CN114420947A - Silicon sulfide rubber injection molding material, integrated sealing membrane electrode, preparation method of integrated sealing membrane electrode and fuel cell - Google Patents
Silicon sulfide rubber injection molding material, integrated sealing membrane electrode, preparation method of integrated sealing membrane electrode and fuel cell Download PDFInfo
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- 238000007789 sealing Methods 0.000 title claims abstract description 156
- 239000012528 membrane Substances 0.000 title claims abstract description 146
- 238000001746 injection moulding Methods 0.000 title claims abstract description 76
- 239000012778 molding material Substances 0.000 title claims abstract description 68
- 239000000446 fuel Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920001971 elastomer Polymers 0.000 title claims description 140
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 title description 17
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 83
- 239000004945 silicone rubber Substances 0.000 claims abstract description 80
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920002545 silicone oil Polymers 0.000 claims abstract description 35
- 239000011787 zinc oxide Substances 0.000 claims abstract description 33
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000000741 silica gel Substances 0.000 claims abstract description 22
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000000806 elastomer Substances 0.000 claims description 124
- 238000009792 diffusion process Methods 0.000 claims description 82
- 239000007789 gas Substances 0.000 claims description 80
- 239000003054 catalyst Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000002347 injection Methods 0.000 claims description 30
- 239000007924 injection Substances 0.000 claims description 30
- -1 polymethylsiloxane Polymers 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 208000005156 Dehydration Diseases 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 6
- 238000009966 trimming Methods 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- ARGICNMLPHJXTP-UHFFFAOYSA-N [SiH4].C(=C)C(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O Chemical compound [SiH4].C(=C)C(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O ARGICNMLPHJXTP-UHFFFAOYSA-N 0.000 claims description 2
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- OUGKFJZADGTJRG-UHFFFAOYSA-N [SiH4].CC(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O Chemical compound [SiH4].CC(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O OUGKFJZADGTJRG-UHFFFAOYSA-N 0.000 claims 1
- 150000003609 titanium compounds Chemical class 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 235000010215 titanium dioxide Nutrition 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- JRFBNCLFYLUNCE-UHFFFAOYSA-N zinc;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Zn+2] JRFBNCLFYLUNCE-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- 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]
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a vulcanized silicone rubber injection molding material, an integrated sealing membrane electrode, a preparation method thereof and a fuel cell, wherein the preparation method of the vulcanized silicone rubber injection molding material comprises the following steps: mixing silica gel, silicone oil, an auxiliary agent, a cross-linking agent and a vulcanizing agent to obtain the vulcanized silicone rubber injection molding material; the auxiliary agent comprises nano zinc oxide and nano titanium dioxide. The addition of the auxiliary agent remarkably improves the tolerance of the vulcanized silicone rubber injection molding material in high-humidity high-temperature and acidic environments, and the injection molding material used as a membrane electrode can meet the requirement of a commercial vehicle fuel cell on sealing property, thereby further prolonging the service life of the commercial vehicle fuel cell.
Description
Technical Field
The invention belongs to the technical field of fuel cells for new energy vehicles, and particularly relates to a vulcanized silicone rubber injection molding material, an integrated sealing membrane electrode, a preparation method of the integrated sealing membrane electrode and a fuel cell.
Background
The hydrogen fuel cell directly converts chemical energy into electric energy by utilizing the reaction of hydrogen and oxygen, and is widely applied to automobiles as the proton exchange membrane fuel cell has the characteristics of low working temperature, quick start, high power density, mature application and the like. However, the durability of the current commercial vehicle hydrogen fuel cell is poor, the average service life is 15000 hours, and the service life requirement comparable to that of an internal combustion engine cannot be achieved, so that the service life is prolonged, and the service life is one of the most important problems in popularization and application of the commercial vehicle hydrogen fuel cell.
The membrane electrode is an important component of a commercial vehicle hydrogen fuel cell, is a place for generating electrochemical reaction, is compared with a chip of the fuel cell, and has the cost accounting for more than 60 percent of the cost of the fuel cell, so the cost and the service life of the membrane electrode directly determine the cost and the service life of the fuel cell. In order to ensure that hydrogen fuel and oxidant air in the proton exchange membrane fuel cell can be respectively arranged on the surfaces of two sides of the membrane electrode without generating a turn, the sealing technology around the membrane electrode is also very important besides the requirement on the self-sealing property of the membrane electrode, and the performance and the durability of the cell are directly influenced. At present, the membrane electrode seal mainly comprises two plastic frames and injection molding integrated seal.
CN107534166A discloses a sealing member for solid polymer electrolyte fuel cell, which is formed by arranging a frame around the periphery of a membrane electrode assembly, bonding (or hot pressing) the frame and a proton exchange membrane together, and injecting and sealing a flowable sealing material by using through holes on the frame, and has good integration effect and high production efficiency.
CN112103542A discloses a preparation device and a preparation method of an integrated membrane electrode, wherein an electrode product is placed in a lower die, and then injection molding is carried out from an upper die to a positioning concave cavity, so that the processing of the electrode product is completed, the automatic production of the membrane electrode is realized, and the labor cost is low; and the edge sealing is carried out on the electrode product by using an injection molding mode, the sealing effect of the finished product is good, the edge sealing is not easy to lose effectiveness, and the structure of the membrane electrode is stable.
CN112310431A discloses an elastomeric cell frame for a fuel cell, a method of manufacturing the same, and a unit cell, using an elastomeric cell frame for a fuel cell, comprising: a membrane electrode assembly including an electrolyte membrane and a pair of catalyst layers disposed at both sides of the electrolyte membrane, respectively, and a pair of gas diffusion layers disposed at both sides of the membrane electrode assembly; an elastomeric cell frame surrounding an outer edge of the membrane electrode assembly. The overlapping portions of the membrane electrode assembly and the elastic body frame are thermally melt-bonded by applying a hot press to the overlapping portions, whereby the membrane electrode assembly and the elastic body frame are integrated with each other to constitute an integrated membrane electrode. The method can reduce material cost, save adhesive coating process and sealing member forming process, and improve production efficiency; the cell distance can be reduced, the weight is reduced, and the volume/mass power of the fuel cell stack is improved.
The above documents are all based on the improvement of the integrated membrane electrode on the aspect of mold design, the problem of air tightness of the membrane electrode is solved, the sealing effect of the finished product is good, the continuous and rapid production is realized, and the production efficiency is further improved. However, the problems of attack of precipitates of the injection molding material on a proton membrane and a catalyst in an aging process, water repellency of an integrated membrane electrode and the like are not considered, and the influence on the durability and the service life of the fuel cell of the commercial vehicle is not considered.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the vulcanized silicone rubber injection molding material, the integrated sealing membrane electrode, the preparation method thereof and the fuel cell, the tolerance of the vulcanized silicone rubber injection molding material under high-humidity high-temperature and acidic environments is obviously improved by adding the auxiliary agent, the integrated sealing membrane electrode is suitable for being used as the injection molding material of the membrane electrode in the fuel cell of the commercial vehicle, the air tightness and the durability of the membrane electrode can be obviously improved, the requirement of the fuel cell of the commercial vehicle on the sealing property is met, and the service life of the fuel cell of the commercial vehicle is further prolonged.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a vulcanized silicone rubber injection molding material, the method comprising:
mixing silica gel, silicone oil, an auxiliary agent, a cross-linking agent and a vulcanizing agent, and reacting to obtain the vulcanized silicone rubber injection molding material;
the auxiliary agent comprises nano zinc oxide and nano titanium dioxide.
