CN112225999B - Sealing material, preparation method and application thereof, and fuel cell - Google Patents
Sealing material, preparation method and application thereof, and fuel cell Download PDFInfo
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- CN112225999B CN112225999B CN202010929014.7A CN202010929014A CN112225999B CN 112225999 B CN112225999 B CN 112225999B CN 202010929014 A CN202010929014 A CN 202010929014A CN 112225999 B CN112225999 B CN 112225999B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0855—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using microwave
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a sealing material, a preparation method and application thereof, and a fuel cell. The main technical scheme adopted is as follows: the sealing material comprises the following raw materials in parts by weight: 95-105 parts by weight of EPDM raw rubber, preferably 100 parts by weight of reinforcing carbon black, 5-50 parts by weight of plasticizer, 1-6 parts by weight of release agent, 0.2-12 parts by weight of peroxide vulcanizing agent, 0.2-6 parts by weight of accelerator and 0.5-8 parts by weight of anti-aging agent. Wherein the accelerator is one or more of PDM, TAIC and TAC; the anti-aging agent is one or more of phenols, imidazoles and waxes. The sealing material is prepared by adopting a microwave vulcanization process, the heating is rapid, the vulcanization time is greatly shortened, the heating uniformity is good, the vulcanization quality is higher, and the tear resistance of the sealing material is greatly improved. The invention is mainly used for providing a sealing material which can not pollute a membrane electrode of a fuel cell, can not cause platinum catalyst poisoning of the fuel cell and has better tearing strength.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a sealing material, a preparation method and application thereof, and a fuel cell.
Background
A pem fuel cell is a power generation device that directly converts chemical energy stored in a fuel and an oxidant into electrical energy. The energy conversion system has the advantages of high energy conversion efficiency, cleanness, no pollution, operability at normal temperature, low working noise, good reliability and maintainability and the like, is the most promising new energy, and is widely applied to power sources of automobiles, trains, ships, submersibles, aircrafts and the like and standby power sources of electric power, communication, data centers, public facilities and the like.
The single proton exchange membrane fuel cell consists of membrane electrode assembly, double polar plate and sealing part. The membrane electrode assembly consists of a gas diffusion layer, a cathode and anode catalyst layer containing platinum and a proton exchange membrane. The proton exchange membrane generally uses a fluororesin polymer membrane having a sulfonic acid group, which is capable of proton conduction after absorbing water. The fuel cell generally operates at 70-80 ℃ and the pH of the sulfonic acid group is 1-2, which belongs to a strong acid environment.
In order to ensure the long-term normal operation of the fuel cell, the sealing material of the proton exchange membrane fuel cell is required to have the following characteristics: (1) high airtightness: sealing the fuel gas and the oxidant gas; (2) low moisture permeability: the polymer film is in a saturated water vapor state to work and keep the acidity inside; (3) acid resistance: when a fuel cell generates electricity, the fuel cell is usually in a strongly acidic environment with low pH; (4) moisture resistance: when the battery works, the inner part is in a saturated water vapor state; (5) Heat resistance: the working environment of the polymer film is determined; (6) low ion elution property: the dissolved ions can affect the proton conductivity of the polymer membrane, and some of the ions can also cause the platinum catalyst to be poisoned; (7) electrical insulation: preventing short circuit between single cells; (8) rubber elasticity: vibration absorption and impact resistance; (9) chemical stability: chemical stability to coolant, chemical stability to various fuels.
In the prior art, ethylene propylene diene monomer rubber is mainly used as a sealing material of a proton exchange membrane fuel cell. Because the main chain of the ethylene propylene diene monomer rubber is composed of chemically stable saturated hydrocarbon, the ethylene propylene diene monomer rubber has excellent ozone resistance, heat resistance, weather resistance and other aging resistance, and has good chemical resistance, electrical insulation property, impact elasticity, low-temperature performance, low density, high filling property, hot water resistance, steam resistance, low compression set, high strength, high elongation and the like. Therefore, the ethylene propylene diene monomer is very suitable for being used as a sealing material of a proton exchange membrane fuel cell.
