CN115050987A - Sealing material for protecting membrane electrode of fuel cell and preparation method thereof - Google Patents
Sealing material for protecting membrane electrode of fuel cell and preparation method thereof Download PDFInfo
- Publication number
- CN115050987A CN115050987A CN202210753733.7A CN202210753733A CN115050987A CN 115050987 A CN115050987 A CN 115050987A CN 202210753733 A CN202210753733 A CN 202210753733A CN 115050987 A CN115050987 A CN 115050987A
- Authority
- CN
- China
- Prior art keywords
- parts
- resin emulsion
- fuel cell
- membrane electrode
- water
- 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.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 68
- 239000012528 membrane Substances 0.000 title claims abstract description 67
- 239000003566 sealing material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims abstract description 87
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 229920001971 elastomer Polymers 0.000 claims abstract description 17
- 239000000806 elastomer Substances 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000004831 Hot glue Substances 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- 210000004027 cell Anatomy 0.000 claims description 46
- 230000001681 protective effect Effects 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 210000000170 cell membrane Anatomy 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000012948 isocyanate Substances 0.000 claims description 16
- 150000002513 isocyanates Chemical class 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 239000002562 thickening agent Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 239000002518 antifoaming agent Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 239000006184 cosolvent Substances 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims 3
- 235000013824 polyphenols Nutrition 0.000 claims 3
- 238000001035 drying Methods 0.000 abstract description 15
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 description 22
- 229920002635 polyurethane Polymers 0.000 description 21
- 239000010410 layer Substances 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000000306 component Substances 0.000 description 9
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 6
- 238000004026 adhesive bonding Methods 0.000 description 6
- 238000007731 hot pressing Methods 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 229920003051 synthetic elastomer Polymers 0.000 description 6
- 239000005061 synthetic rubber Substances 0.000 description 6
- 239000003292 glue Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- -1 Polytetrafluoroethylene Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0284—Organic resins; Organic polymers
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a sealing material for protecting a membrane electrode of a fuel cell and a preparation method thereof, and the sealing material comprises epoxy resin emulsion, polyphenol-oxygen resin emulsion, hot melt adhesive emulsion, elastomer resin emulsion, hydroxyl organic silicon resin emulsion, a curing agent and a functional assistant, and particularly discloses two sealing materials of a sealing material for protecting the membrane electrode of the fuel cell and a sealing material for protecting the membrane electrode of the fuel cell in a self-drying manner; under the condition that the film thickness is the same or similar, the higher the film crosslinking density of the thermosetting product is, the better the compactness of the film is, the better the mechanical property is, and meanwhile, the higher the compactness of the film is, the stronger the permeability of the anti-medium is, and the stronger the anti-corrosion property of the film is; the longer the service performance of the membrane, the longer the service life of the fuel cell.
Description
Technical Field
The invention relates to a material for protecting a membrane electrode of a battery, in particular to a sealing material for protecting the membrane electrode of the fuel battery, which has strong corrosion resistance and long service life.
Background
Fuel cells (Fuel cells) are power generation devices that directly convert chemical energy in externally supplied Fuel and oxide into electric energy, heat energy and other reaction products through electrochemical reaction, and are classified into proton exchange membrane Fuel cells, solid oxide Fuel cells and the like according to different electrolytes, wherein a stack is a core component of the proton exchange membrane Fuel cells, single cells form a Cell stack in a stacking manner, and the single cells include bipolar plates, membrane electrodes and sealing rings.
The Membrane Electrode (MEA) is the most central component of a Proton Exchange Membrane Fuel Cell (PEMFC), is a site of heterogeneous material transmission and electrochemical reaction for energy conversion, relates to three-phase interfacial reaction and complex mass and heat transfer process, and directly determines the performance, life and cost of the PEMFC.
The membrane electrode is a place for multiphase substance transmission and electrochemical reaction, which determines the performance, service life and cost of the proton exchange membrane fuel cell, and the high-performance membrane electrode should have: 1) the gas transmission resistance is reduced to the maximum extent, so that the reaction gas smoothly generates electrochemical reaction from the diffusion layer to the catalyst layer; 2) a good ion channel is formed, and the ion transmission resistance is reduced; 3) forming a good electronic channel; 4) the gas diffusion layer should ensure good mechanical strength and thermal conductivity; 5) proton exchange membranes have high proton conductivity and good chemical, thermal and hydrolysis resistance.
