicals in the operation process of a fuel cell, and can reduce degradation of the photo-curing adhesive due to free radical attack, thereby prolonging the service life of a membrane electrode; the invention adopts specific organic photosensitizer, can realize the effect that one additive has two optimizing functions, does not need to add a plurality of additives with single function, and avoids the decrease of the adhesive property and the sealing property of the adhesive caused by the plurality of additives contained in the adhesive.
Drawings
FIG. 1 is a graph showing the adhesion performance test of the photo-curable adhesive for membrane electrode of the present invention.
Fig. 2 is a schematic structural diagram of embodiment 9 of the present invention.
Detailed Description
The drawings are for illustrative purposes only and are not to be construed as limiting the invention. For better illustration of the following embodiments, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the actual product dimensions; it will be appreciated by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
The embodiment provides a photocuring adhesive for a membrane electrode, which consists of a photocuring adhesive body and an organic photosensitizer, wherein the photocuring adhesive body is a UV light curing adhesive HENKEL Loctite EA3355, the organic photosensitizer is manganese phthalocyanine, the addition amount of the organic photosensitizer accounts for 1% of the adhesive body by mass, and the photocuring adhesive for the membrane electrode is prepared by uniformly mixing the photocuring adhesive body and the organic photosensitizer.
The adhesive prepared in this example was tested for curing efficiency by the following method:
placing the adhesive prepared in the embodiment in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this example was tested for stability by the following method:
the adhesive film with the initial weight of 1.5368 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 0.8179 g of freshly prepared 0.1% FeSO is weighed out 4 The solution was added to a beaker (Fe in the mixed solution in the beaker) 2+ After the concentration of the adhesive film is 10 ppm), placing the beaker in a constant temperature environment of 90 ℃ for reaction for 3 hours, taking out the adhesive film after the reaction is finished, and flushing the adhesive film for multiple times by using a large amount of ultrapure water to remove H on the surface of the adhesive film 2 O 2 And Fe (Fe) 2+ And (3) waiting for residual substances, drying the adhesive film at 80 ℃ under vacuum overnight, weighing the adhesive film mass to obtain a final weight value, calculating the weight loss ratio of the adhesive film according to the initial weight value and the final weight value, and recording the weight loss ratio in table 2.
Example 2
This example provides a photocurable adhesive for a membrane electrode, which is substantially the same as in example 1 except that the addition amount of manganese phthalocyanine is 2% of the mass of the adhesive body.
The adhesive prepared in this example was tested for curing efficiency by the following method:
placing the adhesive prepared in the embodiment in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this example was tested for stability by the following method:
the adhesive film with the initial weight of 1.3721 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 0.8179 g of freshly prepared 0.1% FeSO is weighed out 4 The solution was added to a beaker (Fe in the mixed solution in the beaker) 2+ After the concentration of the polymer is 10 ppm), placing the beaker in a constant temperature environment of 90 ℃ for reaction for 3 hours, taking out the adhesive film after the reaction is finished, and flushing the adhesive film for a plurality of times by using a large amount of ultrapure waterH for removing surface of adhesive film 2 O 2 And Fe (Fe) 2+ And (3) waiting for residual substances, drying the adhesive film at 80 ℃ under vacuum overnight, weighing the adhesive film mass to obtain a final weight value, calculating the weight loss ratio of the adhesive film according to the initial weight value and the final weight value, and recording the weight loss ratio in table 2.
Example 3
This example provides a photocurable adhesive for a membrane electrode, which is substantially the same as in example 1 except that the manganese phthalocyanine is added in an amount of 5% by mass of the adhesive body.