The prepared vulcanized silicone rubber is room temperature vulcanized silicone Rubber (RTV), nano zinc oxide is used as an auxiliary agent and is dispersed and filled into the silicone rubber, nano zinc oxide particles are adsorbed on the surface of the silicone rubber to wrap silicon hydroxyl (O-Si-R) at the tail end of the silicone rubber, and the movement of polymer molecular chains is limited, so that the silicone rubber is difficult to generate tripping degradation reaction and hydrolysis reaction caused by the hydroxyl at the tail end, the breakage of the silicon hydroxyl at the tail end of the silicone rubber in a damp and hot environment is inhibited, and the thermal stability of the room temperature vulcanized silicone rubber is improved.
Meanwhile, the nano titanium dioxide is added as an acid-resistant auxiliary agent, and the nano titanium dioxide has strong adhesive force and good chemical stability in an acid-base environment, and is dispersed in the room-temperature vulcanized silicone rubber, so that the acid resistance of the silicone rubber can be effectively improved. By adding the auxiliary agent, the tolerance of the vulcanized silicone rubber in high humidity and high temperature and acidic environment is improved. Therefore, the silicon sulfide rubber material provided by the invention is suitable for being used as a membrane electrode injection molding material, and the stability and durability of the injection molding material under the working environment (high temperature, high humidity and acidity) of a fuel cell are improved.
The addition of the auxiliary agent remarkably improves the tolerance of the vulcanized silicone rubber injection molding material in high-humidity high-temperature and acidic environments, and the injection molding material serving as a membrane electrode can meet the requirement of a vehicle fuel cell on sealing property, thereby further prolonging the service life of the commercial vehicle fuel cell. In addition, the auxiliary agent in the invention can also comprise nano aluminum oxide and/or nano calcium oxide.
As a preferred technical scheme of the present invention, the preparation method specifically comprises:
(1) mixing the silica gel and the silica oil, adding an auxiliary agent, and then sequentially performing dispersion treatment and dehydration treatment to obtain a base material;
(2) and after mixing the base material and the cross-linking agent, adding the vulcanizing agent to react to obtain the vulcanized silicone rubber injection molding material.
Preferably, the silica gel comprises any one of polymethylsiloxane, α, ω -dihydroxypolydimethylsiloxane or polydimethylsiloxane, and more preferably hydroxyl-terminated polydimethylsiloxane.
The silica gel in the present invention may be polymethylsiloxane containing alkoxy or other active groups, α, ω -dihydroxypolydimethylsiloxane, polydimethylsiloxane, and most preferably polydimethylsiloxane end-capped with hydroxyl groups.
Preferably, the silicone oil comprises any one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil and methyl vinyl silicone oil or the combination of at least two of the methyl silicone oil, the ethyl silicone oil, the phenyl silicone oil and the methyl hydrogen-containing silicone oil.
Preferably, the silica gel and the silicone oil are mixed under stirring.
Preferably, the silica gel and the silica oil are mixed for 30-60 min, such as 30min, 32min, 35min, 38min, 40min, 42min, 45min, 48min, 50min, 52min, 55min, 58min or 60min, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the temperature of the mixture of the silica gel and the silica oil is 100 to 130 ℃, and for example, 100 ℃, 102 ℃, 105 ℃, 108 ℃, 110 ℃, 112 ℃, 115 ℃, 118 ℃, 120 ℃, 122 ℃, 125 ℃, 128 ℃ or 130 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mixing speed of the silica gel and the silica oil is 200 to 500rpm/min, such as 200rpm/min, 220rpm/min, 250rpm/min, 280rpm/min, 300rpm/min, 320rpm/min, 350rpm/min, 380rpm/min, 400rpm/min, 420rpm/min, 450rpm/min, 480rpm/min or 500rpm/min, but is not limited to the enumerated values, and other non-enumerated values within the range are also applicable.
Preferably, the silica gel is added in an amount of 80 to 100 parts, for example, 80 parts, 82 parts, 85 parts, 90 parts, 92 parts, 95 parts, 98 parts or 100 parts, but not limited to the recited values, and other values not recited within the range of values are also applicable.
The silica gel preferably has a viscosity of 15000 to 40000 mPas, for example 15000 mPas, 20000 mPas, 25000 mPas, 30000 mPas, 35000 mPas or 40000 mPas, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the silicone oil is added in an amount of 5 to 10 parts, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, but not limited to the recited values, and other values not recited within the range of the values are also applicable.
The viscosity of the silicone oil is preferably 100 to 400 mPas, and may be, for example, 100 mPas, 150 mPas, 200 mPas, 250 mPas, 300 mPas, 350 mPas or 400 mPas, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, an additive is also added during the dispersion treatment.
Preferably, the additive comprises nano calcium carbonate or white carbon black.
Preferably, the dispersion treatment is carried out under stirring conditions.
Preferably, the time of the dispersion treatment is 1 to 2 hours, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours or 2 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the stirring speed of the dispersion treatment is 200 to 500rpm/min, for example, 200rpm/min, 220rpm/min, 250rpm/min, 280rpm/min, 300rpm/min, 320rpm/min, 350rpm/min, 380rpm/min, 400rpm/min, 420rpm/min, 450rpm/min, 480rpm/min or 500rpm/min, but is not limited to the enumerated values, and other values not enumerated within the range are also applicable.
In the invention, the dispersion treatment process adopts stirring by a stirring paddle or a power mixer.
Preferably, the temperature of the dispersion treatment is 100 to 130 ℃, for example, 100 ℃, 102 ℃, 105 ℃, 108 ℃, 110 ℃, 112 ℃, 115 ℃, 118 ℃, 120 ℃, 122 ℃, 125 ℃, 128 ℃ or 130 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the additive is added in an amount of 80 to 150 parts, for example, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts or 150 parts, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the nano zinc oxide is added in an amount of 0.5 to 2 wt%, for example, 0.5 wt%, 0.7 wt%, 0.9 wt%, 1.1 wt%, 1.3 wt%, 1.5 wt%, 1.7 wt%, 1.9 wt% or 2 wt%, based on 100 wt% of the mass fraction of the vulcanized silicone rubber injection molding material, but is not limited to the enumerated values, and other unrecited values within the range of the enumerated values are also applicable.
The addition amount of the nano zinc oxide is limited to be 0.5-2 wt%, and when the addition amount is less than 0.5 wt%, the thermal stability of the vulcanized silicone rubber cannot be obviously improved, because the addition amount of the nano zinc oxide is too low, the silicon hydroxyl at the tail end of the silicone rubber cannot be fully wrapped, the movement of a polymer molecular chain cannot be limited, and thus the tripping degradation reaction and the hydrolysis reaction caused by the silicon rubber hydroxyl at the tail end cannot be inhibited; when the amount is more than 2 wt%, the elasticity of the vulcanized silicone rubber is lowered, which is disadvantageous for injection molding in the subsequent membrane electrode preparation process.
Preferably, the nano titanium dioxide is added in an amount of 0.1 to 3 wt%, for example, 0.1 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.7 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.7 wt% or 3 wt%, based on 100 wt% of the mass fraction of the vulcanized silicone rubber injection molding material, but is not limited to the enumerated values, and other non-enumerated values within the range of values are also applicable.
The addition amount of the nano titanium dioxide is limited to be 0.1-3 wt%, and when the addition amount is less than 0.1 wt%, the acid resistance of the vulcanized silicone rubber cannot be improved, because the nano titanium dioxide is too small to be uniformly dispersed in the vulcanized silicone rubber, the acid resistance of the vulcanized silicone rubber cannot be effectively improved; when the amount is more than 3 wt%, the elasticity of the vulcanized silicone rubber is lowered, which is disadvantageous for injection molding in the subsequent membrane electrode preparation process.
Preferably, the dehydration treatment is performed under stirring conditions.