Suitable materials for the MEA protective film layer are typically organic thermoplastic materials, synthetic rubbers or rigid plastic polymers, such as Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyphenylene sulfide (PPS), Polyethylene (PE), polypropylene (PP), Polyester (PET), Polyamide (PA), Polyimide (PI), Polyurethane (PU), Silicone (SI), and synthetic rubbers, such as silicone rubber, polyurethane synthetic rubber, polyamide synthetic rubber, silicon-based synthetic rubber, etc., preferably polyimide, polyphenylene sulfide, polyester, and polyurethane synthetic rubbers thereof, which are resistant to salt, ionic contaminants, water and organic molecules, and thus, the protective film layer serves as a barrier layer to prevent contamination.
In the research aspect of the membrane electrode, there are many domestic and foreign patents on the material, construction, assembly and the like of the membrane electrode, but few research patents or published papers relating to the material for sealing and protecting the membrane electrode are few.
EP0604683a1 describes a membrane electrode sealing device which is prone to mechanical damage of the membrane during assembly due to the thinness of the polymer electrolyte membrane, and which is subject to degradation and to breakage due to direct contact with the sealing material under pressure over a long period of time, resulting in poor sealing performance.
EP 1403949 a1 was used as a protective film layer on both sides of the CCM of the MEA, which is a polyurethane-based film having a thickness of 50 μm made of Walopur 4201AU polyurethane supplied from Epurex, Germany, and overlapped with the electrode layer in a very small area.
CN 1954450a describes a multi-layer membrane-electrode-assembly (ML-MEA) in which a bi-layer protective membrane layer coated with polyurethane Platilon U073(Epurex co., Walsrode, germany) is placed on both sides of an ionomer sheet.
CN1871731B describes a core assembly and a membrane electrode with sealing material, which uses thermoplastic polymer, elastic sealing body and thermosetting polymer as sealing material, the edge of the polymer electrolyte membrane is protected by the sealing material, and the gas diffusion layer uses the sealing material to isolate the cathode and anode reactants.
CN 104617310B discloses a method for preparing a fuel cell membrane electrode with a sealing frame, which comprises hot-pressing a polymer electrolyte membrane with a hot melt adhesive to two sides of the prepared polymer electrolyte membrane through a hot-pressing device, and sealing with the hot melt adhesive as a gasket material, wherein the hot melt adhesive has an adhesive overflow phenomenon during the use of the fuel cell, which may cause pollution to the membrane electrode, thereby affecting the performance of the cell; on the other hand, the sealing method requires special processing equipment and is long in curing time, thereby affecting the production efficiency.
In view of the above patent literature, the prior art has defects and the existing problems in the market are all the technical problems to be solved in the field, and the following improvements are specifically needed:
1. considering that the manufacturing and processing of the membrane electrode are all operated in a factory workshop, the provided membrane electrode sealing protective membrane material must be a solvent-free or water-based product according to the requirements of environmental protection laws and regulations;
2. according to the characteristics of membrane electrode manufacturing process, the frame of the membrane electrode of the fuel cell adopts a hot-press sealing forming process, so that the sealing protection membrane material provided by suppliers must be synchronous with the membrane electrode manufacturing process.
The specific requirements and key technical indexes of the existing market comprise: firstly, the water-based functional protective film material is colorless and transparent; coating the film on the surface of a membrane electrode and fusing the film electrode and the membrane electrode together by hot pressing, wherein the hot pressing temperature is less than or equal to 100 ℃; ③ the thickness of the dry film is between 50 +/-5 mu m; fourthly, interlayer adhesion: not less than 1.0 MPa; boiling resistance: the temperature is more than or equal to 90 ℃, and the RH is 100 percent for 2000 h; acid-resistant medium: 90 ℃ and 0.05M H 2 SO 4 And no foaming occurs after 2000h, and a paint film is intact.
In order to solve the technical problems, the application provides a sealing material for protecting a membrane electrode of a fuel cell and a preparation method thereof.
Disclosure of Invention
Based on the defects of the prior art, the invention provides a sealing material for protecting a membrane electrode of a fuel cell, and the higher the compactness of the sealing material is, the stronger the permeation of a medium is, so that the membrane electrode of the fuel cell has strong corrosion resistance and longer service life.
The invention also aims to provide a preparation method of the sealing material for protecting the membrane electrode of the fuel cell, which comprises the preparation methods of two sealing materials.
The technical scheme is as follows:
a thermosetting sealing material for protecting a membrane electrode of a fuel cell comprises the following components in parts by weight:
10-15 parts of epoxy resin emulsion;
15-20 parts of a poly (phenol-oxygen) resin emulsion;
20-25 parts of hot melt adhesive emulsion;
5-10 parts of elastomer resin emulsion;
5-10 parts of hydroxyl organic silicon resin emulsion;
3-8 parts of a low-temperature deblocking latent epoxy curing agent;
20-25 parts of a water-based blocked isocyanate curing agent;
0.1-0.5 part of water-based multifunctional auxiliary agent;
1-3 parts of a water-based silane coupling agent;
0.1-0.5 part of water-based defoaming agent;
0.5-1.0 part of water-based thickening agent;
an appropriate amount of deionized water (added according to the viscosity of the glue solution to adjust the gluing state).