The adhesive prepared in this example was tested for curing efficiency by the following method:
placing the adhesive prepared in the embodiment in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this example was tested for stability by the following method:
the adhesive film with the initial weight of 1.5902 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 0.8179 g of freshly prepared 0.1% FeSO is weighed out 4 The solution was added to a beaker (Fe in the mixed solution in the beaker) 2+ After the concentration of the adhesive film is 10 ppm), placing the beaker in a constant temperature environment of 90 ℃ for reaction for 3 hours, taking out the adhesive film after the reaction is finished, and flushing the adhesive film for multiple times by using a large amount of ultrapure water to remove H on the surface of the adhesive film 2 O 2 And Fe (Fe) 2+ And (3) waiting for residual substances, drying the adhesive film at 80 ℃ under vacuum overnight, weighing the adhesive film mass to obtain a final weight value, calculating the weight loss ratio of the adhesive film according to the initial weight value and the final weight value, and recording the weight loss ratio in table 2.
Example 4
This example provides a photocurable adhesive for a membrane electrode, which is substantially the same as in example 1 except that the addition amount of manganese phthalocyanine is 10% of the mass of the adhesive body.
The adhesive prepared in this example was tested for curing efficiency by the following method:
placing the adhesive prepared in the embodiment in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this example was tested for stability by the following method:
the adhesive film with the initial weight of 1.2945 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 0.8179 g of freshly prepared 0.1% FeSO is weighed out 4 The solution was added to a beaker (Fe in the mixed solution in the beaker) 2+ After the concentration of the adhesive film is 10 ppm), placing the beaker in a constant temperature environment of 90 ℃ for reaction for 3 hours, taking out the adhesive film after the reaction is finished, and flushing the adhesive film for multiple times by using a large amount of ultrapure water to remove H on the surface of the adhesive film 2 O 2 And Fe (Fe) 2+ And (3) waiting for residual substances, drying the adhesive film at 80 ℃ under vacuum overnight, weighing the adhesive film mass to obtain a final weight value, calculating the weight loss ratio of the adhesive film according to the initial weight value and the final weight value, and recording the weight loss ratio in table 2.
Example 5
This example provides a photocurable adhesive for a membrane electrode, which is substantially the same as in example 1, except that the organic photosensitizer is cerium stearate.
The adhesive prepared in this example was tested for curing efficiency by the following method:
placing the adhesive prepared in the embodiment in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this example was tested for stability by the following method:
the adhesive film with the initial weight of 1.5943 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 0.8173 g of freshly prepared 0.1% FeSO is weighed out 4 The solution was added to a beaker (Fe in the mixed solution in the beaker) 2+ After the concentration of the adhesive film is 10 ppm), placing the beaker in a constant temperature environment of 90 ℃ for reaction for 3 hours, taking out the adhesive film after the reaction is finished, and flushing the adhesive film for multiple times by using a large amount of ultrapure water to remove H on the surface of the adhesive film 2 O 2 And Fe (Fe) 2+ And (3) waiting for residual substances, drying the adhesive film at 80 ℃ under vacuum overnight, weighing the adhesive film mass to obtain a final weight value, calculating the weight loss ratio of the adhesive film according to the initial weight value and the final weight value, and recording the weight loss ratio in table 2.
Example 6
This example provides a photocurable adhesive for a membrane electrode, which is substantially the same as in example 5 except that cerium stearate is added in an amount of 2% by mass of the adhesive body.
The adhesive prepared in this example was tested for curing efficiency by the following method:
placing the adhesive prepared in the embodiment in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this example was tested for stability by the following method:
the adhesive film with the initial weight of 1.3746 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 0.8179 g of freshly prepared 0.1% FeSO is weighed out 4 The solution was added to a beaker (Fe in the mixed solution in the beaker) 2+ After the concentration of the adhesive film is 10 ppm), placing the beaker in a constant temperature environment of 90 ℃ for reaction for 3 hours, taking out the adhesive film after the reaction is finished, and flushing the adhesive film for multiple times by using a large amount of ultrapure water to remove H on the surface of the adhesive film 2 O 2 And Fe (Fe) 2+ And (3) waiting for residual substances, drying the adhesive film at 80 ℃ under vacuum overnight, weighing the adhesive film mass to obtain a final weight value, calculating the weight loss ratio of the adhesive film according to the initial weight value and the final weight value, and recording the weight loss ratio in table 2.