However, the inventor of the present invention has found that the use of the conventional ethylene propylene diene monomer as a sealing material for a proton exchange membrane fuel cell has at least the following problems:
(1) The existing ethylene propylene diene monomer contains zinc oxide, calcium carbonate and the like, so that zinc ions and calcium ions are easily dissolved out from a sealing material under a strong acid environment, a membrane electrode of a fuel cell is polluted, and the performance of the membrane electrode is reduced;
(2) The sulfur contained in the existing ethylene propylene diene monomer or a vulcanizing agent which can be decomposed into sulfur can generate hydrogen sulfide under a strong acid environment to cause the platinum catalyst of the fuel cell to be poisoned;
(3) The existing ethylene propylene diene monomer prepared by a peroxide vulcanizing agent has the defect of poor tearing strength performance.
Disclosure of Invention
The present invention provides a sealing material, a preparation method and an application thereof, and a fuel cell, and mainly aims to provide a sealing material which does not pollute a membrane electrode of the fuel cell and does not cause poisoning of a platinum catalyst of the fuel cell.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, an embodiment of the present invention provides a sealing material, where the sealing material includes the following components in parts by weight:
EPDM raw rubber: 95 to 105 parts by weight, preferably 100 parts by weight;
reinforcing carbon black: 20-160 parts by weight;
plasticizer: 5-50 parts by weight;
releasing agent: 1-6 parts by weight;
peroxide vulcanizing agent: 0.2 to 12 parts by weight;
accelerator (b): 0.2-6 parts by weight;
an anti-aging agent: 0.5-8 parts by weight;
wherein the accelerator is one or a mixture of more of PDM, TAIC and TAC;
the anti-aging agent is one or a mixture of several of phenols, imidazoles and waxes.
Preferably, the ethylene content in the raw EPDM rubber is 40-60wt%; and/or the diene content in the raw EPDM rubber is 3-15wt%.
Preferably, the reinforcing carbon black is one or a mixture of two of N550 carbon black and N774 carbon black; and/or the plasticizer is one or a mixture of two of paraffin oil and PAO; and/or the release agent is stearic acid; and/or the peroxide vulcanizing agent is one or a mixture of more of DCP, DTBP and BPMC.
Preferably, the phenols are phenolic antioxidants 1010; and/or 2-mercaptobenzimidazole is selected as the imidazole; and/or the wax is microcrystalline wax.
Preferably, the Shore A hardness of the sealing material is 45-75, preferably 50-60; and/or the tear strength of the sealing material is from 40 to 80kN/m, preferably from 50 to 60kN/m.
In another aspect, the use of a sealing material according to any one of the preceding claims as or in the manufacture of a sealing structure for a fuel cell; preferably, the sealing structure is used to seal the membrane electrode assembly between the bipolar plates.
In another aspect, the method for preparing a sealing material according to any one of the above aspects comprises the steps of:
mixing for the first time: mixing EPDM raw rubber, reinforcing carbon black, a plasticizer, a release agent and an anti-aging agent, and cooling to obtain a rubber compound;
and (3) mixing for the second time: mixing the rubber compound, a peroxide vulcanizing agent and an accelerator to obtain a second mixing product;
die pressing: carrying out die pressing on the second mixed product to obtain a die pressing product with a set shape and size;
microwave vulcanization: and putting the mould pressing product into microwave vulcanization equipment for microwave vulcanization to obtain the sealing material.
Preferably, in the step of microwave vulcanization: the microwave curing temperature is 120-150 deg.C, and the microwave curing time is 2-10min.
Preferably, the first mixing step is performed in an internal mixer; and/or
The second mixing step is carried out in an open mill (the temperature of the second mixing is room temperature, so as to prevent the reaction of the mixing gum and the peroxide vulcanizing agent and the accelerator); and/or
In the first mixing step: the mixing treatment time is 2-8min, preferably 4-6 min; the temperature of the mixing treatment is 115-125 ℃.
In yet another aspect, embodiments of the present invention provide a fuel cell, wherein the fuel cell includes a sealing structure; wherein the sealing structure is the sealing material of any one of the above; preferably, the sealing structure is used for sealing the membrane electrode assembly in the fuel cell unit between the bipolar plates; preferably, the fuel cell is a proton exchange membrane fuel cell.