The raw materials are uniformly mixed to obtain the sealing material for the membrane electrode of the thermosetting protective fuel cell, and the sealing material is processed on the membrane electrode of the fuel cell by a hot melting and curing process.
TABLE 1 specification requirements for sealing materials for thermosetting fuel cell membrane electrodes
Note: hot pressing fusion adopts a hot pressing machine; the thickness of the dry film is measured by a micrometer; the sizing process adopts a roller coating method; testing the interlayer adhesion according to GB 5210-85; boiling water resistance and acid water boiling test, and detecting according to GB/T1733-939.2 method B.
A sealing material for self-drying type fuel cell membrane electrode protection comprises the following components in parts by weight:
group A:
20-30 parts of epoxy resin emulsion;
25-35 parts of a poly (phenol-oxygen resin) emulsion;
5-15 parts of elastomer resin emulsion;
15-25 parts of hydroxyl organic silicon resin emulsion;
0.1-0.5 part of water-based multifunctional auxiliary agent;
1-3 parts of a water-based silane coupling agent;
0.1-0.5 part of water-based defoaming agent; (ii) a
0.5-1.0 part of water-based thickening agent
An appropriate amount of deionized water (added according to the viscosity of the glue solution to adjust the gluing state).
Group B:
20-25 parts of a water-based isocyanate curing agent.
The mass ratio of the group A to the group B is 4-5: 1 (wt).
The raw materials are uniformly mixed to obtain the sealing material for self-drying type fuel cell membrane electrode protection, and the sealing material is processed on the membrane electrode of the fuel cell by a normal temperature curing process.
TABLE 2 specification requirements for sealing materials for self-drying fuel cell membrane electrode protection
Note: interlayer adhesion is adopted; the thickness of the dry film is measured by a micrometer; the sizing process adopts a roller coating method; testing the interlayer adhesion according to GB 5210-85; boiling water resistance and acid water boiling test, and detecting according to GB/T1733-939.2 method B.
Wherein, the epoxy resin is 609(E-03) solid resin with large molecular weight, and in order to meet the requirement of environmental protection of products, the epoxy resin needs to be made into water; the water-based process comprises the steps of putting 40% of 609 solid resin into an emulsifying container, adding 10% of cosolvent, heating to a molten state, adding 10% of epoxy emulsifier (JT-801), 5% of protective colloid (KRN8060 silicone wax oil) and 50% of stabilizer, and adding 30% of deionized water; further, the mixture is emulsified under the action of high-speed shearing of an emulsifying machine to prepare epoxy resin emulsion with the solid content of 55 percent for standby.
The preparation method comprises the following steps of putting 40% of YP-50S solid resin into an emulsification container, adding 10% of cosolvent, heating to a molten state, adding 10% of epoxy emulsifier (JT-801), 5% of protective colloid (KRN8060 silicone wax oil) and 50% of stabilizer, and adding 30% of deionized water; further, the mixture is emulsified under the action of high-speed shearing of an emulsifying machine to prepare the polyphenoxy resin emulsion with the solid content of 55 percent for standby.
Wherein, 15 parts of 609 epoxy resin emulsion, 20 parts of YP-50S polyphenoxy resin emulsion, 25 parts of PU-2402 hot melt adhesive emulsion, 5 parts of PU-2540 elastomer resin emulsion, 10 parts of JH3013 hydroxyl organic silicon resin emulsion, 3 parts of HAA-1021 low-temperature deblocking latent epoxy curing agent, 20 parts of EMI-24 aqueous blocked isocyanate curing agent, 0.2 part of AMP-95 aqueous multifunctional auxiliary agent, 1 part of Z-6040 aqueous silane coupling agent, 0.3 part of BYK-044 aqueous defoaming agent, 0.5 part of ASE-60 aqueous thickening agent and a proper amount of deionized water (added according to the viscosity of glue solution to adjust the gluing state) are mixed uniformly to obtain the sealing material of the thermosetting protective fuel cell.
Wherein, 609 epoxy resin emulsion 30 parts, YP-50S polyphenoxy resin emulsion 30 parts, JH3013 hydroxyl organic silicon resin emulsion 20 parts, PU-2540 elastomer resin emulsion 10 parts, AMP-95 aqueous multifunctional auxiliary agent 0.2 parts, aqueous silane coupling agent 2 parts, BYK-044 aqueous defoaming agent 0.3 parts, ASE-60 aqueous thickening agent 0.5 parts and right amount of deionized water 7 parts; group B: 25 parts of N3100 aqueous isocyanate curing agent. The use ratio is as follows: and (3) uniformly mixing the raw materials according to the weight ratio of the group A to the group B of 4: 1 to obtain the sealing material for the self-drying type fuel cell membrane electrode protection.