Example 7
This example provides a photocurable adhesive for a membrane electrode, which is substantially the same as in example 5 except that the addition amount of cerium stearate is 5% of the mass of the adhesive body.
The adhesive prepared in this example was tested for curing efficiency by the following method:
placing the adhesive prepared in the embodiment in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this example was tested for stability by the following method:
the adhesive film with the initial weight of 1.6144 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 0.8179 g of freshly prepared 0.1% FeSO is weighed out 4 The solution was added to a beaker (Fe in the mixed solution in the beaker) 2+ After 10ppm of the concentration of (C) in the flask, the flask was placed in a constant temperature environment at 90℃for 3 hours,after the reaction is finished, taking out the adhesive film, and repeatedly flushing the adhesive film with a large amount of ultrapure water to remove H on the surface of the adhesive film 2 O 2 And Fe (Fe) 2+ And (3) waiting for residual substances, drying the adhesive film at 80 ℃ under vacuum overnight, weighing the adhesive film mass to obtain a final weight value, calculating the weight loss ratio of the adhesive film according to the initial weight value and the final weight value, and recording the weight loss ratio in table 2.
Example 8
This example provides a photocurable adhesive for a membrane electrode, which is substantially the same as in example 5 except that the addition amount of cerium stearate is 10% of the mass of the adhesive body.
The adhesive prepared in this example was tested for curing efficiency by the following method:
placing the adhesive prepared in the embodiment in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this example was tested for stability by the following method:
the adhesive film with the initial weight of 1.3754 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 0.8179 g of freshly prepared 0.1% FeSO is weighed out 4 The solution was added to a beaker (Fe in the mixed solution in the beaker) 2+ After the concentration of the adhesive film is 10 ppm), placing the beaker in a constant temperature environment of 90 ℃ for reaction for 3 hours, taking out the adhesive film after the reaction is finished, and flushing the adhesive film for multiple times by using a large amount of ultrapure water to remove H on the surface of the adhesive film 2 O 2 And Fe (Fe) 2+ And (3) waiting for residual substances, drying the adhesive film at 80 ℃ under vacuum overnight, weighing the adhesive film mass to obtain a final weight value, calculating the weight loss ratio of the adhesive film according to the initial weight value and the final weight value, and recording the weight loss ratio in table 2.
Example 9
The embodiment provides a membrane electrode, including frame 2 and membrane electrode body, frame 2 and membrane electrode body pass through the adhesive bonding, the membrane electrode body includes through the positive pole gas diffusion layer 3, proton exchange membrane 1 and the negative pole gas diffusion layer 4 of adhesive bonding lamination in proper order, proton exchange membrane 1 is setting up the positive pole gas diffusion layer 3's one side coating anode catalyst layer, on the opposite side coating negative pole catalyst layer, the adhesive is any one of the membrane electrode photocuring adhesive of embodiment 1 through 6 preparation.
Comparative example 1
The present comparative example provides a photo-curable adhesive for a membrane electrode, which is a UV light curable adhesive HENKEL Loctite EA3355, and does not contain the organic photosensitizer of the present invention.
The adhesive prepared in this comparative example was tested for curing efficiency by the following method:
placing the adhesive prepared in the comparative example in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this comparative example was tested for stability as follows:
the adhesive film with the initial weight of 1.5212 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 0.8179 g of freshly prepared 0.1% FeSO4 solution was weighed into a beaker (Fe in the mixed solution in the beaker) 2+ After the concentration of the adhesive film is 10 ppm), placing the beaker in a constant temperature environment of 90 ℃ for reaction for 3 hours, taking out the adhesive film after the reaction is finished, and flushing the adhesive film for multiple times by using a large amount of ultrapure water to remove H on the surface of the adhesive film 2 O 2 And Fe (Fe) 2+ Then vacuum drying the adhesive film at 80 ℃ overnight, weighing the adhesive film mass to obtain a final weight value, and obtaining the final weight value according to the initial weight value and the final weight valueThe weight loss ratio of the adhesive film was calculated from the weight values and recorded in table 2.