Compared with the prior art, the sealing material, the preparation method and the application thereof and the fuel cell have at least the following beneficial effects:
the sealing material provided by the embodiment of the invention comprises raw materials of EPDM (ethylene propylene diene monomer) raw rubber, reinforcing carbon black, a plasticizer, a release agent, a peroxide vulcanizing agent, an accelerator (specifically one or more of PDM, TAIC and TAC), and an anti-aging agent (specifically one or more of phenols, imidazoles and waxes) in set parts by weight; the EPDM raw rubber and other components do not contain substances such as zinc oxide, calcium carbonate and the like, so that the sealing material of the invention does not dissolve out metal ions under a strong acid environment, and further does not influence the performance of a membrane electrode of a fuel cell. Furthermore, the vulcanizing agent of the sealing material provided by the embodiment of the invention is selected from peroxide vulcanizing agents, so that the sealing material does not generate sulfur or decompose sulfur, and the sealing material does not cause platinum catalyst poisoning of the fuel cell.
Furthermore, as the vulcanizing agent in the sealing material provided by the embodiment of the invention is a peroxide vulcanizing agent, the problems of long vulcanizing time and poor tearing performance of the sealing material can be caused by adopting the conventional vulcanizing method such as heating vulcanization; therefore, the preparation method of the sealing material provided by the embodiment of the invention is specially used for vulcanizing a peroxide vulcanizing agent by adopting a microwave vulcanization process, and microwave energy penetrates into a heated medium to be directly and integrally heated, so that the heating is rapid, the efficiency and the energy are high, the vulcanization time is greatly shortened, the heating uniformity is better, the vulcanization quality is higher, and the tearing strength of the prepared sealing material is greatly improved.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present application will be provided in conjunction with the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In one aspect, embodiments of the present invention provide a sealing material; the sealing material comprises the following raw material components in parts by weight:
EPDM raw rubber: 95 to 105 parts by weight, preferably 100 parts by weight;
reinforcing carbon black: 20-160 parts by weight;
plasticizer: 5-50 parts by weight;
mold release agent (stearic acid): 1-6 parts by weight;
peroxide vulcanizing agent: 0.2 to 12 parts by weight;
accelerator (b): 0.2-6 parts by weight;
an anti-aging agent: 0.5-8 parts by weight.
The accelerator is one or a mixture of more of PDM (N, N' -m-phenylene maleimide), TAIC (triallyl isocyanurate) and TAC (triallyl cyanurate) (the accelerator improves the crosslinking density and strength).
The anti-aging agent is one or a mixture of several of phenols, imidazoles and waxes.
The raw materials of the sealing material provided by the embodiment of the invention are composed of the raw EPDM rubber (ethylene propylene diene monomer), the reinforcing carbon black, the plasticizer, the release agent, the peroxide vulcanizing agent, the accelerator (specifically, one or more of PDM, TAIC and TAC), the anti-aging agent (specifically, one or more of phenols, imidazoles and waxes) in the set weight parts; the EPDM raw rubber and other components do not contain substances such as zinc oxide, calcium carbonate and the like, so that the sealing material of the invention does not dissolve out metal ions under a strong acid environment, and further does not influence the performance of a membrane electrode of a fuel cell. Furthermore, the vulcanizing agent of the sealing material provided by the embodiment of the invention is selected from peroxide vulcanizing agents, so that the sealing material does not generate sulfur or decompose sulfur, and therefore, the sealing material of the invention does not cause platinum catalyst poisoning of a fuel cell.
Preferably, the ethylene content in the EPDM raw rubber is 40-60wt%; the EPDM green rubber has a diene content of 3 to 15 weight percent (the more diene, the greater the crosslink density). The reinforcing agent is reinforcing carbon black; the reinforcing carbon black includes low-reinforcing carbon black and high-reinforcing carbon black. The plasticizer is used for preventing solid substances from exuding, and is selected from one or a mixture of two of paraffin oil and PAO; stearic acid is used to improve the release performance; the peroxide vulcanizing agent is one or a mixture of more of DCP (dicumyl peroxide), DTBP (dual-tert-butyl peroxide) and BPMC (1, 1-di-tert-butyl peroxy-3, 5-trimethylcyclohexane) (the consumption of the peroxide is too small, the crosslinking is insufficient, the consumption of the peroxide is too large, the crosslinking density is too large, and the tensile property is reduced).
The preparation method of the sealing material mainly comprises the following steps:
mixing for the first time: and (3) putting the EPDM raw rubber, the reinforcing carbon black, the plasticizer, the stearic acid and the anti-aging agent into an internal mixer according to the proportion, mixing and cooling to obtain a rubber compound.
And (3) mixing for the second time: adding peroxide vulcanizing agent and accelerator into the rubber compound, mixing on an open mill, and discharging.
Die pressing: and molded into a molded product of a desired shape and size in a molding press.
Microwave vulcanization: and putting the mould pressing product into a microwave vulcanization device for vulcanization at the temperature of 120-150 ℃ for 2-10 minutes.
Here, the vulcanizing agent in the raw material formulation of the sealing material provided by the embodiment of the invention is a peroxide vulcanizing agent; the existing heating vulcanization method not only ensures that the vulcanization time is long, but also ensures that the prepared sealing material has poor tearing performance. Therefore, the invention firstly proposes and selects the microwave vulcanization process, the microwave energy penetrates into the heated medium to be directly heated integrally, the heating is rapid, the efficiency and the energy are high, the vulcanization time is greatly shortened, the heating uniformity is better, the vulcanization quality is higher, and the tearing strength of the prepared sealing material is greatly improved.
The invention is further illustrated by the following specific examples:
example 1
This example prepares a sealing material, which is prepared from the following raw materials in parts by weight: 100 parts of EPDM raw rubber, 20 parts of N550 carbon black, 5 parts of paraffin oil, 1 part of stearic acid, 0.5 part of DCP, 0.2 part of PDM and 0.5 part of phenolic antioxidant 1010. Here, the weight of each part of the raw materials was 10g, that is, in this example, 100 parts of EPDM raw rubber was 1000g, 20 parts of N550 carbon black was 200g, 5 parts of paraffin oil was 50g, 1 part of stearic acid was 10g, 0.5 part of DCP was 5g, 0.2 part of PDM was 2g, and 0.5 part of phenol antioxidant 1010 was 5g.
The preparation method comprises the following specific steps: 100 parts of EPDM raw rubber, 20 parts of reinforcing carbon black (N550 carbon black), 5 parts of plasticizer (paraffin oil), 1 part of stearic acid and 0.5 part of anti-aging agent (phenolic antioxidant 1010) are put into an internal mixer for mixing for 5min, the mixing temperature is controlled at 120 ℃, then rubber is discharged, sheets are filtered out, and the internal mixer is placed and cooled for 8 hours to obtain rubber compound. Then, adding 0.5 part of peroxide curing agent (DCP) and 0.2 part of accelerator (PDM) into the rubber compound, mixing on an open mill, and discharging to obtain a secondary mixed product; and molding the secondary mixed product into a required shape and size in a molding press, and then putting the molded product into a microwave oven for vulcanization (wherein the vulcanization temperature is 150 ℃ and the vulcanization time is 2 min); and cooling the vulcanized product to obtain the sealing material.
Example 2
The embodiment prepares a sealing material, which is prepared from the following raw materials in parts by weight: 100 parts of EPDM raw rubber, 80 parts of N550 carbon black, 20 parts of PAO, 2 parts of stearic acid, 3 parts of DCP, 1.5 parts of TAIC and 1010 2 parts of phenolic antioxidant. Here, the weight of each part of the raw material was 10g, that is, in this example, the weight of 100 parts of EPDM raw rubber was 1000g, the weight of 80 parts of N550 carbon black was 800g, the weight of 20 parts of PAO was 200g, the weight of 2 parts of stearic acid was 20g, the weight of 3 parts of DCP was 30g, the weight of 1.5 parts of TAIC was 15g, and the weight of 2 parts of phenolic antioxidant 1010 was 20g.
The preparation method comprises the following specific steps: 100 parts of EPDM raw rubber, 80 parts of reinforcing carbon black (N550 carbon black), 20 parts of Plasticizer (PAO), 2 parts of stearic acid and 2 parts of anti-aging agent (phenolic antioxidant 1010) are put into an internal mixer for mixing for 5min, the mixing temperature is controlled at 120 ℃, then rubber is discharged, sheets are filtered out, and the internal mixer is placed and cooled for 8 hours to obtain the rubber compound. Then, adding 3 parts of peroxide curing agent (DCP) and 1.5 parts of accelerator (TAIC) into the rubber compound, mixing on an open mill, and discharging to obtain a secondary mixed product; and molding the secondary mixed product into a required shape and size in a molding press, and then putting the molded product into a microwave oven for vulcanization (wherein the vulcanization temperature is 150 ℃, and the vulcanization time is 2 min); and cooling the vulcanized product to obtain the sealing material.
Example 3
This example prepares a sealing material, which is prepared from the following raw materials in parts by weight: 100 parts of EPDM raw rubber, 100 parts of N550 carbon black, 30 parts of paraffin oil, 4 parts of stearic acid, 8 parts of DCP, 4 parts of TAIC and 5 parts of 2-mercaptobenzimidazole. Here, the weight of each part of the raw materials was 10g, that is, in this example, the weight of 100 parts of EPDM raw rubber was 1000g, the weight of 100 parts of N550 carbon black was 1000g, the weight of 30 parts of paraffin oil was 300g, the weight of 4 parts of stearic acid was 40g, the weight of 8 parts of DCP was 80g, the weight of 4 parts of TAIC was 40g, and the weight of 5 parts of 2-mercaptobenzimidazole was 50g.
The preparation method comprises the following specific steps: 100 parts of EPDM raw rubber, 100 parts of reinforcing agent carbon black (N550 carbon black), 30 parts of plasticizer (paraffin oil), 4 parts of stearic acid and 5 parts of anti-aging agent (2-mercaptobenzimidazole) are put into an internal mixer for mixing for 5min, the mixing temperature is controlled at 120 ℃, then rubber is discharged, sheets are filtered out, and the internal mixer is placed and cooled for 8 hours to obtain rubber compound. Then, adding 8 parts of peroxide curing agent (DCP) and 4 parts of accelerator (TAIC) into the rubber compound, mixing on an open mill, and discharging to obtain a secondary mixed product; and molding the secondary mixed product into a required shape and size in a molding press, and then putting the molded product into a microwave oven for vulcanization (wherein the vulcanization temperature is 150 ℃, and the vulcanization time is 2 min); and cooling the vulcanized product to obtain the sealing material.
Example 4
The embodiment prepares a sealing material, which is prepared from the following raw materials in parts by weight: 100 parts of EPDM raw rubber, 115 parts of N550 carbon black, 30 parts of PAO, 3 parts of stearic acid, 6 parts of DTBP, 3 parts of TAIC and 4 parts of microcrystalline wax. The weight of each raw material was 10g, that is, in this example, 100 parts of EPDM raw rubber was 1000g, 115 parts of N550 carbon black was 1150g, 30 parts of PAO was 300g, 3 parts of stearic acid was 30g, 6 parts of DTBP was 60g, 3 parts of TAIC was 30g, and 4 parts of microcrystalline wax was 40g.
The preparation method comprises the following specific steps: 100 parts of EPDM raw rubber, 115 parts of reinforcing agent carbon black (N550 carbon black), 30 parts of Plasticizer (PAO), 3 parts of stearic acid and 4 parts of anti-aging agent (microcrystalline wax) are put into an internal mixer for mixing for 5min, the mixing temperature is controlled at 120 ℃, then rubber is discharged, sheets are filtered out, and the internal mixer is placed and cooled for 8 hours to obtain rubber compound. Then, adding 6 parts of peroxide vulcanizing agent (DTBP) and 3 parts of accelerator (TAIC) into the rubber compound, mixing on an open mill, and discharging to obtain a secondary mixed product; and molding the secondary mixed product into a required shape and size in a molding press, and then putting the molded product into a microwave oven for vulcanization (wherein the vulcanization temperature is 150 ℃, and the vulcanization time is 2 min); and cooling the vulcanized product to obtain the sealing material.
Example 5
The embodiment prepares a sealing material, which is prepared from the following raw materials in parts by weight: 100 parts of EPDM raw rubber, 130 parts of N774 carbon black, 40 parts of paraffin oil, 4 parts of stearic acid, 10 parts of DTBP, 5 parts of TAC and 7 parts of 2-mercaptobenzimidazole. Here, the weight of each raw material was 10g, that is, 100 parts of EPDM raw rubber in this example was 1000g, 130 parts of N774 carbon black was 1300g, 40 parts of paraffin oil was 400g, 4 parts of stearic acid was 40g, 10 parts of DTBP was 100g, 5 parts of TAC was 50g, and 7 parts of 2-mercaptobenzimidazole was 70g.
The preparation method comprises the following specific steps: 100 parts of EPDM raw rubber, 130 parts of reinforcing agent carbon black (N774 carbon black), 40 parts of plasticizer (paraffin oil), 4 parts of stearic acid and 7 parts of anti-aging agent (2-mercaptobenzimidazole) are placed into an internal mixer for mixing for 5min, the mixing temperature is controlled at 120 ℃, then rubber is discharged, sheets are filtered out, and the internal mixer is placed and cooled for 8 hours to obtain rubber compound. Then, adding 10 parts of peroxide vulcanizing agent (DTBP) and 5 parts of accelerator (TAC) into the rubber compound, mixing on an open mill, and discharging to obtain a secondary mixed product; and molding the secondary mixed product into a required shape and size in a molding press, and then putting the molded product into a microwave oven for vulcanization (wherein the vulcanization temperature is 150 ℃, and the vulcanization time is 2 min); and cooling the vulcanized product to obtain the sealing material.
Example 6
The embodiment prepares a sealing material, which is prepared from the following raw materials in parts by weight: 100 parts of EPDM raw rubber, 140 parts of N774 carbon black, 40 parts of PAO, 6 parts of stearic acid, 12 parts of BPMC, 6 parts of TAC and 6 parts of microcrystalline wax. The weight of each part of raw material was 10g, that is, 100 parts of EPDM raw rubber, 140 parts of N774 carbon black, 40 parts of PAO, 6 parts of stearic acid, 12 parts of BPMC, 6 parts of TAC and 6 parts of microcrystalline wax were respectively 1000g, 1400g, 120g, 6 parts of PAO, 60g and 60g, respectively.
The preparation method comprises the following specific steps: 100 parts of EPDM raw rubber, 140 parts of reinforcing agent carbon black (N774 carbon black), 40 parts of Plasticizer (PAO), 6 parts of stearic acid and 6 parts of anti-aging agent (microcrystalline wax) are put into an internal mixer for mixing for 5min, the mixing temperature is controlled at 120 ℃, then rubber is discharged, sheets are filtered out, and the internal mixer is placed and cooled for 8 hours to obtain the rubber compound. Then, adding 12 parts of peroxide vulcanizing agent (BPMC) and 6 parts of accelerator (TAC) into the rubber compound, mixing on an open mill, and discharging to obtain a secondary mixed product; and molding the secondary mixed product into a required shape and size in a molding press, and then putting the molded product into a microwave oven for vulcanization (wherein the vulcanization temperature is 150 ℃, and the vulcanization time is 2 min); and cooling the vulcanized product to obtain the sealing material.
Example 7
The embodiment prepares a sealing material, which is prepared from the following raw materials in parts by weight: 100 parts of EPDM raw rubber, 160 parts of N774 carbon black, 50 parts of paraffin oil, 5 parts of stearic acid, 10 parts of BPMC, 5 parts of TAC and 8 parts of 2-mercaptobenzimidazole. Here, the weight of each raw material was 10g, that is, in this example, the weight of 100 parts EPDM raw rubber was 1000g, the weight of 160 parts N774 carbon black was 1600g, the weight of 50 parts paraffin oil was 500g, the weight of 5 parts stearic acid was 50g, the weight of 10 parts BPMC was 100g, the weight of 5 parts TAC was 50g, and the weight of 8 parts 2-mercaptobenzimidazole was 80g.
The preparation method comprises the following specific steps: 100 parts of EPDM raw rubber, 160 parts of reinforcing agent carbon black (N774 carbon black), 50 parts of plasticizer (paraffin oil), 5 parts of stearic acid and 8 parts of anti-aging agent (2-mercaptobenzimidazole) are placed into an internal mixer for mixing for 5min, the mixing temperature is controlled at 120 ℃, then rubber is discharged, sheets are filtered out, and the internal mixer is placed and cooled for 8 hours to obtain rubber compound. Then, adding 10 parts of peroxide vulcanizing agent (BPMC) and 5 parts of accelerator (TAC) into the rubber compound, mixing on an open mill, and discharging to obtain a secondary mixed product; and molding the secondary mixed product into a required shape and size in a molding press, and then putting the molded product into a microwave oven for vulcanization (wherein the vulcanization temperature is 150 ℃, and the vulcanization time is 2 min); and cooling the vulcanized product to obtain the sealing material.
Comparative example 1
Comparative example 1 a sealing material was prepared having a raw material composition identical to that of the sealing material prepared in example 1.
The preparation method comprises the following steps: putting the EPDM raw rubber, the reinforcing agent carbon black, the plasticizer, the stearic acid and the anti-aging agent into an internal mixer according to the proportion, mixing for 5min, controlling the temperature at 120 ℃, then discharging rubber, filtering out pieces, standing and cooling for 8 hours to obtain rubber compound; then adding peroxide vulcanizing agent and accelerator in corresponding weight parts into the rubber compound, mixing on an open mill, and discharging to obtain a secondary mixed product; molding the secondary mixed product into a required shape and size in a molding press, and then putting the secondary mixed product into a flat vulcanizing machine for vulcanization (the vulcanization temperature is 160 ℃, and the vulcanization time is 12 min); and cooling the vulcanized product to obtain the sealing material.
Comparative example 2
Comparative example 2A sealing material having a raw material composition identical to that of the sealing material prepared in example 2 was prepared; the procedure for preparing the sealing material of comparative example 2 was identical to that of comparative example 1.
Comparative example 3
Comparative example 3A sealing material having a raw material composition identical to that of the sealing material prepared in example 3 was prepared; the procedure for preparing the sealing material of comparative example 3 was identical to that of comparative example 1.
Comparative example 4
Comparative example 4 a sealing material was prepared which had a raw material composition in accordance with that of the sealing material prepared in example 4; the preparation procedure of the sealing material of comparative example 4 was identical to that of comparative example 1.
Comparative example 5
Comparative example 5 a sealing material was prepared which had a raw material composition in accordance with that of the sealing material prepared in example 5; the procedure for preparing the sealing material of comparative example 5 was identical to that of comparative example 1.
Comparative example 6
Comparative example 6 a sealing material was prepared which had a raw material composition in accordance with that of the sealing material prepared in example 6; the preparation procedure of the sealing material of comparative example 6 was identical to that of comparative example 1.
Comparative example 7
Comparative example 7A sealing material having a raw material composition identical to that of the sealing material prepared in example 7 was prepared; the procedure for preparing the sealing material of comparative example 7 was identical to that of comparative example 1.
The sealing materials prepared in examples 1 to 7 and comparative examples 1 to 7 were subjected to hardness and tear strength tests. The hardness was measured according to the national standard GB/T1698-2003 for hard rubber hardness, the tear strength was measured according to the national standard GB/T529-2008 for vulcanized rubber or thermoplastic rubber tear strength, a rectangular test specimen was used, the tensile rate was 500mm/min, and the test results are shown in Table 1.
TABLE 1
As is evident from the data in table 1: compared with the sealing material prepared by the traditional heating vulcanization mode, the tearing strength of the sealing material prepared by the microwave vulcanization process is obviously improved for the raw materials with the same components. Moreover, it can be seen from the preparation steps of examples 1 to 7 and comparative examples 1 to 7 that: the microwave vulcanization process is used, so that the vulcanization time can be shortened.
While the invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (11)
1. A sealing material, characterized in that the sealing material is used as a sealing structure of a fuel cell; or the sealing material is used for preparing a sealing structure of a fuel cell;
wherein the sealing structure is used for sealing the membrane electrode assembly between the bipolar plates; the sealing material comprises the following raw materials in parts by weight:
EPDM raw rubber: 95-105 parts by weight;
reinforcing carbon black: 20-160 parts by weight;
plasticizer: 5-50 parts by weight;
releasing agent: 1-6 parts by weight;
peroxide vulcanizing agent: 0.2-12 parts by weight;
accelerator (b): 0.2-6 parts by weight;
an anti-aging agent: 0.5-8 parts by weight;
wherein the accelerator is one or a mixture of more of PDM, TAIC and TAC;
the anti-aging agent is one or a mixture of more of phenols, imidazoles and waxes;
the preparation method of the sealing material comprises the following steps:
mixing for the first time: mixing EPDM raw rubber, reinforcing carbon black, a plasticizer, a release agent and an anti-aging agent, and cooling to obtain a rubber compound;
and (3) mixing for the second time: mixing the rubber compound, a peroxide vulcanizing agent and an accelerator to obtain a second mixing product;
die pressing: carrying out die pressing on the second mixing product to obtain a die pressing product with a set shape and size;
microwave vulcanization: putting the mould pressing product into microwave vulcanization equipment for microwave vulcanization to obtain a sealing material; wherein the microwave vulcanization temperature is 120-150 ℃, and the microwave vulcanization time is 2-10min.
2. The sealing material according to claim 1, wherein the raw material of the sealing material comprises 100 parts by weight of raw EPDM rubber.
3. The sealing material according to claim 1,
the ethylene content in the EPDM raw rubber is 40-60wt%; and/or
The content of the diene in the EPDM raw rubber is 3-15wt%.
4. The sealing material according to claim 1,
the reinforcing carbon black is one or a mixture of N550 carbon black and N774 carbon black; and/or
The plasticizer is one or a mixture of two of paraffin oil and PAO; and/or
The release agent is stearic acid; and/or
The peroxide vulcanizing agent is one or a mixture of more of DCP, DTBP and BPMC.
5. The sealing material according to claim 1,
the phenols are phenol antioxidants 1010; and/or
2-mercaptobenzimidazole is selected as the imidazole; and/or
The wax is microcrystalline wax.
6. Sealing material according to any of claims 1 to 5,
the Shore A hardness of the sealing material is 45-75; and/or
The tear strength of the sealing material is 40-80kN/m.
7. The sealing material according to claim 6,
the Shore A hardness of the sealing material is 50-60; and/or
The tear strength of the sealing material is 50-60kN/m.
8. The sealing material according to claim 1,
the first mixing step is carried out in an internal mixer; and/or
The second mixing step is carried out in an open mill; and/or
In the first mixing step: the mixing treatment time is 2-8min; the temperature of the mixing treatment is 115-125 ℃.
9. The sealing material according to claim 8, wherein in the first kneading step: the mixing time is 4-6min.
10. A fuel cell comprising a sealing structure, wherein the sealing structure is the sealing material according to any one of claims 1 to 9; wherein the sealing structure is used for sealing the membrane electrode assembly in the fuel cell between the bipolar plates.
11. The fuel cell of claim 10, wherein the fuel cell is a proton exchange membrane fuel cell.
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| CN202010929014.7A CN112225999B (en) | 2020-09-07 | 2020-09-07 | Sealing material, preparation method and application thereof, and fuel cell |
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| CN202010929014.7A CN112225999B (en) | 2020-09-07 | 2020-09-07 | Sealing material, preparation method and application thereof, and fuel cell |
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|---|---|---|---|---|
| CN101701628A (en) * | 2009-11-23 | 2010-05-05 | 青岛开世密封工业有限公司 | Insulation pressure-resistant liner mouth sealing ring and preparation method thereof |
| CN103421248A (en) * | 2012-05-16 | 2013-12-04 | 江阴市文明体育塑胶有限公司 | Ethylene-propylene rubber particles of active hydrogen-containing compound, and production method thereof |
| CN108219300A (en) * | 2018-03-02 | 2018-06-29 | 合肥铭佑高温技术有限公司 | A kind of temperature variation resistant rubber for Air-conditioning Cycle pipe insulation |
| CN110265686A (en) * | 2019-06-27 | 2019-09-20 | 上海骥翀氢能科技有限公司 | The metal plate fuel battery list pool structure and pile of long-life and reliability |
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2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701628A (en) * | 2009-11-23 | 2010-05-05 | 青岛开世密封工业有限公司 | Insulation pressure-resistant liner mouth sealing ring and preparation method thereof |
| CN103421248A (en) * | 2012-05-16 | 2013-12-04 | 江阴市文明体育塑胶有限公司 | Ethylene-propylene rubber particles of active hydrogen-containing compound, and production method thereof |
| CN108219300A (en) * | 2018-03-02 | 2018-06-29 | 合肥铭佑高温技术有限公司 | A kind of temperature variation resistant rubber for Air-conditioning Cycle pipe insulation |
| CN110265686A (en) * | 2019-06-27 | 2019-09-20 | 上海骥翀氢能科技有限公司 | The metal plate fuel battery list pool structure and pile of long-life and reliability |
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