Compared with the prior art, the sealing material for protecting the membrane electrode of the fuel cell and the preparation method thereof have the following beneficial effects: because the raw materials contain epoxy resin, poly phenol-oxygen resin with hydroxyl functional groups and hydroxyl organic silicon resin, and two low-temperature (80 ℃) deblocking type latent curing agents, namely HAA-1021 epoxy curing agent (curing temperature is 90 ℃) and EMI-24 blocking type isocyanate curing agent (deblocking temperature is 80 ℃), the synchronous curing reaction of the two functional groups (epoxy group and hydroxyl) is realized, the crosslinking density of the sealing protective film is obviously enhanced, and the film performance is greatly improved, such as the mechanical strength, adhesive force, flexibility, wear resistance, water resistance and corrosion resistance of the film, which all reach the best state, and the service life of the fuel cell is longer; the used raw materials are all water-based products, so the method is more environment-friendly and pollution-free.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in further detail below.
Wherein, the epoxy resin is 609 solid epoxy resin (E-03) with large molecular weight, and the preparation method of the aqueous emulsion comprises the following steps: adding a proper amount of cosolvent, a certain amount of epoxy emulsifier (JT-801) and protective colloid (KRN8060 silicone wax oil) into 609 epoxy resin in a molten state, adding the balance of deionized water, and preparing 609 epoxy resin emulsion with 50% of solid content for later use under the high-speed shearing action of an emulsifying machine;
the preparation method of the aqueous emulsion of the polyphenolic oxygen resin is that the polyphenolic oxygen resin is a daily-produced large-volume solid resin (YP-50S): YP-50S polyphenolic oxygen resin is in a molten state, then a proper amount of cosolvent, a certain amount of epoxy emulsifier (JT-801) and protective colloid (KRN8060 silicone wax oil) are added, and the balance of deionized water is added, so that YP-50S polyphenolic oxygen resin emulsion with 50% of solid content is prepared for standby application under the high-speed shearing action of an emulsifying machine;
the hot melt adhesive is an emulsion type polyurethane (PU-2402) product;
the elastomer resin is an emulsion type polyurethane (PU-2540) product;
the organic silicon resin is a hydroxyl-terminated methyl silicone oil emulsion (JH3013) product;
the epoxy curing agent is a low-temperature deblocking latent type (HAA-1021) powder product;
the isocyanate is a blocked latent curing agent (EMI-24) or a Bayer N3100 aqueous curing agent product.
Example 1
The embodiment provides a thermosetting sealing material for protecting a membrane electrode of a fuel cell, which comprises the following components in parts by mass: 609 epoxy resin emulsion 12 parts, YP-50S polyphenoxy resin emulsion 20 parts, PU-2540 elastomer resin emulsion 10 parts, PU-2402 hot melt adhesive emulsion 20 parts, JH3013 hydroxyl organosilicon emulsion 10 parts, HAA-1021 low temperature deblocking latent type epoxy curing agent 5 parts, EMI-24 water-based closed isocyanate curing agent 20 parts, AMP-95 water-based multifunctional additive 0.1 part, Z-6040 water-based silane coupling agent 1 part, BYK-044 water-based defoaming agent 0.4 part, ASE-60 water-based thickening agent 1.5 parts and a proper amount of deionized water (added according to the viscosity of the adhesive liquid to adjust the gluing state), and the raw materials are uniformly mixed to obtain the sealing material I for the membrane electrode of the heat-set type protective fuel cell.
Example 2
The embodiment provides a thermosetting sealing material for protecting a membrane electrode of a fuel cell, which comprises the following components in parts by mass: 609 epoxy resin emulsion 15 parts, YP-50S polyphenoxy resin emulsion 15 parts, PU-2402 hot melt adhesive emulsion 25 parts, PU-2540 elastomer resin emulsion 8 parts, JH3013 hydroxyl organosilicon emulsion 10 parts, HAA-1021 low temperature deblocking latent type epoxy curing agent 5 parts, EMI-24 aqueous blocked isocyanate curing agent 20 parts, AMP-95 aqueous multifunctional auxiliary agent 0.1 part, Z-6040 aqueous silane coupling agent 1 part, BYK-044 aqueous defoaming agent 0.4 part, RM-2020NPR aqueous thickening agent 0.5 part and a proper amount of deionized water (added according to the viscosity of glue solution to adjust the gluing state), and the raw materials are uniformly mixed to obtain the sealing material II of the membrane electrode of the thermosetting protective fuel cell.