Comparative example 2
The comparative example provides a photo-curable adhesive for a membrane electrode, which consists of a photo-curable adhesive body and a free radical scavenger, wherein the photo-curable adhesive body is a UV light curable adhesive HENKEL Loctite EA3355, and the free radical scavenger is Ce (NO 3 ) 3 ，Ce(NO 3 ) 3 The addition amount of the photo-curing adhesive for the membrane electrode is 1% of the mass fraction of the adhesive body, and the photo-curing adhesive for the membrane electrode is prepared by uniformly mixing the photo-curing adhesive body and the free radical scavenger.
The adhesive prepared in this comparative example was tested for curing efficiency by the following method:
placing the adhesive prepared in the comparative example in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this comparative example was tested for stability as follows:
the adhesive film with the initial weight of 1.5401 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 0.8179 g of freshly prepared 0.1% FeSO4 solution was weighed into a beaker (Fe in the mixed solution in the beaker) 2+ After the concentration of the adhesive film is 10 ppm), placing the beaker in a constant temperature environment of 90 ℃ for reaction for 3 hours, taking out the adhesive film after the reaction is finished, and flushing the adhesive film for multiple times by using a large amount of ultrapure water to remove H on the surface of the adhesive film 2 O 2 And Fe (Fe) 2+ And (3) waiting for residual substances, drying the adhesive film at 80 ℃ under vacuum overnight, weighing the adhesive film mass to obtain a final weight value, calculating the weight loss ratio of the adhesive film according to the initial weight value and the final weight value, and recording the weight loss ratio in table 2.
Comparative example 3
This comparative example provides a photocurable adhesive for a membrane electrode, which is substantially the same as comparative example 2, except that the radical scavenger is MnSO 4 。
The adhesive prepared in this comparative example was tested for curing efficiency by the following method:
placing the adhesive prepared in the comparative example in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this comparative example was tested for stability as follows:
the adhesive film with the initial weight of 1.5462 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 0.8179 g of freshly prepared 0.1% FeSO4 solution was weighed into a beaker (Fe in the mixed solution in the beaker) 2+ After the concentration of the adhesive film is 10 ppm), placing the beaker in a constant temperature environment of 90 ℃ for reaction for 3 hours, taking out the adhesive film after the reaction is finished, and flushing the adhesive film for multiple times by using a large amount of ultrapure water to remove H on the surface of the adhesive film 2 O 2 And Fe (Fe) 2+ And (3) waiting for residual substances, drying the adhesive film at 80 ℃ under vacuum overnight, weighing the adhesive film mass to obtain a final weight value, calculating the weight loss ratio of the adhesive film according to the initial weight value and the final weight value, and recording the weight loss ratio in table 2.
Comparative example 4
The comparative example provides a photo-curing adhesive for a membrane electrode, which consists of a photo-curing adhesive body and a photosensitizer, wherein the photo-curing adhesive body is a UV light irradiation curing adhesive HENKEL Loctite EA3355, the photosensitizer is conventional photosensitizer 2,4, 6-trimethylbenzoyl ethyl phenylphosphonate (TPO-L), the addition amount of the TPO-L accounts for 1% of the mass of the adhesive body, and the photo-curing adhesive for the membrane electrode is prepared by uniformly mixing the photo-curing adhesive body and the photosensitizer.
The adhesive prepared in this comparative example was tested for curing efficiency by the following method:
placing the adhesive prepared in the comparative example in a surface dish, after the adhesive is leveled on the bottom surface of the surface dish, irradiating the adhesive with UV light with the wavelength of 405nm to completely cure the adhesive, wherein the UV light irradiation time required for the adhesive to reach the complete curing is recorded in Table 1; and (3) after the adhesive is completely solidified, a film is obtained, a large amount of ultrapure water is used for flushing residual substances on the surface of the film, the flushed film is dried overnight under vacuum at 80 ℃ to sufficiently remove moisture in the film, and then the film is taken out for standby after being cooled to room temperature.