Preferably, the stirring speed of the dehydration treatment is 50 to 120rpm/min, for example, 50rpm/min, 60rpm/min, 70rpm/min, 80rpm/min, 90rpm/min, 100rpm/min, 110rpm/min or 1200rpm/min, but is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
Preferably, the temperature of the dehydration treatment is 100 to 130 ℃, for example, 100 ℃, 102 ℃, 105 ℃, 108 ℃, 110 ℃, 112 ℃, 115 ℃, 118 ℃, 120 ℃, 122 ℃, 125 ℃, 128 ℃ or 130 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time of the dehydration treatment is 1.5 to 3 hours, for example, 1.5 hours, 1.7 hours, 1.9 hours, 2.1 hours, 2.3 hours, 2.5 hours, 2.7 hours, 2.9 hours or 3 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the stirring speed is reduced to 50-120 rpm/min, and a vacuum valve is opened for dehydration treatment.
In a preferred embodiment of the present invention, the crosslinking agent includes any one or a combination of at least two of methyltributanone oxime silane, vinyl tributone oxime silane, triallyl isocyanurate, vinyl triethoxysilane, an alkoxysilane compound, or a partially hydrolyzed polycondensate of an alkoxysilane compound.
Preferably, the binder and the crosslinking agent are mixed under stirring.
Preferably, the temperature of the binder and the cross-linking agent is 20 to 30 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the binder and the cross-linking agent are mixed for 10-20 min, such as 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or 20min, but not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the stirring speed for mixing the base material and the cross-linking agent is 50-120 rpm/min, such as 50rpm/min, 60rpm/min, 70rpm/min, 80rpm/min, 90rpm/min, 100rpm/min, 110rpm/min or 1200rpm/min, but is not limited to the enumerated values, and other non-enumerated values in the range are also applicable.
Preferably, the crosslinking agent is added in an amount of 3 to 7 parts, for example, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, or 7 parts, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the binder and cross-linker are mixed under vacuum conditions.
Preferably, the reaction in step (2) is carried out under stirring conditions;
preferably, a coupling agent is also added during the reaction in step (2).
Preferably, the coupling agent comprises any one of KH-550, KH-560, KH-570, KH-792, DL-602, or DL-171, or a combination of at least two thereof.
Preferably, the sulphurising agent comprises any one or a combination of at least two of DCP, HC-6, H-850, H-101 or HC-750.
Preferably, the coupling agent is added in an amount of 1 to 3 parts, for example, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.3 parts, 2.5 parts, 2.8 parts or 3 parts, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the vulcanizing agent is added in an amount of 1 to 5 parts, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts, but not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the process of the reaction in step (2) is carried out under vacuum.
Preferably, the reaction in step (2) is carried out under stirring.
Preferably, the reaction time in step (2) is 10-30 min, such as 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction in step (2) is stirred at a speed of 200 to 500rpm/min, such as 200rpm/min, 220rpm/min, 250rpm/min, 280rpm/min, 300rpm/min, 320rpm/min, 350rpm/min, 380rpm/min, 400rpm/min, 420rpm/min, 450rpm/min, 480rpm/min or 500rpm/min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the reaction temperature in step (2) is 20 to 30 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, in the step (2), after the reaction process is finished, a catalyst is further added to perform a stirring reaction to obtain the vulcanized silicone rubber injection molding material.
Preferably, the catalyst comprises any one of dibutyltin dilaurate, Kat245 or an organotitanium compound or a combination of at least two thereof.
Preferably, the reaction is stirred under vacuum after the catalyst is added.
Preferably, the time for stirring the catalyst for reaction is 20-40 min, such as 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min or 40min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the catalyst is stirred at a speed of 200 to 500rpm/min, such as 200rpm/min, 220rpm/min, 250rpm/min, 280rpm/min, 300rpm/min, 320rpm/min, 350rpm/min, 380rpm/min, 400rpm/min, 420rpm/min, 450rpm/min, 480rpm/min or 500rpm/min, but not limited to the enumerated values, and other values not enumerated within the range are equally applicable.
Preferably, the temperature of the catalyst for stirring reaction is 20-30 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the catalyst is added in an amount of 0.1 to 0.7 parts, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part or 0.7 part, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the catalyst is present in a mass fraction of 0.1 to 1 wt.%, for example 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.% or 1 wt.%, but not limited to the recited values, and other values not recited within this range are equally applicable.
As a preferable technical solution of the present invention, the preparation method comprises:
(1) stirring and mixing 80-100 parts of silica gel with the viscosity of 15000-40000 mPas and 5-10 parts of silicone oil with the viscosity of 100-400 mPas for 30-60 min at the rotating speed of 200-500 rpm/min and the temperature of 100-130 ℃;
(2) adding nano zinc oxide, nano titanium dioxide and an additive into the mixture obtained in the step (1) at a rotating speed of 200-500 rpm/min and a temperature of 100-130 ℃ for stirring dispersion treatment for 1-2 h, wherein the addition amount of the additive is 80-150 parts, the addition amount of the nano zinc oxide is 0.5-2 wt% and the addition amount of the nano titanium dioxide is 0.1-3 wt% based on 100 wt% of the vulcanized silicone rubber injection molding material, then reducing the stirring speed to 50-120 rmp/min, and dehydrating the mixture obtained in the step (2) at a temperature of 100-130 ℃ for 1.5-3 h to obtain a base material;
(3) adding 3-7 parts of cross-linking agent into the base material obtained in the step (2), stirring and mixing for 10-20 min at the rotating speed of 50-120 rpm/min and at the temperature of 20-30 ℃ under vacuum conditions, then adding 1-3 parts of coupling agent and 1-5 parts of vulcanizing agent, and reacting for 10-30 min at the rotating speed of 200-500 rpm/min and at the temperature of 20-30 ℃ under vacuum conditions;
(4) and (3) adding 0.1-0.7 part of catalyst with the mass fraction of 0.1-1 wt% into the mixture obtained in the step (3), and carrying out stirring reaction for 20-40 min at the rotating speed of 200-500 rpm/min and at the temperature of 20-30 ℃ under vacuum conditions to obtain the vulcanized silicone rubber injection molding material.
In the invention, the preparation process of the vulcanized silicone rubber injection molding material is carried out in a dust-free environment.
In a second aspect, the invention provides a vulcanized silicone rubber injection molding material, which is prepared by the preparation method of the first aspect.
In a third aspect, the invention provides an integrated seal membrane electrode, which comprises a proton exchange membrane, and a cathode and an anode on two sides of the proton exchange membrane, wherein a cathode elastomer seal frame is arranged around the cathode, an anode elastomer seal frame is arranged around the anode, the cathode elastomer seal frame and the anode elastomer seal frame are asymmetrically arranged, and the anode, the proton exchange membrane and the cathode are sealed into a whole through the anode elastomer seal frame and the cathode elastomer seal frame.
The anode elastomer sealing frame and the cathode elastomer sealing frame are both prepared from the vulcanized silicone rubber injection molding material in the second aspect.
The anode elastic sealing frame and the cathode elastic sealing frame are in a shape of Chinese character 'hui', only the peripheries of the anode and the cathode are respectively coated, so that the anode, the proton exchange membrane and the cathode are sealed into a whole, and the middle areas of the surfaces of the anode and the cathode are exposed.
The elastomer sealing frame of the membrane electrode in the vehicle fuel cell is prepared by adopting the vulcanized silicone rubber injection molding material provided by the second aspect, so that the elastomer sealing frame can be ensured to have excellent tolerance in a high-humidity high-temperature and acidic cell working environment, the main chain of vulcanized silicone rubber can be effectively prevented from being damaged in the high-humidity high-temperature and acidic environment, and silicon ions separated out can damage a proton exchange membrane and a catalyst layer, so that the durability and the stability of the membrane electrode are improved, and the service life of the commercial vehicle fuel cell is further prolonged.
In addition, the cathode elastomer sealing frame and the anode elastomer sealing frame adopt asymmetric design, so that water generated by the cathode can be effectively discharged in time, and the cathode elastomer sealing frame is prevented from being separated from the cathode gas diffusion layer under a high-humidity environment to influence the air tightness of the membrane electrode.