Example 3
The embodiment provides a thermosetting sealing material for protecting a membrane electrode of a fuel cell, which comprises the following components in parts by mass: 609 epoxy resin emulsion 15 parts, YP-50S polyphenoxy resin emulsion 20 parts, PU-2402 hot melt adhesive emulsion 25 parts, PU-2540 elastomer resin emulsion 5 parts, JH3013 hydroxyl organosilicon emulsion 10 parts, HAA-1021 low temperature deblocking latent epoxy curing agent 3 parts, EMI-24 aqueous blocked isocyanate curing agent 20 parts, AMP-95 aqueous multifunctional additive 0.2 parts, Z-6040 aqueous silane coupling agent 1 part, BYK-044 aqueous defoaming agent 0.3 parts, ASE-60 aqueous thickening agent 0.5 parts and a proper amount of deionized water (added according to the viscosity of glue solution to adjust the gluing state), and the raw materials are uniformly mixed to obtain the sealing material III of the membrane electrode of the thermosetting protective fuel cell.
Table 3 was obtained by comparative tests on the sealing materials for a membrane electrode of a thermosetting protective fuel cell in the above three examples, and it is understood from the table that the sealing material for a membrane electrode of a thermosetting protective fuel cell in example 3 was prepared in a combination of formulations optimized in cost performance.
Table 3 comparative test results of sealing materials for membrane electrodes of thermosetting protective fuel cells of examples 1 to 3
Note: the boiling is carried out intermittently every day, and the cumulative time is shown in the table.
Example 4
The embodiment provides a sealing material for self-drying type protection of a membrane electrode of a fuel cell, which comprises the following components in parts by mass: group A: 609 epoxy resin emulsion 25 parts, YP-50S polyphenoxy resin emulsion 30 parts, JH3013 hydroxyl organosilicon emulsion 20 parts, PU-2540 elastomer resin emulsion 10 parts, AMP-95 water-based multifunctional auxiliary agent 0.1 part, Z-6040 water-based silane coupling agent 2 parts, ASE-60 water-based thickener 0.5 part, BYK-044 water-based defoamer 0.4 part and deionized water 12 parts; group B: 20 parts of N3100 aqueous isocyanate curing agent; the use ratio is as follows: and (3) uniformly mixing the raw materials to obtain the sealing material IV for the membrane electrode of the self-drying type protective fuel cell, wherein the ratio of the group A to the group B is 5: 1 (wt).
Example 5
The embodiment provides a sealing material for self-drying type protection of a membrane electrode of a fuel cell, which comprises the following components in parts by mass: group A: 609 epoxy resin emulsion 30 parts, YP-50S polyphenoxy resin emulsion 30 parts, JH3013 hydroxyl organosilicon emulsion 20 parts, PU-2540 elastomer resin emulsion 10 parts, AMP-95 water-based multifunctional auxiliary agent 0.2 parts, water-based silane coupling agent 2 parts, BYK-044 water-based defoaming agent 0.3 parts, ASE-60 water-based thickening agent 0.5 parts and a proper amount of deionized water 7 parts; group B: 25 parts of N3100 aqueous isocyanate curing agent. The use ratio is as follows: and (3) uniformly mixing the raw materials to obtain the sealing material V for the membrane electrode of the self-drying type protective fuel cell, wherein the ratio of the group A to the group B is 4: 1 (wt).
Example 6
The embodiment provides a sealing material for self-drying type protection of a membrane electrode of a fuel cell, which comprises the following components in parts by mass: group A: 609 epoxy resin emulsion 25 parts, YP-50S polyphenoxy resin emulsion 35 parts, JH3013 hydroxyl organosilicon emulsion 15 parts, PU-2540 elastomer resin emulsion 10 parts, AMP-95 water-based multifunctional auxiliary agent 0.2 parts, Z-6040 water-based silane coupling agent 2 parts, BYK-044 water-based defoaming agent 0.3 parts, ASE-60 water-based thickening agent 0.5 parts and a proper amount of deionized water 12 parts; group B: 25 parts of N3100 aqueous isocyanate curing agent. The use ratio is as follows: and (3) uniformly mixing the raw materials to obtain the sealing material VI for the membrane electrode of the self-drying type protective fuel cell, wherein the ratio of the group A to the group B is 4: 1 (wt).
The sealing materials of the self-drying protective fuel cell membrane electrode of the three examples are compared and tested to obtain table 4, and the formula combination with the optimized cost performance is the sealing material of the self-drying protective fuel cell membrane electrode of the example 5.