The adhesive prepared in this comparative example was tested for stability as follows:
the adhesive film with the initial weight of 1.3428 g is weighed and placed in a 100ml beaker, and 30ml of 10% H is taken 2 O 2 And weighing 0.8179 g of freshly prepared 0.1% FeSO4 solution, adding the solution into a beaker (the concentration of Fe < 2+ > in the mixed solution in the beaker is 10 ppm), placing the beaker into a constant temperature environment of 90 ℃ for reaction for 3 hours, taking out the adhesive film after the reaction is finished, and flushing the adhesive film for multiple times by using a large amount of ultrapure water to remove H on the surface of the adhesive film 2 O 2 And Fe (Fe) 2+ And (3) waiting for residual substances, drying the adhesive film at 80 ℃ under vacuum overnight, weighing the adhesive film mass to obtain a final weight value, calculating the weight loss ratio of the adhesive film according to the initial weight value and the final weight value, and recording the weight loss ratio in table 2.
Comparative example 5
The comparative example provides a photo-curing adhesive for a membrane electrode, which consists of a photo-curing adhesive body, a photosensitizer and a free radical scavenger, wherein the photo-curing adhesive body is a UV light curing adhesive HENKEL Loctite EA3355, the photosensitizer is TPO-L, the addition amount of the TPO-L accounts for 1% of the adhesive body by mass, and the free radical scavenger is Ce (NO 3 ) 3 ，Ce(NO 3 ) 3 The addition amount of the adhesive accounts for 1 percent of the mass of the adhesive body, and the membrane electrode is used upThe curing adhesive is prepared by uniformly mixing the photo-curing adhesive body, the photosensitizer and the free radical scavenger.
The curing efficiency test results of examples 1 to 8 and comparative examples 1 to 4 are shown in table 1.
Table 1:
as is clear from Table 1, under the same curing conditions, except for example 4, the curing time of the adhesive added with manganese phthalocyanine or cerium stearate was far longer than that of the adhesive added with Ce (NO) having only a single radical trapping function 3 ) 3 And MnSO 4 And the adhesive without the photosensitizer is short, which shows that a certain amount of manganese phthalocyanine and cerium stearate can effectively promote the crosslinking curing efficiency of the photo-curing adhesive.
The stability test results of examples 1 to 8 and comparative examples 1 to 4 are shown in table 2.
The stability test described above was a process that utilized the Fenton (Fenton) reaction to simulate the generation of free radicals during operation of a fuel cell. The Fenton (Fenton) reaction generates free radicals by the reaction of hydrogen peroxide and ferrous ions, and in the Fenton (Fenton) reaction, hydroxyl free radicals and peroxy free radicals can be generated simultaneously, as follows:
Fe 2+ +H 2 O 2 →Fe 3+ +(OH) - +OH·①
H 2 O 2 +Fe 3+ →Fe 2+ +HO 2 ·+H + ②
as is clear from Table 2, under the same reaction conditions, the weight loss ratio of the adhesive added with manganese phthalocyanine or cerium stearate was far smaller than that of the adhesive added with photosensitizer TPO-L having only a single function and without photosensitizer, wherein the adhesive added with cerium stearate and the adhesive added with Ce (NO 3 ) 3 Or MnSO 4 Compared with the adhesive, the weight loss ratio of the adhesive is smaller, which indicates that the manganese phthalocyanine and the cerium stearate can simultaneously play the roles of a photosensitizer and a free radical scavenger, and after the adhesive is promoted to be solidified, the adhesive still has a certain activity and can trap and eliminate free radicals, thereby improving the chemical stability of the adhesive in the free radical environment.