The integrated sealing membrane electrode provided by the invention is 1.2A/cm2Under the current density, the voltage attenuation is only 5% after 3000h operation, and the durability is improved by 7% compared with the conventional membrane electrode.
In a preferred embodiment of the present invention, the cathode includes a cathode catalyst layer and a cathode gas diffusion layer which are sequentially stacked on the surface of the proton exchange membrane.
Preferably, the anode includes an anode catalyst layer and an anode gas diffusion layer which are sequentially stacked from the surface of the proton exchange membrane.
Preferably, the width of the cathode elastomer sealing frame covering the edge of the cathode gas diffusion layer is 0.05-3 mm, for example, 0.05mm, 0.1mm, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm or 3mm, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the width of the anode elastomer sealing frame covering the edge of the anode gas diffusion layer is 0.05-3 mm, for example, 0.05mm, 0.1mm, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm or 3mm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In the invention, the cathode elastomer sealing frame and the anode elastomer sealing frame are subjected to edge locking design to ensure that the membrane electrode cannot leak gas and blow-by gas during working, and part of the membrane electrode is wrapped in an elastomer frame consisting of the cathode elastomer sealing frame and the anode elastomer sealing frame.
Preferably, the contact area of the cathode elastomer sealing frame and the surface of the cathode gas diffusion layer is recorded as S1The contact area of the anode elastomer sealing frame and the surface of the anode gas diffusion layer is marked as S2Wherein S is1＞S2。
In the present invention, the contact area refers to the area of the cathode elastomer sealing frame covered on the surface of the cathode gas diffusion layer, or the area of the anode elastomer sealing frame covered on the surface of the anode gas diffusion layer. The contact area of the cathode elastomer sealing frame and the cathode gas diffusion layer is larger than that of the anode elastomer sealing frame and the anode gas diffusion layer, because the cathode can be generated along with water in the reaction process, the contact area of the cathode elastomer sealing frame to the cathode gas diffusion layer is larger, and the cathode elastomer sealing frame and the cathode gas diffusion layer can be prevented from being separated in a high-humidity and high-heat environment to influence the air tightness.
Preferably, the cathode elastomer sealing frame is 0.1 to 2mm higher than the cathode gas diffusion layer, for example, 0.1mm, 0.12mm, 0.14mm, 0.16mm, 0.18mm, 1mm, 1.2mm, 1.4mm, 1.6mm, 1.8mm or 2mm, but not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the anode elastomer sealing frame is 0.1-2 mm higher than the anode gas diffusion layer; for example, it may be 0.1mm, 0.12mm, 0.14mm, 0.16mm, 0.18mm, 1mm, 1.2mm, 1.4mm, 1.6mm, 1.8mm or 2mm, but it is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the thickness of the cathode elastomer sealing frame is recorded as H1The thickness of the anode elastomer sealing frame is marked as H2Wherein H is1＜H2。
In the present invention, the cathode elastomer sealing frame has a small thickness, because the thin cathode elastomer sealing frame can rapidly discharge water generated from the cathode, preventing the water from staying and gathering.
In the invention, a cathode plate is arranged on one side of the cathode gas diffusion layer away from the cathode catalyst layer, an anode plate is arranged on one side of the anode gas diffusion layer away from the anode catalyst layer, and a convex sealing strip and a gas conveying channel for sealing the cathode plate and the anode plate are respectively arranged at two ends of the cathode elastomer sealing frame and the anode elastomer sealing frame.
Preferably, the area of the proton exchange membrane is marked as S3And the area of the catalyst layer is marked as S4And the area of the diffusion layer is marked as S5Wherein S is3＞S4＝S5。
The area of the proton exchange membrane is limited to be larger than the areas of the catalyst layer and the diffusion layer, so that the diffusion layers on two sides of the proton exchange membrane are prevented from contacting to cause a short circuit phenomenon. In addition, the areas of the catalyst layer and the diffusion layer should be larger than the active area of the membrane electrode.
In a fourth aspect, the present invention provides a method for preparing the integrated sealed membrane electrode of the third aspect, wherein the method for preparing the integrated sealed membrane electrode comprises:
and sequentially laminating the anode, the proton exchange membrane and the cathode in an injection mold, then injecting a vulcanized silicone rubber injection molding material into the injection mold to form an elastomer sealing frame, and curing to obtain the integrated sealing membrane electrode.
In the invention, an anode gas diffusion layer, an anode catalyst layer, a proton exchange membrane, a cathode catalyst layer and a cathode gas diffusion layer are sequentially stacked and placed in an injection mold. In addition, the preparation process of the integrated sealed membrane electrode is carried out in a dust-free environment. Meanwhile, the preparation method of the integrated sealed membrane electrode provided by the invention is simple and convenient to operate, reduces the influence of a large number of human factors on the preparation of the integrated membrane electrode, improves the quality and consistency of the membrane electrode, has quick production beat, reduces the labor input cost, and improves the working efficiency
In a preferred embodiment of the present invention, the injection mold is preheated to 70 to 140 ℃, and then the injection material is injected into the injection mold, and the injection mold may be, for example, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or 140 ℃, but the injection mold is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
In the invention, the device for preheating the injection mold can be an oven, a muffle furnace or an infrared heating device.
Preferably, the curing time is 5-10 min, such as 5min, 6min, 7min, 8min, 9min or 10min, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, after the curing, mold opening and trimming are further performed in sequence to obtain the integrated sealing film electrode.
After the integrated sealing membrane electrode is taken out of the injection mold, the invention trims and removes redundant gates, dead heads and flash, and obtains the integrated sealing membrane electrode finished product.
In a fifth aspect, the present invention provides a fuel cell comprising the integrated sealed membrane electrode of the third aspect.
Compared with the prior art, the invention has the beneficial effects that:
(1) the addition of the auxiliary agent remarkably improves the tolerance of the vulcanized silicone rubber injection molding material in high-humidity high-temperature and acidic environments, and is suitable for being used as an injection molding material of a membrane electrode in a fuel cell of a commercial vehicle;
(2) the elastic sealing frame of the membrane electrode in the vehicle fuel cell is prepared by adopting the vulcanized silicone rubber injection molding material, so that the main chain of the vulcanized silicone rubber can be effectively prevented from being damaged under high-humidity high-temperature and acidic working environments, and the precipitated silicon ions can damage a proton exchange membrane and a catalyst layer, thereby improving the durability and stability of the membrane electrode and further prolonging the service life of the commercial vehicle fuel cell;
(3) the cathode elastomer sealing frame and the anode elastomer sealing frame are designed asymmetrically, so that water generated by the cathode can be effectively discharged in time, the cathode elastomer sealing frame is prevented from being separated from the cathode gas diffusion layer under a high-humidity environment to influence the air tightness, and the stability and the service life of the commercial vehicle fuel cell are further improved.
Drawings
Fig. 1 is a schematic cross-sectional view of an integrated sealed membrane electrode according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of an anode gas diffusion layer and an anode elastic sealing frame according to an embodiment of the present invention.
Fig. 3 is a schematic structural diagram of a cathode gas diffusion layer and a cathode elastic sealing frame according to an embodiment of the present invention.
FIG. 4 is a graph of tensile strength as a function of time for vulcanized silicone rubber materials provided in example 1 and comparative example 1 under ambient conditions of temperature of 90 ℃ and pH 2.
Wherein, 1 is a proton exchange membrane; 2-an anode catalyst layer; 3-an anode gas diffusion layer; 4-anode elastomer sealing frame; 5, an anode plate; 6-cathode catalyst layer; 7-cathode gas diffusion layer; 8-cathode elastomer sealing frame; 9-cathode plate.
Detailed Description
It is to be understood that in the description of the present invention, the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be taken as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
It should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "disposed," "connected" and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In a specific embodiment, the invention provides an integrated sealed membrane electrode, as shown in fig. 1, the integrated sealed membrane electrode includes a proton exchange membrane 1, and a cathode and an anode on both sides of the proton exchange membrane 1, a cathode elastomer sealing frame 8 is disposed around the cathode, an anode elastomer sealing frame 4 is disposed around the anode, the cathode elastomer sealing frame 8 and the anode elastomer sealing frame 4 are asymmetrically disposed, and the anode, the proton exchange membrane 1 and the cathode are sealed and integrated by the anode elastomer sealing frame 4 and the cathode elastomer sealing frame 8. The anode elastomer sealing frame 4 and the cathode elastomer sealing frame 8 are both prepared from vulcanized silicone rubber injection molding materials.
Further, the cathode includes a cathode catalyst layer 6 and a cathode gas diffusion layer 7 laminated in this order from the surface of the proton exchange membrane 1; the anode includes an anode catalyst layer 2 and an anode gas diffusion layer 3 which are sequentially stacked from the surface of the proton exchange membrane 1.
In the invention, the cathode elastomer sealing frame 8 and the anode elastomer sealing frame 4 are designed to be locked, so that the membrane electrode can not leak gas and blow-by gas during working, and part of the membrane electrode is wrapped in an elastomer frame consisting of the cathode elastomer sealing frame 8 and the anode elastomer sealing frame 4.
Further, as shown in fig. 2 and 3, the contact area of the cathode elastomer sealing frame 8 and the cathode gas diffusion layer 7 is denoted by S1The anode elastomer sealing frame 4 and the anode gas diffusion layer 3Is denoted as S2Wherein S is1＞S2(ii) a The thickness of the cathode elastomer sealing frame 8 is marked as H1The thickness of the anode elastomer sealing frame 4 is marked as H2Wherein H is1＜H2。
In the invention, a cathode plate 9 is arranged on one side of the cathode gas diffusion layer 7 away from the cathode catalyst layer 6, an anode plate 5 is arranged on one side of the anode gas diffusion layer 3 away from the anode catalyst layer 2, and a convex sealing strip and a gas conveying channel for sealing with the cathode plate 9 and the anode plate 5 are respectively arranged at two ends of the cathode elastomer sealing frame 8 and the anode elastomer sealing frame 4.
Further, the cathode catalyst layer 6 and the anode catalyst layer 2 are collectively called a catalyst layer, the cathode gas diffusion layer 7 and the anode gas diffusion layer 3 are collectively called a diffusion layer, and the area of the proton exchange membrane 1 is denoted by S3And the area of the catalyst layer is marked as S4And the area of the diffusion layer is marked as S5Wherein S is3＞S4＝S5。
Example 1
The embodiment provides a preparation method of a vulcanized silicone rubber injection molding material, which comprises the following steps:
(1) 80 parts of alpha, omega-dihydroxy polydimethylsiloxane having a viscosity of 15000 mPas and 5 parts of methyl silicone oil having a viscosity of 100 mPas are stirred and mixed for 30min at a rotation speed of 500rpm/min and a temperature of 100 ℃;
(2) adding nano zinc oxide, nano titanium dioxide and nano calcium carbonate into the mixture obtained in the step (1) at the rotating speed of 500rpm/min and the temperature of 100 ℃ for stirring dispersion treatment for 1h, wherein the adding amount of the nano calcium carbonate is 80 parts, the adding amount of the nano zinc oxide is 0.5 wt% and the adding amount of the titanium dioxide is 0.1 wt% based on the mass fraction of the silicon sulfide rubber injection molding material, then reducing the stirring speed to 120rmp/min, and dehydrating the mixture obtained in the step (2) at the temperature of 100 ℃ for 1.5h to obtain a base material;
(3) adding 3 parts of methyl tributyl ketoxime silane into the base material obtained in the step (2), stirring and mixing for 10min at the rotating speed of 120rpm/min and the temperature of 20 ℃ under vacuum conditions, then adding 1 part of KH550 and 1 part of DCP, and reacting for 10min at the rotating speed of 500rpm/min and the temperature of 20 ℃ under vacuum conditions;
(4) and (4) adding 0.1 part of dibutyltin dilaurate with the mass fraction of 0.1 wt% into the mixture obtained in the step (3), and carrying out stirring reaction for 20min at the rotating speed of 500rpm/min and the temperature of 20 ℃ under vacuum conditions to obtain the silicon sulfide rubber injection molding material.
Based on the integrated seal membrane electrode provided in the above specific embodiment and the vulcanized silicone rubber injection molding material prepared in this embodiment, this embodiment further provides a preparation method of the integrated seal membrane electrode, where the preparation method includes:
sequentially laminating an anode gas diffusion layer 3, an anode catalyst layer 2, a proton exchange membrane 1, a cathode catalyst layer 6 and a cathode gas diffusion layer 7 in an injection mold, preheating the injection mold to 70 ℃, injecting a silicon sulfide rubber injection molding material into the injection mold to form an anode elastomer sealing frame 4 and a cathode elastomer sealing frame 8, curing for 10min, and sequentially performing die sinking and trimming treatment to obtain an integrated sealing membrane electrode; the height of the anode elastomer sealing frame 4 in the integrated sealing membrane electrode, which is higher than the anode gas diffusion layer 3, is 2mm, and the width of the anode elastomer sealing frame 4 covering the edge of the anode gas diffusion layer 3 is 0.05 mm; the height of the cathode elastomer sealing frame 8 higher than the cathode gas diffusion layer 7 is 0.1mm, and the width of the cathode elastomer sealing frame 8 covering the edge of the cathode gas diffusion layer 7 is 3 mm.
Example 2
The embodiment provides a preparation method of a vulcanized silicone rubber injection molding material, which comprises the following steps:
(1) stirring and mixing 100 parts of polymethylsiloxane with viscosity of 40000 mPas and 10 parts of ethyl silicone oil with viscosity of 400 mPas for 60min at the rotating speed of 500rpm/min and the temperature of 130 ℃;
(2) adding nano zinc oxide, nano titanium dioxide and white carbon black into the mixture obtained in the step (1) at the rotating speed of 500rpm/min and the temperature of 130 ℃ for secondary stirring and mixing for 2h, wherein the addition amount of the white carbon black is 150 parts, the addition amount of the nano zinc oxide is 2 wt% and the addition amount of the titanium dioxide is 3 wt% based on the mass fraction of the vulcanized silicone rubber injection molding material being 100 wt%, then reducing the stirring speed to 50rmp/min, and dehydrating the mixture obtained in the step (2) at the temperature of 130 ℃ for 3h to obtain a base material;
(3) adding 7 parts of vinyl tributyrinoxime silane into the base material obtained in the step (2), stirring and mixing for 20min at the rotating speed of 50rpm/min and the temperature of 30 ℃ under vacuum conditions, then adding 3 parts of KH560 and 5 parts of HC-6, and reacting for 30min at the rotating speed of 200rpm/min and the temperature of 30 ℃ under vacuum conditions;
(4) and (3) adding 0.7 part of 1 wt% Kat245 into the mixture obtained in the step (3), and carrying out stirring reaction for 40min at the rotating speed of 200rpm/min and the temperature of 30 ℃ under vacuum conditions to obtain the silicon sulfide rubber injection molding material.
Based on the integrated seal membrane electrode provided in the above specific embodiment and the vulcanized silicone rubber injection molding material prepared in this embodiment, this embodiment further provides a preparation method of the integrated seal membrane electrode, where the preparation method includes:
sequentially laminating an anode gas diffusion layer 3, an anode catalyst layer 2, a proton exchange membrane 1, a cathode catalyst layer 6 and a cathode gas diffusion layer 7 in an injection mold, preheating the injection mold to 140 ℃, injecting a silicon sulfide rubber injection molding material into the injection mold to form an anode elastomer sealing frame 4 and a cathode elastomer sealing frame 8, curing for 5min, and sequentially performing die sinking and trimming treatment to obtain an integrated sealing membrane electrode; the height of the anode elastomer sealing frame 4 in the integrated sealing membrane electrode, which is higher than the anode gas diffusion layer 3, is 1mm, and the width of the anode elastomer sealing frame 4 covering the edge of the anode gas diffusion layer 3 is 1 mm; the height of the cathode elastomer sealing frame 8 higher than the cathode gas diffusion layer 7 is 0.5mm, and the width of the cathode elastomer sealing frame 8 covering the edge of the cathode gas diffusion layer 7 is 2 mm.
Example 3
The embodiment provides a preparation method of a vulcanized silicone rubber injection molding material, which comprises the following steps:
(1) stirring and mixing 90 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 30000 mPas and 7 parts of methyl ethoxy silicone oil with the viscosity of 300 mPas for 40min at the rotating speed of 300rpm/min and the temperature of 120 ℃;
(2) adding nano zinc oxide, nano titanium dioxide and nano calcium carbonate into the mixture obtained in the step (1) at the rotating speed of 300rpm/min and the temperature of 120 ℃ for stirring dispersion treatment for 1.5h, wherein the addition amount of the nano calcium carbonate is 130 parts, the addition amount of the nano zinc oxide is 1 wt% and the addition amount of the titanium dioxide is 2 wt% based on the mass fraction of the vulcanized silicone rubber injection molding material being 100 wt%, then reducing the stirring speed to 70rmp/min, and dehydrating the mixture obtained in the step (2) at the temperature of 120 ℃ for 1.5h to obtain a base material;
(3) adding 5 parts of triallyl isocyanurate into the base material obtained in the step (2), stirring and mixing for 15min at the rotating speed of 70rpm/min and the temperature of 25 ℃ under vacuum conditions, then adding 3 parts of KH570 and 2 parts of H-850, and reacting for 15min at the rotating speed of 300rpm/min and the temperature of 25 ℃ under vacuum conditions;
(4) and (4) adding 0.5 part of dibutyltin dilaurate with the mass fraction of 0.5 wt% into the mixture obtained in the step (3), and carrying out stirring reaction for 25min at the rotating speed of 300rpm/min and the temperature of 25 ℃ under vacuum conditions to obtain the silicon sulfide rubber injection molding material.
Based on the integrated seal membrane electrode provided in the above specific embodiment and the vulcanized silicone rubber injection molding material prepared in this embodiment, this embodiment further provides a preparation method of the integrated seal membrane electrode, where the preparation method includes:
sequentially laminating an anode gas diffusion layer 3, an anode catalyst layer 2, a proton exchange membrane 1, a cathode catalyst layer 6 and a cathode gas diffusion layer 7 in an injection mold, preheating the injection mold to 110 ℃, injecting a silicon sulfide rubber injection molding material into the injection mold to form an anode elastomer sealing frame 4 and a cathode elastomer sealing frame 8, curing for 7min, and sequentially performing die sinking and trimming treatment to obtain an integrated sealing membrane electrode; the height of the anode elastomer sealing frame 4 in the integrated sealing membrane electrode, which is higher than the anode gas diffusion layer 3, is 1.5mm, and the width of the anode elastomer sealing frame 4 covering the edge of the anode gas diffusion layer 3 is 1.5 mm; the height of the cathode elastomer sealing frame 8 above the cathode gas diffusion layer 7 is 0.2mm, and the width of the cathode elastomer sealing frame 8 covering the edge of the cathode gas diffusion layer 7 is 2.5 mm.
Example 4
This example differs from example 1 in that: the amount of the nano zinc oxide added in the step (2) is 0.3 wt%, and the rest of the process parameters and the operation steps are the same as those in the example 1.
Example 5
This example differs from example 1 in that: the amount of the added nano zinc oxide in the step (2) is 2.5 wt%, and the rest of the process parameters and the operation steps are the same as those in the example 1.
Example 6
This example differs from example 1 in that: the amount of the added nano titanium dioxide in the step (2) is 0.05 wt%, and the rest of the process parameters and the operation steps are the same as those in the example 1.
Example 7
This example differs from example 1 in that: the amount of the added nano titanium dioxide in the step (2) was 3.5 wt%, and the remaining process parameters and the operation steps were the same as those in example 1.
Example 8
This example differs from example 1 in that: the height of the cathode elastomer sealing frame 8 higher than the cathode gas diffusion layer 7 in the integrated sealed membrane electrode is 2mm, the width of the cathode elastomer sealing frame 8 covering the edge of the cathode gas diffusion layer 7 is 0.05mm, and the rest process parameters and operation steps are the same as those in the embodiment 1.
Example 9
This example differs from example 1 in that: the height of the cathode elastomer sealing frame 8 in the integrated sealed membrane electrode, which is higher than the cathode gas diffusion layer 7, is 2mm, and the rest of the process parameters and the operation steps are the same as those in the embodiment 1.
Example 10
This example differs from example 1 in that: the width of the cathode elastomer sealing frame 8 covering the edge of the cathode gas diffusion layer 7 in the integrated sealed membrane electrode is 0.05mm, and the rest of the process parameters and the operation steps are the same as those in the embodiment 1.
Comparative example 1
The present comparative example provides a method of preparing an integrated seal membrane electrode, the method comprising:
the commercially available vulcanized silicone rubber material is adopted as the material of the anode elastomer sealing frame 4 and the cathode elastomer sealing frame 8; sequentially laminating an anode gas diffusion layer 3, an anode catalyst layer 2, a proton exchange membrane 1, a cathode catalyst layer 6 and a cathode gas diffusion layer 7 in an injection mold, preheating the injection mold to 70 ℃, injecting a commercially available vulcanized silicone rubber material into the injection mold to form an anode elastomer sealing frame 4 and a cathode elastomer sealing frame 8, curing for 10min, and sequentially performing die sinking and trimming treatment to obtain an integrated sealing membrane electrode; the height of the anode elastomer sealing frame 4 in the integrated sealing membrane electrode, which is higher than the anode gas diffusion layer 3, is 2mm, and the width of the anode elastomer sealing frame 4 covering the edge of the anode gas diffusion layer 3 is 0.05 mm; the height of the cathode elastomer sealing frame 8 higher than the cathode gas diffusion layer 7 is 2mm, and the width of the cathode elastomer sealing frame 8 covering the edge of the cathode gas diffusion layer 7 is 0.05 mm.
Comparative example 2
This comparative example differs from example 1 in that: the step of adding the nano zinc oxide is omitted in the step (2), the adding amount of the nano zinc oxide is distributed to other components according to the formula proportion of the vulcanized silicone rubber injection molding material, and other process parameters and operation steps are the same as those in the embodiment 1.
Comparative example 3
This comparative example differs from example 1 in that: the step of adding the nano titanium dioxide is omitted in the step (2), the adding amount of the nano zinc oxide titanium dioxide is distributed to other components according to the formula proportion of the vulcanized silicone rubber injection molding material, and other process parameters and operation steps are the same as those in the embodiment 1.
Comparative example 4
This comparative example differs from example 1 in that: the step of adding the nano zinc oxide and the nano titanium dioxide is omitted in the step (2), the total amount of the added nano zinc oxide and the added nano titanium dioxide is distributed to other components according to the formula proportion of the vulcanized silicone rubber injection material, and other process parameters and operation steps are the same as those in the embodiment 1.
The membrane electrodes prepared in examples 1 to 10 and comparative examples 1 to 4 were subjected to a single cell test, and the test results are shown in table 1; tensile strength tests were performed on the vulcanized silicone rubber materials of example 1 and comparative example 1, and the test results are shown in fig. 4.
TABLE 1
From the data analysis of table 1 it can be derived:
(1) the membrane electrode in the embodiments 1 to 3 has excellent stability and durability, which shows that the elastomer sealing frame of the membrane electrode is prepared by using the silicon sulfide injection molding material provided by the invention, and the cathode elastomer sealing frame 8 and the anode elastomer sealing frame 4 are designed asymmetrically, so that the main chain of the silicon sulfide rubber can be effectively prevented from being damaged in a high-humidity, high-temperature and acidic battery working environment, silicon ions are precipitated to damage the proton exchange membrane 1 and the catalyst layer, the durability and stability of the membrane electrode are improved, and the service life of the fuel battery of a commercial vehicle is further prolonged.
(2) The stability and durability of the membrane electrodes in examples 4 and 5 are lower than those of example 1 because the amount of nano zinc oxide added in example 4 is too low and the amount of nano zinc oxide added in example 5 is too high. When the addition amount of the nano zinc oxide is too low, the silicon hydroxyl at the end of the silicon rubber can not be fully wrapped, and the movement of a polymer molecular chain can not be limited, so that the tripping degradation reaction and the hydrolysis reaction caused by the silicon rubber hydroxyl at the end can not be inhibited; when the addition amount of the nano zinc oxide is too high, the elasticity of the vulcanized silicone rubber is reduced, and the injection molding in the subsequent membrane electrode preparation process is not facilitated.
(3) The stability and durability of the membrane electrodes in examples 6 and 7 were lower than those of example 1 because the amount of nano titania added was too low in example 6 and too high in example 7. When the addition amount of the nano titanium dioxide is too low, the nano titanium dioxide cannot be uniformly dispersed in the silicon sulfide rubber, so that the acid resistance of the silicon sulfide rubber cannot be effectively improved; when the addition amount of the nano titanium dioxide is too high, the elasticity of the vulcanized silicone rubber is reduced, and the injection molding in the subsequent membrane electrode preparation process is not facilitated.
(4) The stability and durability of the membrane electrode in example 8 are lower than those of example 1 because the cathode elastomer sealing frame 8 and the anode elastomer sealing frame 4 in example 8 are designed symmetrically, the water generated in the cathode cannot be discharged out in time and efficiently, and the cathode elastomer sealing frame 8 cannot be prevented from separating from the cathode gas diffusion layer 7 in a high-humidity environment. Therefore, the membrane electrode has poor airtightness and low durability and stability.
(5) The stability and durability of the membrane electrodes in examples 9 and 10 were lower than those of example 1, because the cathode elastomer sealing frame 8 in example 9 had a large thickness and could not rapidly discharge the water generated from the cathode; in example 10, the contact area between the cathode elastomer sealing frame 8 and the surface of the cathode gas diffusion layer 7 is small, and it is impossible to prevent the cathode elastomer sealing frame 8 and the cathode gas diffusion layer 7 from being separated from each other in a high-humidity and high-heat working environment, which affects the air tightness of the membrane electrode.
(6) The stability and durability of the membrane electrode in comparative example 1 are much lower than those of example 1 because the anode elastomer sealing frame 4 and the cathode elastomer sealing frame 8 of the membrane electrode are prepared using commercially available silicon sulfide rubber materials in comparative example 1, and the cathode elastomer sealing frame 8 and the anode elastomer sealing frame 4 are symmetrically designed. The commercially available vulcanized silicone rubber material has poor tolerance to high temperature, high humidity and acidic working environment, and the precipitated silicon ions damage the proton exchange membrane 1 and the catalyst layer, so that the membrane electrode has poor durability and stability; and the air tightness of the membrane electrode cannot be effectively ensured by the symmetric injection molding design of the cathode and the anode. Therefore, the membrane electrode in comparative example 1 cannot satisfy the sealing and life-prolonging requirements of the fuel cell for a commercial vehicle.
In addition, when the tensile strength of the vulcanized silicone rubber injection molded material provided in example 1 of the present invention and the commercially available vulcanized silicone rubber material in comparative example 1 was tested over time at a temperature of 90 ℃ and a pH of 2, as shown in fig. 4, the tensile strength of the commercially available vulcanized silicone rubber material showed a significantly decreasing trend, while the change in tensile strength of the vulcanized silicone rubber injection molded material provided in example 1 tended to be smooth. The vulcanized silicone rubber injection molding material provided by the invention has excellent heat resistance, moisture resistance and acid resistance, and can meet the requirement of a fuel cell of a commercial vehicle on sealing property when being used as a membrane cell elastomer sealing frame material.
(7) The stability and durability of the membrane electrode in comparative examples 2 to 4 are much lower than those of example 1, because the nano zinc oxide aid is not added in comparative example 2, the titanium dioxide aid is not added in comparative example 3, and the nano zinc oxide and nano titanium dioxide aids are not added in comparative example 4 when the vulcanized silicone rubber injection molding material is prepared. The nanometer zinc oxide assistant can improve the stability of the silicon sulfide rubber injection molding material in high humidity and high heat environment, and the nanometer titanium dioxide assistant can improve the stability of the silicon sulfide rubber injection molding material in acid condition. Therefore, when the nano zinc oxide and the nano titanium dioxide are added simultaneously to prepare the vulcanized silicone rubber injection molding material as the elastomer material of the membrane electrode, the requirements of the commercial vehicle fuel cell on the stability and durability of the membrane electrode can be met.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a vulcanized silicone rubber injection molding material is characterized by comprising the following steps:
mixing silica gel, silicone oil, an auxiliary agent, a cross-linking agent and a vulcanizing agent, and reacting to obtain the vulcanized silicone rubber injection molding material;
the auxiliary agent comprises nano zinc oxide and nano titanium dioxide.
2. The preparation method according to claim 1, wherein the preparation method specifically comprises:
(1) mixing the silica gel and the silica oil, adding an auxiliary agent, and then sequentially performing dispersion treatment and dehydration treatment to obtain a base material;
(2) after the base material and the cross-linking agent are mixed, adding the vulcanizing agent for reaction to obtain the vulcanized silicone rubber injection molding material;
preferably, the silica gel comprises any one of polymethylsiloxane, alpha, omega-dihydroxy polydimethylsiloxane or polydimethylsiloxane, and is further preferably hydroxyl-terminated polydimethylsiloxane;
preferably, the silicone oil comprises any one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil and methyl vinyl silicone oil or the combination of at least two of the methyl silicone oil, the ethyl silicone oil, the phenyl silicone oil and the methyl hydrogen-containing silicone oil;
preferably, the silica gel and the silicone oil are mixed under stirring conditions;
preferably, the mixing time of the silica gel and the silica oil is 30-60 min;
preferably, the temperature for mixing the silica gel and the silica oil is 100-130 ℃;
preferably, the mixing stirring speed of the silica gel and the silica oil is 200-500 rpm/min;
preferably, the adding amount of the silica gel is 80-100 parts;
preferably, the viscosity of the silica gel is 15000-40000 mPa & s;
preferably, the addition amount of the silicone oil is 5-10 parts;
preferably, the viscosity of the silicone oil is 100-400 mPa & s;
preferably, an additive is also added in the process of the dispersion treatment;
preferably, the additive comprises nano calcium carbonate or white carbon black;
preferably, the dispersion treatment is carried out under stirring conditions;
preferably, the time of the dispersion treatment is 1-2 h;
preferably, the stirring speed of the dispersion treatment is 200-500 rpm/min;
preferably, the temperature of the dispersion treatment is 100-130 ℃;
preferably, the addition amount of the additive is 80-150 parts;
preferably, the addition amount of the nano zinc oxide is 0.5-2 wt% based on 100 wt% of the mass fraction of the vulcanized silicone rubber injection molding material;
preferably, the nano titanium dioxide is added in an amount of 0.1-3 wt% based on 100 wt% of the mass fraction of the vulcanized silicone rubber injection molding material;
preferably, the dehydration treatment is carried out under stirring conditions;
preferably, the stirring speed of the dehydration treatment is 50-120 rpm/min;
preferably, the temperature of the dehydration treatment is 100-130 ℃;
preferably, the time of the dehydration treatment is 1.5-3 h.
3. The production method according to claim 2, wherein the crosslinking agent comprises any one of methyl tributyrinoxime silane, vinyl tributyrinoxime silane, triallyl isocyanurate, vinyl triethoxysilane, an alkoxysilane compound, or a partially hydrolyzed polycondensate of an alkoxysilane compound, or a combination of at least two thereof;
preferably, the base material and the cross-linking agent are mixed under stirring conditions;
preferably, the temperature for mixing the base material and the cross-linking agent is 20-30 ℃;
preferably, the mixing time of the base material and the cross-linking agent is 10-20 min;
preferably, the stirring speed of mixing the base material and the cross-linking agent is 50-120 rpm/min;
preferably, the addition amount of the cross-linking agent is 3-7 parts;
preferably, the binder is mixed with the cross-linking agent under vacuum conditions;
preferably, the reaction in step (2) is carried out under stirring conditions;
preferably, a coupling agent is also added during the reaction in the step (2);
preferably, the coupling agent comprises any one of KH-550, KH-560, KH-570, KH-792, DL-602, or DL-171, or a combination of at least two thereof;
preferably, the sulfurizing agent comprises any one or a combination of at least two of DCP, HC-6, H-850, H-101 or HC-750;
preferably, the adding amount of the coupling agent is 1-3 parts;
preferably, the addition amount of the vulcanizing agent is 1-5 parts;
preferably, the process of the reaction in step (2) is carried out under vacuum conditions;
preferably, the reaction in step (2) is carried out under stirring conditions;
preferably, the reaction time in the step (2) is 10-30 min;
preferably, the stirring speed of the reaction in the step (2) is 200-500 rpm/min;
preferably, the temperature of the reaction in the step (2) is 20-30 ℃;
preferably, in the step (2), after the reaction process is finished, a catalyst is further added for stirring reaction to obtain the vulcanized silicone rubber injection molding material;
preferably, the catalyst comprises any one or a combination of at least two of dibutyltin dilaurate, Kat245 or an organic titanium compound;
preferably, after the catalyst is added, stirring reaction is carried out under vacuum condition;
preferably, the time for stirring and reacting the catalyst is 20-40 min;
preferably, the rotation speed of the stirring reaction of the catalyst is 200-500 rpm/min;
preferably, the temperature of the catalyst for stirring reaction is 20-30 ℃;
preferably, the addition amount of the catalyst is 0.1-0.7 part;
preferably, the mass fraction of the catalyst is 0.1-1 wt%.
4. The production method according to any one of claims 1 to 3, characterized by comprising:
(1) stirring and mixing 80-100 parts of silica gel with the viscosity of 15000-40000 mPas and 5-10 parts of silicone oil with the viscosity of 100-400 mPas for 30-60 min at the rotating speed of 200-500 rpm/min and the temperature of 100-130 ℃;
(2) adding nano zinc oxide, nano titanium dioxide and an additive into the mixture obtained in the step (1) at a rotating speed of 200-500 rpm/min and a temperature of 100-130 ℃ for stirring dispersion treatment for 1-2 h, wherein the addition amount of the additive is 80-150 parts, the addition amount of the nano zinc oxide is 0.5-2 wt% and the addition amount of the nano titanium dioxide is 0.1-3 wt% based on 100 wt% of the vulcanized silicone rubber injection molding material, then reducing the stirring speed to 50-120 rmp/min, and dehydrating the mixture obtained in the step (2) at a temperature of 100-130 ℃ for 1.5-3 h to obtain a base material;
(3) adding 3-7 parts of cross-linking agent into the base material obtained in the step (2), stirring and mixing for 10-20 min at the rotating speed of 50-120 rpm/min and at the temperature of 20-30 ℃ under vacuum conditions, then adding 1-3 parts of coupling agent and 1-5 parts of vulcanizing agent, and reacting for 10-30 min at the rotating speed of 200-500 rpm/min and at the temperature of 20-30 ℃ under vacuum conditions;
(4) and (3) adding 0.1-0.7 part of catalyst with the mass fraction of 0.1-1 wt% into the mixture obtained in the step (3), and carrying out stirring reaction for 20-40 min at the rotating speed of 200-500 rpm/min and at the temperature of 20-30 ℃ under vacuum conditions to obtain the vulcanized silicone rubber injection molding material.
5. A vulcanized silicone rubber injection molding material characterized by being produced by the production method according to any one of claims 1 to 4.
6. An integrated seal membrane electrode is characterized in that the integrated seal membrane electrode comprises a proton exchange membrane, and a cathode and an anode which are arranged on two sides of the proton exchange membrane, wherein a cathode elastomer seal frame is arranged on the periphery of the cathode, an anode elastomer seal frame is arranged on the periphery of the anode, the cathode elastomer seal frame and the anode elastomer seal frame are arranged asymmetrically, and the anode, the proton exchange membrane and the cathode are sealed into a whole through the anode elastomer seal frame and the cathode elastomer seal frame;
the anode elastomer sealing frame and the cathode elastomer sealing frame are both prepared from the vulcanized silicone rubber injection molding material of claim 5.
7. The integrated sealed membrane electrode of claim 6, wherein the cathode includes a cathode catalyst layer and a cathode gas diffusion layer laminated in this order from the surface of the proton exchange membrane;
preferably, the anode includes an anode catalyst layer and an anode gas diffusion layer sequentially stacked from a surface of the proton exchange membrane;
preferably, the width of the cathode elastomer sealing frame covering the edge of the cathode gas diffusion layer is 0.05-3 mm;
preferably, the width of the anode elastomer sealing frame covering the edge of the anode gas diffusion layer is 0.05-3 mm;
preferably, the contact area of the cathode elastomer sealing frame and the surface of the cathode gas diffusion layer is recorded as S1The contact area of the anode elastomer sealing frame and the surface of the anode gas diffusion layer is marked as S2Wherein S is1＞S2；
Preferably, the cathode elastomer sealing frame is 0.1-2 mm higher than the cathode gas diffusion layer;
preferably, the anode elastomer sealing frame is 0.1-2 mm higher than the anode gas diffusion layer;
preferably, the thickness of the cathode elastomer sealing frame is recorded as H1The thickness of the anode elastomer sealing frame is marked as H2Wherein H is1＜H2；
Preferably, the cathode catalyst layer and the anode catalyst layer are collectively called a catalyst layer, the cathode gas diffusion layer and the anode gas diffusion layer are collectively called a diffusion layer, and the area of the proton exchange membrane is marked as S3And the area of the catalyst layer is marked as S4And the area of the diffusion layer is marked as S5Wherein S is3＞S4＝S5。
8. A method for producing an integrated seal membrane electrode assembly according to claim 6 or 7, comprising:
and sequentially laminating the anode, the proton exchange membrane and the cathode in an injection mold, then injecting a vulcanized silicone rubber injection molding material into the injection mold to form an anode elastomer sealing frame and a cathode elastomer sealing frame, and curing to obtain the integrated sealing membrane electrode.
9. The preparation method of the injection mold according to claim 8, wherein the injection mold is preheated to 70-140 ℃, and then the injection molding material is injected into the injection mold;
preferably, the curing time is 5-10 min;
preferably, after the curing, mold opening and trimming are further performed in sequence to obtain the integrated sealing film electrode.
10. A fuel cell comprising the integrated sealed membrane electrode of claim 6 or 7.
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