Table 4 examples 4 to 6 comparative test results of sealing materials for self-drying type fuel cell membrane electrode
Note: the boiling is carried out intermittently every day, and the cumulative time is shown in the table.
Compared with the prior art, the sealing material for protecting the membrane electrode of the fuel cell has the following beneficial effects: by comparing the product performances of the sealing materials with different curing and film-forming mechanisms in the table 3 and the table 4, although the boiling resistance (including acidic water) can meet the technical index requirements of the current market, the sealing materials of the thermosetting type protective fuel cell membrane electrode are superior to the sealing materials of the self-drying type protective fuel cell membrane electrode in the comparison of the mechanical properties, and the difference is in great relation with the crosslinking density after the coating film is cured; under the condition that the film thickness is the same or similar, the higher the crosslinking density of the film, namely the better the compactness of the film, the better the mechanical property, meanwhile, the higher the compactness of the film, the stronger the penetration of the anti-medium, which is directly related to the anti-corrosion performance of the film and the durability of the service life of the film, and the strong anti-corrosion performance of the film and the long service life of the film also lead the strong anti-corrosion performance and the long service life of the film of the fuel cell; the used raw materials are all water-based products, so the method is more environment-friendly and pollution-free.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. A seal material for protecting a membrane electrode assembly of a fuel cell, characterized in that: comprises epoxy resin emulsion, poly phenol-oxygen resin emulsion, hot melt adhesive emulsion, elastomer resin emulsion, hydroxyl organic silicon resin emulsion, curing agent and functional auxiliary agent.
2. The seal material for protecting a fuel cell membrane electrode assembly according to claim 1, characterized in that: the paint comprises the following components in parts by weight: 10-15 parts of epoxy resin emulsion, 15-20 parts of polyphenol oxygen resin emulsion, 20-25 parts of hot melt adhesive emulsion, 5-10 parts of elastomer resin emulsion, 5-10 parts of hydroxyl organic silicon resin emulsion, 3-8 parts of low-temperature deblocking latent epoxy curing agent, 20-25 parts of water-based blocked isocyanate curing agent, 0.1-0.5 part of water-based multifunctional additive, 1-3 parts of water-based silane coupling agent, 0.1-0.5 part of water-based defoaming agent, 0.5-1.0 part of water-based thickening agent and a proper amount of deionized water.
3. The seal material for protecting a fuel cell membrane electrode assembly according to claim 1, characterized in that: the paint comprises the following components in parts by weight: the component A comprises 20-30 parts of epoxy resin emulsion, 25-35 parts of polyphenol-oxygen resin emulsion, 5-15 parts of elastomer resin emulsion, 15-25 parts of hydroxyl organic silicon resin emulsion, 0.1-0.5 part of water-based multifunctional auxiliary agent, 1-3 parts of water-based silane coupling agent, 0.1-0.5 part of water-based defoaming agent, 0.5-1.0 part of water-based thickening agent and a proper amount of deionized water; the group B is 20-25 parts of a water-based isocyanate curing agent; the mass ratio of the group A to the group B is 4-5: 1 (wt).
4. The seal material for protecting a fuel cell membrane electrode assembly according to claim 2 or 3, characterized in that: the preparation method of the epoxy resin emulsion comprises the following steps: under the condition of melting epoxy resin, adding proper quantity of cosolvent, epoxy emulsifier and protective colloid, then adding the rest quantity of deionized water, and under the action of high-speed shearing of emulsifying machine making epoxy resin emulsion with 50% solid portion be made.
5. The seal material for protecting a fuel cell membrane electrode assembly according to claim 2 or 3, characterized in that: the preparation method of the poly (phenol-oxygen) resin emulsion comprises the following steps: under the condition of melting state of polyphenoxy resin, adding proper quantity of cosolvent, epoxy emulsifier and protective colloid, then adding the rest quantity of deionized water, and under the action of high-speed shearing of emulsifying machine making the polyphenoxy resin emulsion whose solid content is 50%.
6. The seal material for protecting a fuel cell membrane electrode assembly according to claim 2, characterized in that: the epoxy resin emulsion comprises 15 parts of epoxy resin emulsion, 20 parts of polyphenol oxygen resin emulsion, 25 parts of hot melt adhesive emulsion, 5 parts of elastomer resin emulsion, 10 parts of hydroxyl organic silicon resin emulsion, 3 parts of low-temperature deblocking latent epoxy curing agent, 20 parts of waterborne blocked isocyanate curing agent, 0.2 part of waterborne multifunctional auxiliary agent, 1 part of waterborne silane coupling agent, 0.3 part of waterborne defoamer, 0.5 part of waterborne thickener and a proper amount of deionized water.
7. The seal material for protecting a fuel cell membrane electrode assembly according to claim 3, characterized in that: group A: 30 parts of the epoxy resin emulsion, 30 parts of the polyphenol oxygen resin emulsion, 20 parts of the hydroxyl organic silicon resin emulsion, 10 parts of the elastomer resin emulsion, 0.2 part of the aqueous multifunctional additive, 2 parts of the aqueous silane coupling agent, 0.3 part of the aqueous defoaming agent, 0.5 part of the aqueous thickening agent and 7 parts of deionized water; group B: 25 parts of the water-based isocyanate curing agent; the mass ratio of the group A to the group B is 4: 1 (wt).
8. The method for producing a sealing material for protecting a membrane electrode of a fuel cell according to any one of claims 1 to 3, characterized in that: and uniformly mixing all the raw materials to obtain the sealing material.
9. The method of producing a sealing material for protecting a fuel cell membrane electrode assembly according to claim 2, characterized in that: the sealing material is processed on the membrane electrode of the fuel cell through a hot melting and curing process.
10. The method of producing a sealing material for protecting a fuel cell membrane electrode assembly according to claim 3, characterized in that: the sealing material is processed on the membrane electrode of the fuel cell by a normal-temperature curing process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210753733.7A CN115050987B (en) | 2022-06-28 | 2022-06-28 | Sealing material for protecting fuel cell membrane electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210753733.7A CN115050987B (en) | 2022-06-28 | 2022-06-28 | Sealing material for protecting fuel cell membrane electrode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115050987A true CN115050987A (en) | 2022-09-13 |
| CN115050987B CN115050987B (en) | 2024-06-14 |
Family
ID=83165169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210753733.7A Active CN115050987B (en) | 2022-06-28 | 2022-06-28 | Sealing material for protecting fuel cell membrane electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115050987B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000230113A (en) * | 1998-09-25 | 2000-08-22 | Shin Etsu Chem Co Ltd | Epoxy resin composition, laminate film and semiconductor apparatus using the same |
| JP2003138225A (en) * | 2001-11-01 | 2003-05-14 | Kansai Paint Co Ltd | Coating composition for primer |
| JP2004307556A (en) * | 2003-04-02 | 2004-11-04 | Auto Kagaku Kogyo Kk | Curable composition and sealing material composition |
| KR20060006600A (en) * | 2004-07-16 | 2006-01-19 | 삼성에스디아이 주식회사 | Adhesive composition for fabricating solid polymer fuel cell and fuel cell manufactured therefrom |
| KR100727742B1 (en) * | 2005-12-17 | 2007-06-13 | 제일모직주식회사 | Resin formulation of anisotropic conductive adhesive used blocked isocyanate and connection structure using the same |
| JP2007169550A (en) * | 2005-12-26 | 2007-07-05 | Dainippon Ink & Chem Inc | Composition for resin molding and fuel cell separator |
| CN102311612A (en) * | 2011-04-03 | 2012-01-11 | 广东生益科技股份有限公司 | Resin composition and resin coated copper foil made of same |
| CN107698740A (en) * | 2017-11-02 | 2018-02-16 | 合众（佛山）化工有限公司 | A kind of low form epoxy hardener and its epoxide terrace paint based on POSS |
| CN108410133A (en) * | 2018-03-16 | 2018-08-17 | 苏州生益科技有限公司 | The low flow prepreg of its preparation of resin combination and application |
| CN109810468A (en) * | 2019-01-25 | 2019-05-28 | 常熟生益科技有限公司 | A kind of compositions of thermosetting resin and prepreg and laminate using its preparation |
| CN111108169A (en) * | 2017-08-10 | 2020-05-05 | 日清纺化学株式会社 | One-pack type adhesive and fuel cell separator |
| CN112391122A (en) * | 2021-01-19 | 2021-02-23 | 泽铱(佛山)工业技术有限公司 | Titanium-based polymer alloy high-temperature-resistant anticorrosive paint and preparation method thereof |
| CN114316746A (en) * | 2022-01-06 | 2022-04-12 | 广东顺德大地缘新材料有限公司 | Water-based nano insulating paint and preparation method and application thereof |
-
2022
- 2022-06-28 CN CN202210753733.7A patent/CN115050987B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000230113A (en) * | 1998-09-25 | 2000-08-22 | Shin Etsu Chem Co Ltd | Epoxy resin composition, laminate film and semiconductor apparatus using the same |
| JP2003138225A (en) * | 2001-11-01 | 2003-05-14 | Kansai Paint Co Ltd | Coating composition for primer |
| JP2004307556A (en) * | 2003-04-02 | 2004-11-04 | Auto Kagaku Kogyo Kk | Curable composition and sealing material composition |
| KR20060006600A (en) * | 2004-07-16 | 2006-01-19 | 삼성에스디아이 주식회사 | Adhesive composition for fabricating solid polymer fuel cell and fuel cell manufactured therefrom |
| KR100727742B1 (en) * | 2005-12-17 | 2007-06-13 | 제일모직주식회사 | Resin formulation of anisotropic conductive adhesive used blocked isocyanate and connection structure using the same |
| JP2007169550A (en) * | 2005-12-26 | 2007-07-05 | Dainippon Ink & Chem Inc | Composition for resin molding and fuel cell separator |
| CN102311612A (en) * | 2011-04-03 | 2012-01-11 | 广东生益科技股份有限公司 | Resin composition and resin coated copper foil made of same |
| CN111108169A (en) * | 2017-08-10 | 2020-05-05 | 日清纺化学株式会社 | One-pack type adhesive and fuel cell separator |
| CN107698740A (en) * | 2017-11-02 | 2018-02-16 | 合众（佛山）化工有限公司 | A kind of low form epoxy hardener and its epoxide terrace paint based on POSS |
| CN108410133A (en) * | 2018-03-16 | 2018-08-17 | 苏州生益科技有限公司 | The low flow prepreg of its preparation of resin combination and application |
| CN109810468A (en) * | 2019-01-25 | 2019-05-28 | 常熟生益科技有限公司 | A kind of compositions of thermosetting resin and prepreg and laminate using its preparation |
| CN112391122A (en) * | 2021-01-19 | 2021-02-23 | 泽铱(佛山)工业技术有限公司 | Titanium-based polymer alloy high-temperature-resistant anticorrosive paint and preparation method thereof |
| CN114316746A (en) * | 2022-01-06 | 2022-04-12 | 广东顺德大地缘新材料有限公司 | Water-based nano insulating paint and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHUANG YANG 等: ""Synthesis of a phosphorus/nitrogen-containing compound based on maleimide and cyclotriphosphazene and its flame-retardant mechanism on epoxy resin"", 《POLYMER DEGRADATION AND STABILITY》, vol. 126, pages 9 - 16, XP029461558, DOI: 10.1016/j.polymdegradstab.2016.01.011 * |
| 彭桂荣 等: ""改性环氧树脂涂料的制备及性能研究"", 《热固性树脂》, vol. 27, no. 05, pages 22 - 26 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115050987B (en) | 2024-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101383404B (en) | Fluorine/hydrocarbon composite ion exchange film and preparation thereof | |
| US20060199059A1 (en) | Ion conductive polymer electrolyte and its membrane electrode assembly | |
| US20120122012A1 (en) | Fuel cell and method for manufacturing same | |
| CN109233715A (en) | The double-component epoxy adhesive and preparation method thereof of resistance to lithium-ion battery electrolytes | |
| EP1561255A2 (en) | Fuel cell gasket | |
| CN115050987B (en) | Sealing material for protecting fuel cell membrane electrode and preparation method thereof | |
| EP3200258B1 (en) | Composite membrane containing ion transfer polymer and method for preparing same | |
| CN114864989B (en) | Membrane electrode frame and preparation method thereof and membrane electrode | |
| CN112002923A (en) | Fuel cell module type frame membrane | |
| Pehlivan-Davis | Polymer Electrolyte Membrane (PEM) fuel cell seals durability | |
| CN108129747B (en) | Bipolar plate for flow battery and preparation and application thereof | |
| CN213278137U (en) | Fuel cell membrane electrode assembly | |
| CN114204089A (en) | Proton exchange composite membrane and continuous preparation method thereof | |
| CN113773542A (en) | Perfluorinated proton exchange membrane and preparation method and application thereof | |
| CN111224123B (en) | Preparation method of composite ion-conducting membrane, composite membrane and application thereof | |
| Arcella et al. | Fluoropolymers for sustainable energy | |
| CN112002924A (en) | Fuel cell membrane electrode assembly | |
| EP1374324A2 (en) | Fuel cell | |
| CN113372655B (en) | Ethylene propylene diene monomer rubber sealing material for hydrogen fuel cell, and preparation method and application thereof | |
| JP2004211038A (en) | Adhesive composition | |
| CN212874553U (en) | Fuel cell module type frame membrane | |
| KR100921278B1 (en) | Fluorine rubber coating plate and method for manufacturing the same | |
| CN110483822B (en) | Method for improving oxidation resistance chemical stability of proton exchange membrane | |
| CN110783575B (en) | Method of manufacturing planar membrane electrode assembly for fuel cell and planar membrane electrode assembly for fuel cell manufactured using the same | |
| JP4474837B2 (en) | Proton conducting material, proton conducting material membrane, and fuel cell |
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 |