The photo-curable adhesives of examples 1, 3, 5, and 7 and comparative examples 1 and 5 were used for the adhesion performance test by the following method:
s1, coating the prepared adhesive on a piece of membrane electrode frame material, covering another piece of frame material to form a structure of sequentially laminated frame material-adhesive-frame material, and then irradiating the adhesive with UV light with the wavelength of 405nm for 20 seconds to completely cure the adhesive to obtain a sample;
s2, cutting the sample obtained in the step S1 into strips with the width of 2cm, and testing the peel strength between two pieces of frame materials by using a universal testing machine to characterize the bonding performance of the adhesive.
The peel strength curve of the adhesive is shown in fig. 1, wherein the displacement of the abscissa represents the peel length of the sample, the peel strength of the ordinate represents the force value required for peeling off each centimeter of the sample, and the curves correspond to comparative example 1, example 5, example 1, example 7, comparative example 5 and example 3 from top to bottom in the position of 24mm on the abscissa.
As is clear from the comparison of examples 1 and 3 with comparative example 1, the addition of 1% manganese phthalocyanine or 1% cerium stearate to the UV light curable adhesive has substantially no effect on the adhesion performance of the UV light curable adhesive, but as is clear from the comparison of examples 5 and 7 with examples 1 and 3, the adhesion performance of the adhesive tends to gradually decrease as the amount of the additive increases, and therefore, the amount of the additive preferably does not exceed 10% of the mass of the adhesive body, and is preferably 1 to 5%; comparative example 5 was far lower in the adhesive properties of the adhesive obtained as compared with examples 1, 3, 5, 7 and comparative example 1 than in example 1 to which 1% of manganese phthalocyanine was added, example 5 to which 1% of cerium stearate was added and comparative example 1 to which no additive was added, and lower in example 7 to which 5% of cerium stearate was added, and was similar to example 3 to which 5% of manganese phthalocyanine was added, it was found that a plurality of additives having only a single function were simultaneously added to the UV light curable adhesive to optimize the various properties of the adhesive, and the adhesive properties of the adhesive were remarkably lowered even though the amount of each additive was small, and the organic photosensitizer added to the adhesive of the present invention had both effects of optimizing the adhesive properties, and the influence of the additives on the adhesive properties was reduced.
It should be understood that the foregoing examples of the present invention are merely illustrative of the present invention and are not intended to limit the present invention to the specific embodiments thereof. Any modification, equivalent replacement, improvement, etc. that comes within the spirit and principle of the claims of the present invention should be included in the protection scope of the claims of the present invention.
Claims (4)
1. The photocuring adhesive for the membrane electrode is characterized by comprising a photocuring adhesive body and an organic photosensitizer, wherein the organic photosensitizer is one or more mixtures of metal phthalocyanine complexes containing metal ions and/or one or more mixtures of stearates containing metal ions, and the addition amount of the organic photosensitizer is 1% -5% of the mass of the adhesive body.
2. The photocurable adhesive for a membrane electrode according to claim 1, wherein the metal ion is one or more of cerium ion, manganese ion or cobalt ion.
3. The photocurable adhesive for a membrane electrode according to claim 2, wherein the organic photosensitizer is one or a mixture of two of manganese phthalocyanine or cerium stearate.
4. A membrane electrode comprising a frame and a membrane electrode body, wherein the frame and the membrane electrode body are bonded by an adhesive, the membrane electrode body comprises an anode gas diffusion layer, a proton exchange membrane and a cathode gas diffusion layer which are sequentially bonded and laminated by the adhesive, the proton exchange membrane is coated with an anode catalyst layer on one side where the anode gas diffusion layer is arranged and a cathode catalyst layer on the other side, and the membrane electrode is characterized in that the adhesive is the photocuring adhesive for the membrane electrode according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111033899.3A CN113736390B (en) | 2021-09-03 | 2021-09-03 | Adhesive for membrane electrode and membrane electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111033899.3A CN113736390B (en) | 2021-09-03 | 2021-09-03 | Adhesive for membrane electrode and membrane electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113736390A CN113736390A (en) | 2021-12-03 |
| CN113736390B true CN113736390B (en) | 2023-07-25 |
Family
ID=78735558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111033899.3A Active CN113736390B (en) | 2021-09-03 | 2021-09-03 | Adhesive for membrane electrode and membrane electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113736390B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114854345A (en) * | 2022-06-17 | 2022-08-05 | 苏州摩尔新材料科技有限公司 | Adhesive for membrane electrode and preparation method of membrane electrode |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7605194B2 (en) * | 2003-06-24 | 2009-10-20 | Ppg Industries Ohio, Inc. | Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates |
| US7537857B2 (en) * | 2003-12-17 | 2009-05-26 | Bdf Ip Holdings Ltd. | Reduced degradation of ion-exchange membranes in electrochemical fuel cells |
| CN101013257B (en) * | 2007-01-17 | 2011-08-24 | 中国科学院理化技术研究所 | Application of metal organic acid salt as development accelerant |
-
2021
- 2021-09-03 CN CN202111033899.3A patent/CN113736390B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113736390A (en) | 2021-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1702378B1 (en) | Reduced degradation of ion-exchange membranes in electrochemical fuel cells | |
| Ohma et al. | Phenomenon analysis of PEFC for automotive use (1) membrane degradation behavior during OCV hold test | |
| WO2006026031A2 (en) | Constituents and methods for protecting fuel cell components, including pems | |
| CN113736390B (en) | Adhesive for membrane electrode and membrane electrode | |
| EP2061110B1 (en) | Reinforced electrolyte membrane for fuel cell, method for production thereof, membrane-electrode assembly for fuel cell, and solid polymer-type fuel cell having the assembly | |
| WO2006006357A1 (en) | Electrolyte membrane for solid polymer fuel cell, method for producing same and membrane electrode assembly for solid polymer fuel cell | |
| US20190319287A1 (en) | Antioxidant for polymer electrolyte membrane fuel cells, electrolyte including the same, and membrane-electrode assembly for vehicles including the same | |
| KR100919647B1 (en) | Fluoride ion scavenger for fuel cell components | |
| JP2005190752A (en) | Membrane electrode assembly for fuel cell, and solid polymer fuel cell using it | |
| Venugopalan et al. | Correlating high temperature thin film ionomer electrode binder properties to hydrogen pump polarization | |
| US6949304B2 (en) | Fullerene-based electrolyte for fuel cells | |
| CN112375529A (en) | Adhesive for membrane electrode and membrane electrode | |
| KR20070049917A (en) | Seperater for fuel cell, method of preparing same, and fuel cell system comprising same | |
| Imamura et al. | Effect of air contaminants on the electrolyte degradation in polymer electrolyte membrane fuel cells | |
| Uchida et al. | New evaluation method for degradation rate of polymer electrolytes | |
| KR101922329B1 (en) | Method for activating and long-term storaging of air-breathing polymer electrolyte membrane fuel cell | |
| Kim et al. | Tailor‐Made Charged Catechol‐Based Polymeric Ligands to Build Robust Fuel Cells Containing Antioxidative Nanoparticles | |
| Gubler et al. | Hydrocarbon proton exchange membranes | |
| EP2192646B1 (en) | Solid polymer electrolyte membrane, method for production of solid polymer electrolyte membrane, and fuel cell | |
| JP2005268114A (en) | Membrane electrode assembly for fuel cell, fuel cell, and manufacturing method of the membrane electrode assembly for fuel cell | |
| EP2202832B1 (en) | Solid polymer electrolyte membrane, method for producing the same, membrane-electrode assembly for fuel cell, and fuel cell | |
| Arges | Materials Advances | |
| CN106887633A (en) | A kind of high-temperature fuel cell pile | |
| EP1863110B1 (en) | Electrolyte film with excellent adhesion to electrode | |
| CN117254081A (en) | Anti-aging proton exchange membrane, preparation method thereof and membrane electrode assembly |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |