CN101419851A - Conductivity composite material - Google Patents
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- CN101419851A CN101419851A CNA2007101674482A CN200710167448A CN101419851A CN 101419851 A CN101419851 A CN 101419851A CN A2007101674482 A CNA2007101674482 A CN A2007101674482A CN 200710167448 A CN200710167448 A CN 200710167448A CN 101419851 A CN101419851 A CN 101419851A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a conductive composite material which contains 5-40wt% of multipolymer and 60-95wt% of filler; wherein, the multipolymer is chosen from the multipolymer of end ethylene modifier rubber- styrene- divinylbenzene, the multipolymer of end ethylene modifier rubber- styrene, or the multipolymer of styrene- divinylbenzene. The flexible conductive composite material has the characteristics of high conductivity, high mechanical strength, flexible property and the like, and can be mixed with graphite molecules to form a conductive bipolar plate. The invention also relates to an electrode which is formed by the conductive composite material.
Description
Technical field
The invention relates to the preparation of polymer composite, refer in particular to copolymer or the copolymer of styrene-divinylbenzene and the conducing composite material that conductive filler is made of a kind of copolymer that utilizes terminal ethene to modify rubber-styrene-divinylbenzene, terminal ethene modification rubber-styrene, it can be used as the electrode in the electrochemical reaction, be applied to fuel cell, so that the systematic electricity source to be provided more.
Background technology
Please refer to shown in Figure 1, Proton Exchange Membrane Fuel Cells 10 (proton exchange membrane fuelcell is hereinafter to be referred as PEMFC) by a proton exchange membrane 1 be sandwiched in two catalyst layers 2, diffusion layer 3, bipolar plates 4 (bipolar plate), collector plate 5 (current collector), and end plate 6 (endplate) between institute form.The both sides that mea is separated are adhered to anode (hydrogen or reorganization gas) and negative electrode (oxygen or air) separately.Anode carries out oxidation reaction, negative electrode carries out reduction reaction, when the hydrogen of anode touches the catalyst layer 2 (be generally platinum or platinum alloy) adjacent with proton exchange membrane 1, hydrogen molecule can dissociate becomes hydrogen ion and electronics, wherein electronics can be via being connected anode and the electric bridge of negative electrode, the device that is connected in series with electric bridge, from the past negative electrode of anode trip, hydrogen ion then directly passes through mea from anode and arrives negative electrode, ben is that this mea is to contain moist film, only allow that hydrogen ion follows hydrone to pass through, and other gas molecule can't pass through all.Cathode terminal is under the effect of catalyst, and the electronics and the oxygen that arrive via electric bridge are combined into oxonium ion, combines with the hydrogen ion that passes through proton exchange membrane 1 to form hydrone, Here it is electrochemical oxidation and reduction reaction.
Applied Electrochemistry reaction makes the PEMFC electricity generation system have efficient height, pollution-free, characteristic such as reaction is fast, and can improve bridge voltage or increase the electrode reaction area by series connection to improve the magnitude of current, particularly under hydrogen and oxygen (using air usually) are endlessly supplied with, the sustainable demand that power supply device is provided.Under such characteristics, PEMFC also can be designed to large power plant, distributed power and packaged type electric power except can be used as mini-system electric power.
The bipolar plates of fuel cell accounts for the major part of overall volume and weight, so the bipolar plate material research and development are important indicators of fuel cell development.The effect of bipolar plates comprises: distribute conduction and the fixed film electrode group of reacting gas to reacting gas, electric energy and heat energy such as conversion zone, the hydrogen of separating both sides and oxygen, because bipolar plates is in the conversion zone of fuel cell, therefore need possess chemical resistance and heat-resisting character.In addition, the volume utilization rate of lifting bipolar plates also is to need the subject under discussion of research and development badly with reducing its density.Generally speaking, the primary demand of bipolar plates is conductivity, air-tightness, chemical resistance, thermal endurance, lightweight and thin partization, high mechanical properties and low surface roughness.In specific demand, must have good working properties.Bipolar plates is except meeting above-mentioned specification demand, and prior necessary its cost that reduces comprises material cost and technology cost, and the technology of mass production must be arranged.Have low price and well-behaved bipolar plate assembly, will make fuel cell have more the market competitiveness.
The bipolar plates of conventional art comprises high fine and close carbon plate, compound carbon plate and metallic plate, and the bipolar plates of using at PEMFC, its material mostly is high solid graphite material, and except the material cost costliness, the machining of flow-field channel expense also is expensive expenditure.Therefore, for reducing cost of bipolar plates, utilize traditional composite technology to cooperate fuel cell to be main flow trend.The prescription and the generation type of change composite material cooperate pressing mold or ejection forming technique, can make the bipolar plates that is applicable to fuel cell.With traditional composite technology, material is many can to use mass-produced chemicals, and cost of material is cheap.Moreover high fine and close carbon plate is made into tabular more, must just can use via machining, but the runner and the position, hole of the design of polymer composite straight forming just reduces a large amount of processing costs.In addition, high fine and close carbon plate is a made from porous material, must be via reprocessing with the filling hole, and the cost of reprocessing and mass production all are its significant problems.Otherwise the air-tightness of the material that utilizes composite technology to make own is all good than carbon plate, more needn't clog hole.Generally speaking, be the optimal selection of bipolar plates with the compound carbon plate use level of macromolecule production. art.
TaiWan, China patent announcement numbers 399,348 have disclosed a kind of method of making fuel battery double plates, this method comprises hybrid conductive material, resin and hydrophilizing agent, and in 250 ℃ to 500 ℃ temperature range and about 500psi to 4000psi pressure limit, the moulding bipolar plates.Wherein resin comprises thermoplastic resin, thermosetting resin, and electric conducting material can be graphite powder, carbon black, carbon fiber or the like.
United States Patent (USP) the 6th, 436 has disclosed a kind of fuel cell composite material double pole plate No. 315, and with the ejection forming technique of improvement, penetrating resin is bipolar plates with the powdered graphite mixture forming, and is classified and define for various additive.
United States Patent (USP) the 6th, 248 has disclosed a kind of fuel cell composite material double pole plate No. 467, utilizes vinyl ester group resin (vinylester resin) to mix with powdered graphite, and wherein the graphite powder particle diameter is mainly in 80 mesh to 325 meshes.
The early stage publication number 2005/0001352A1 of the U.S. has disclosed a kind of fuel cell composite material double pole plate, utilizes vinyl ester group resin (vinyl ester resin) to mix with powdered graphite, and wherein the graphite powder particle diameter is mainly in 10 mesh to 80 meshes.
But, aforementioned conventional conducing composite material electrical conductivity deficiency, electric power generation cell is not good, under the requirement of large power plant, distributed power system or packaged type electric power system, is difficult to supply continuously electric power, and range of application is subjected to certain restriction.Therefore, how breaking through this bottleneck, will be the part of most critical in the compound carbon plate technology of macromolecule.
Summary of the invention
Be its flexibility of conducing composite material of solution conventional art and the problem of electrical conductivity deficiency, the purpose of this invention is to provide a kind of conducing composite material, it possesses advantages such as pliability, high conductivity, corrosion resistance, air-tightness, lightening, high mechanical properties and low surface roughness, with the direct blending of graphite in resin, can be made into the bipolar plates of high electrical conductivity behind the mould hardened forming.
A further object of the present invention provides a kind of electrode, and preferably the bipolar plates of a proton exchanging film fuel battery is to utilize described conducing composite material obtained, has the described characteristic of this material.
For reaching above-mentioned purpose, the invention provides a kind of conducing composite material, this conducing composite material comprises: the copolymer of 5-40 weight %; And the conductive filler of 60-95 weight %; Wherein, described copolymer is selected from: terminal ethene is modified the copolymer of rubber-styrene-divinylbenzene, terminal ethene is modified the copolymer of rubber-styrene or the copolymer of styrene-divinylbenzene.
Described conductive filler comprises graphite powder, carbon fiber, expanded graphite, carbon black, coke, CNT (carbon nano-tube) or its composition; The mixture of graphite powder, carbon fiber and expanded graphite more preferably.According to of the present invention one concrete preferred embodiment, described conductive filler is the mixture of the expanded graphite of the carbon fiber of graphite powder, 30wt%-5wt% of 65wt%-90wt% and 5wt%-10wt%.
The copolymer that described terminal ethene is modified rubber-styrene-divinylbenzene is to be formed by following ingredients combined polymerization in the presence of free radical starting agent: the terminal ethene of 1-20 weight % is modified rubber; The styrene of 60-98 weight %; And the divinylbenzene of 1-20 weight %.And should end ethene modifying terminal ethene in the copolymer of rubber-styrene-divinylbenzene, to modify rubber be to be formed by acrylonitrile and polymerizing butadiene.
It is to be formed by following ingredients combined polymerization in the presence of free radical starting agent that described terminal ethene is modified rubber-styrene: the terminal ethene of 1-90 weight % is modified rubber; And the styrene of 10-99 weight %.
The copolymer of described styrene-divinylbenzene is to be formed by following ingredients combined polymerization in the presence of free radical starting agent: the styrene of 90-99 weight %; And the divinylbenzene of 1-10 weight %.
Described free radical starting agent comprises t-butyl peroxybenzoate (benzoyl hydroperoxide tributyl ester) or benzoyl hydroperoxide.
Described terminal ethene in the described conducing composite material is modified rubber and is comprised polybutadiene, natural rubber, polyisobutylene, styrene butadiene rubbers, butyl rubber, nitrile rubber, ethylene propylene rubber, polychlorobutadiene, polyvinyl chloride, siloxane polymer, Viton or its combination.
Described terminal ethene is modified the weight molecular weight of rubber between 1000-10000; Be more preferably between 4500-5500.
Described conducing composite material can further comprise rheology control agent or release agent; This conditioning agent is a magnesium oxide, and this release agent then comprises the plain wax of fluorine, metallic soap, chloroflo, polyethylene, amide waxe, aliphatic acid, fatty alcohol or fatty ester.
The present invention also provides a kind of electrode, and it is made of described conducing composite material, is preferably the bipolar plates of Proton Exchange Membrane Fuel Cells.
Compare with traditional material, conducing composite material electrical conductivity provided by the present invention is higher, after making Proton Exchange Membrane Fuel Cells, more applicable to large-scale or mobile power system.
Description of drawings
Fig. 1 is the generalized section of Proton Exchange Membrane Fuel Cells.Wherein, 1 is proton exchange membrane, and 2 is catalyst layer, and 3 is diffusion layer, and 4 is bipolar plates, and 5 is collector plate, and 6 is end plate, and 10 is Proton Exchange Membrane Fuel Cells.
Fig. 2 is the schematic diagram of expanded graphite structure.
Fig. 3 is the electron micrograph of expanded graphite structure.
Fig. 4 is to use the performance evaluation curve chart of the material prepared fuel battery of embodiment 1.
Embodiment
Be flexibility and the electrical conductivity that improves compound carbon plate, the present invention mainly utilizes the mono-layer graphite molecule as the additional conductive material, and conducing composite material provided by the invention comprises the copolymer of 5-40wt% and the conductive filler of 60-95wt%; Wherein, described copolymer is selected from: terminal ethene is modified the copolymer of rubber-styrene-divinylbenzene, terminal ethene is modified the copolymer of rubber-styrene or the copolymer of styrene-divinylbenzene.
General suitable conductive filler can be graphite powder, carbon fiber, carbon black, coke, CNT (carbon nano-tube), metal powder, metal wire or above-mentioned combination, but above-mentioned conductive filler can't be dissolved among the resin, in order in resin, to add soluble conduction material to increase the electrical conductivity of integral composite, soluble graphite oxide is best selection, the appearance that graphite oxide (graphite oxide) wherein contains the oxygen chemical based causes bulk shape graphite to separate fully, graphite oxide expanded later rapidly graphite linings strutted with 1000 ℃ of processing becomes graphite flake, its structure and electron micrograph such as Fig. 2, shown in Figure 3.In addition, and further utilize the bond of the polymer of the end modified rubber of ethene, polystyrene and divinylbenzene as conductive filler, make this composite material possess conductivity, corrosion resistance, air-tightness, lightening, high flexibility, and the characteristics of surperficial low roughness, can be applicable to the electric conducting material in the corrosive environment such as electrochemical electrode.
In the preferred enforcement aspect of the present invention, conducing composite material comprises: the conductive filler of the copolymer of 5-40 weight % and 60-95 weight %; Wherein said conductive filler is the mixture of graphite powder, carbon fiber and expanded graphite; For example, this conductive filler is the mixture of the expanded graphite of the carbon fiber of graphite powder, 30wt%-5wt% of 65wt%-90wt% and 5wt%-10wt%.
In the copolymer that the present invention uses, the tridimensional network that end modified rubber of ethene (VTBN) and styrene and divinylbenzene copolymer form is as shown in the formula (I); The copolymer structure that styrene and divinylbenzene form is as shown in the formula (II); Terminal ethene is modified copolymer structure that rubber and styrene forms as shown in the formula (III):
Chemical structural formula (I)
Chemical structural formula (II)
Chemical structural formula (III)
R: the copolymer of acrylonitrile-butadiene is the long-chain molecule of skeleton.
In the preferred enforcement aspect of the present invention, this copolymer is the copolymer that terminal ethene is modified rubber-styrene-divinylbenzene.
Described terminal ethene is modified the copolymer of rubber-styrene-divinylbenzene, is to be formed by following ingredients combined polymerization in the presence of free radical starting agent: the terminal ethene of 1-20 weight % is modified rubber; The styrene of 60-98 weight %; And the divinylbenzene of 1-20 weight %.Described terminal ethene is modified rubber and cinnamic copolymer, is to be formed by following ingredients combined polymerization in the presence of free radical starting agent: the terminal ethene of 1-90 weight % is modified rubber; And the styrene of 10-99 weight %.The copolymer of described styrene and divinylbenzene is to be formed by following ingredients combined polymerization in the presence of free radical starting agent: the styrene of 90-99 weight %; And the divinylbenzene of 1-10 weight %.
Described terminal ethene is modified rubber and is preferably formed by acrylonitrile, polymerizing butadiene.
In a preferred embodiment, rubber modified by described terminal ethene and cinnamic copolymer is the copolymer of acrylonitrile-butadiene-styrene (ABS), and it is to be formed by following ingredients combined polymerization in the presence of free radical starting agent: the acrylonitrile of 14-64 weight %; The butadiene of 4-24 weight %; And the styrene of 20-80 weight %.
The free radical starting agent that the present invention is suitable for include, but are not limited to t-butyl peroxybenzoate (benzoyl hydroperoxide tributyl ester, TBPB) or benzoyl hydroperoxide.
Visual its of conducing composite material of the present invention needs, and further adds rheology control agent or release agent, and rheology control agent for example but is not limited to magnesium oxide; Release agent for example but is not limited to the plain wax of fluorine, metallic soap, chloroflo, polyethylene, amide waxe, aliphatic acid, fatty alcohol or fatty ester, and its addition also can be adjusted according to the actual process needs, is not particularly limited.Also can add the polystyrene shrinking agent according to circumstances, shrink the scale error that is caused during with the reduction moulding.
Simultaneously, the present invention also provides a kind of by the electrode that described conducing composite material constituted, for example: the bipolar plates of Proton Exchange Membrane Fuel Cells.Basically, because conducing composite material provided by the invention, it possesses outside the characteristics such as conductivity, corrosion resistance, air-tightness, the more important thing is that this composite material has more high electrical conductivity and high flexibility compared to traditional material, and more lightening, so can be widely used in various electrochemistry or association area.
Conducing composite material of the present invention is after moulding, the bending strength of its finished product is greater than 6000psi, hot strength is greater than 3400psi, conductivity is between 150-200S/cm, and have characteristics such as corrosion resistance, air-tightness, therefore be suitable as the bipolar plates of electrode material, particularly Proton Exchange Membrane Fuel Cells.The porous bipolar plates of this battery has that combustion gas chemical reaction efficiency height, electric power generation cell are big, battery manufacturing and design cost is low, and various advantages such as overall weight and volume be little, can be applicable to the electric power system of means of transportations such as vehicle, ship, aircraft.
Below utilize embodiments of the invention to describe technology of the present invention and characteristics in detail, yet these embodiment are not in order to limit the present invention, any those of ordinary skill in the art, without departing from the spirit and scope of the present invention, when being used for a variety of modifications and variations.
Embodiment
Embodiment 1: VTBN-styrene-divinylbenzene co-polymer with contain the sheet material that expanded graphite carbon material is made
Preparation of Expanded Graphite:
The graphite oxide 200g that buys is put into 3 liters stainless steel tank, send into rapidly in 1000 ℃ of high temperature furnaces, heating made its expansion in 60 seconds under air.Finish that to take out under room temperature cooling after the expansion standby.
The preparation of bipolar plates:
Mediate with VTBN-styrene-divinylbenzene co-polymer and carbon material end, form even model mixture (BMC, bulk molding compound), wherein said carbon material (graphite powder+expanded graphite+carbon fiber) content is at 75 weight %.Free radical starting agent is t-butyl peroxybenzoate (TBPB), and solvent is a styrene, and remover is the plain wax (fluorine wax) of fluorine.Above-mentioned material select principle for use except the character that is fit to bipolar plates, reasonable price also is a Consideration.The ratio of various materials as shown in Table 1.The bipolar plates that present embodiment is made is formed the fuel cell of single-cell structure, and according to testing its performance according to the monocell method known to the present technique field, its test condition is as follows: hydrogen/air (flow 1:1); Article 16, serpentine flow path; Bipolar plates area 20cm*20cm; Response area 16cm*16cm; 65 ℃ of reaction temperatures.Result after tested as shown in Figure 4, at 0-600mA/cm
2Battery current density output voltage be 0.6-0.9V, show that by this figure the fuel cell that utilizes bipolar plates of the present invention to make has good electricity generation efficiency.
Table one
※ phr is the abbreviation of Parts per Parts Hundred Resin.For instance, 100 parts VTBN-divinylbenzene-styrene copolymerized compound is the plain wax of fluorine of 1phr to the plain wax of 1 part fluorine.
The process of embodiment 1 is as follows:
A. with VTBN 200g, divinylbenzene 50g and styrene 750g, free radical starting agent TBPB30g, insert in the beaker with the plain cured 30g of remover fluorine.
B. the solution that a is mixed places high speed agitator, stirs 10 to 20 minutes with the oil-in-water type blade.
C. pour above-mentioned solution and graphite powder 2600g, carbon fiber 200g, expanded graphite 200g into model mixture kneader (BMC Kneader), mediated 60 to 90 minutes with strong (Masticator) stirring vane.
D. preheating hot pressing die to 180 ℃ is got the mixture that an amount of above-mentioned steps makes again, it is inserted penetrate among the cylinder.
E. after the mixture that above-mentioned steps is made was inserted and penetrated cylinder, mould matched moulds to pressing mold pressure up and down reached 100 to 200kg/cm
2, and persistent pressure 3 minutes, make mixture cures.
F. the finished product demoulding was placed on 180 ℃ of baking ovens 24 hours with the taking-up of mold pressing finished product, hardened fully to guarantee mixture.
Comparative example 1: the sheet material that VTBN-styrene-divinylbenzene co-polymer and carbon material are made
Comparative example 1 is that VTBN-styrene-divinylbenzene co-polymer and carbon material are mediated the even model mixture (BMC, bulk molding compound) that forms, and carbon material (graphite powder+carbon fiber) content is about 75 weight %.Free radical starting agent is t-butyl peroxybenzoate (TBPB), and solvent is a styrene, and remover is the plain wax (fluorine wax) of fluorine.Above-mentioned substance select for use principle with embodiment 1.The ratio of various materials is referring to table one.
The process of comparative example 1 is as follows:
A. with VTBN 200g, divinylbenzene 50g and styrene 750g, free radical starting agent TBPB30g, insert in the beaker with the plain cured 30g of remover fluorine.
B. the solution that a is mixed places high speed agitator, stirs 10 to 20 minutes with the oil-in-water type blade.
C. with above-mentioned solution and graphite powder 2800g, carbon fiber 200g, pour model mixture kneader (BMC Kneader) into, mediated 60 to 90 minutes with strong (Masticator) stirring vane.
D. when ejection formation, must look-ahead and the appropriate mixture of scale, it is inserted penetrate among the cylinder.Before this step, hot pressing die must be heated to 180 ℃ earlier.
E. after mixture being inserted the ejaculation cylinder, mould matched moulds to pressing mold pressure up and down reaches 100 to 200kg/cm
2, and persistent pressure 3 minutes, make mixture cures.
F. the finished product demoulding was placed on 180 ℃ of baking ovens 24 hours with the taking-up of mold pressing finished product, hardened fully to guarantee mixture.
The physical property measurement of the sheet material that following table two is made for above embodiment 1 and comparative example 1:
Table two
| Embodiment 1 5wt% expanded graphite | Comparative example 1 expanded graphite 0wt% | |
| Resistivity (specific resistance) | 0.00583Ω-cm | 0.00640Ω-cm |
| Compression strength (compress strength) | 6217psi | 6215psi |
By table two result as can be known, embodiments of the invention 1 are because of adding expanded graphite as conductive filler, therefore the electrical conductivity of the sheet material of making obviously promotes compared to comparative example 1, and compression strength can't be affected, obvious conducing composite material of the present invention can increase electrical conductivity, more is applicable to the bipolar plates of making in the battery.
Embodiment 2: the sheet material that styrene copolymerized compound of VTBN-and carbon material are made
Mediate with styrene copolymerized compound of VTBN-and carbon material, form even model mixture (BMC, bulkmolding compound), wherein carbon material (powdered graphite+carbon fiber) content 75 weight %.Free radical starting agent is t-butyl peroxybenzoate (TBPB), and solvent is a styrene, and remover is the plain wax (fluorine wax) of fluorine.Above-mentioned material select principle for use except the character that is fit to bipolar plates, reasonable price also is a Consideration; The ratio such as the table three of various materials.
Table three
| Material | Embodiment 2 | Comparative example 2 | Comparative example 3 |
| Graphite powder+carbon fiber | 75％ | 75％ | 75％ |
| VTBN | 12.5％ | ||
| Rubber-reinforced vinyl ester group resin | 15％ | ||
| Vinyl ester group resin | 15％ | ||
| Styrene monomer | 12.5％ | 10％ | 10％ |
| T-butyl peroxybenzoate (TBPB) | 3phr | 3phr | 3phr |
| The plain wax of fluorine | 3phr | 3phr | 3phr |
※ Phr is the abbreviation of Parts per Parts Hundred Resin.In table three, the plain wax of the fluorine of 1phr is meant that corresponding 100 parts total amount of material adds 1 part the plain wax of fluorine, and described total amount of material is meant the summation of the rubber-reinforced vinyl ester group resin of VTBN++vinyl ester group resin+styrene monomer.
The process of embodiment 2 is as follows:
A. VTBN 500g and styrene 500g, free radical starting agent TBPB 30g and the plain cured 30g of remover fluorine are inserted in the beaker.
B. the solution that a is mixed places high speed agitator, stirs 10 to 20 minutes with the oil-in-water type blade.
C. with above-mentioned solution and graphite powder 2950g, carbon fiber 50g, pour model mixture kneader (BMC Kneader) into, mediated 60 to 90 minutes with strong (Masticator) stirring vane.
D. when ejection formation, must look-ahead and the appropriate mixture of scale, it is inserted penetrate among the cylinder.Before this step, hot pressing die must be heated to 180 ℃ earlier.
E. after mixture being inserted the ejaculation cylinder, mould matched moulds to pressing mold pressure up and down reaches 100 to 200kg/cm
2, and persistent pressure 3 minutes, make mixture cures.
F. the finished product demoulding was placed on 180 ℃ of baking ovens 24 hours with the taking-up of mold pressing finished product, hardened fully to guarantee mixture.
Comparative example 2: the sheet material that rubber-reinforced vinyl ester group resin and carbon material are made
Comparative example 2 is that rubber-reinforced vinyl ester group resin and carbon material are mediated the even model mixture (BMC that forms, bulk molding compound), wherein rubber-reinforced vinyl ester group resin accounts for 15 weight %, and carbon material (graphite powder+carbon fiber) content is about 75 weight %.Free radical starting agent is t-butyl peroxybenzoate (TBPB), and solvent is that styrene accounts for 10 weight %, and remover is the plain wax (fluorinewax) of fluorine.Above-mentioned substance select for use principle with embodiment 2.The ratio of various materials is referring to table three.
The process of comparative example 2 is as follows:
A. the plain cured 30g of rubber-reinforced vinyl ester group resin 600g, styrene monomer 400g, free radical starting agent 30g and fluorine is placed beaker.
B. the solution that a is mixed places high speed agitator, stirs 10 to 20 minutes with the oil-in-water type blade.
C. with above-mentioned solution and graphite powder 2800g, carbon fiber 200g, pour model mixture kneader (BMC Kneader) into, mediated 60 to 90 minutes with strong (Masticator) stirring vane.
D. when ejection formation, must look-ahead and the appropriate mixture of scale, it is inserted penetrate among the cylinder.Before this step, hot pressing die must be heated to 180 ℃ earlier.
E. after mixture being inserted the ejaculation cylinder, mould matched moulds to pressing mold pressure up and down reaches 100 to 200kg/cm
2, and persistent pressure 3 minutes, make mixture cures.
F. the finished product demoulding was placed on 180 ℃ of baking ovens 24 hours with the taking-up of mold pressing finished product, hardened fully to guarantee mixture.
Comparative example 3: the sheet material that vinyl ester group resin and carbon material are made
Comparative example 3 is that vinyl ester group resin and carbon material are mediated, the even model mixture (BMC that forms, bulk molding compound), therein ethylene base ester base resin accounts for 15wt%, carbon material (graphite powder+carbon fiber) content is about 75wt%, solvent is that styrene accounts for 10 weight %, and free radical starting agent TBPB 30g, remover are the plain wax (fluorine wax) of fluorine.Above-mentioned substance select for use principle with embodiment 2.The ratio of various materials is referring to table three.
The process of comparative example 3 is as follows:
A. solvent is inserted in the container in advance, add the plain wax 30g of vinyl ester group resin 600g, free radical starting agent 30g and remover fluorine respectively.
B. the solution that a is mixed places high speed agitator, stirs 10 to 20 minutes with the oil-in-water type blade.
C. with above-mentioned solution and graphite powder 2950g, carbon fiber 50g, pour model mixture kneader (BMC Kneader) into, mediated 60 to 90 minutes with strong (Masticator) stirring vane.
D. when ejection formation, must look-ahead and the appropriate mixture of scale, it is inserted penetrate among the cylinder.Before this step, hot pressing die must be heated to 180 ℃ earlier.
E. after mixture being inserted the ejaculation cylinder, mould matched moulds to pressing mold pressure up and down reaches 100 to 200kg/cm
2, and persistent pressure 3 minutes, make mixture cures.
F. the finished product demoulding was placed on 180 ℃ of baking ovens 24 hours with the taking-up of mold pressing finished product, hardened fully to guarantee mixture.
The characteristic of the composite material that the foregoing description 2, comparative example 2 and comparative example 3 are made is shown in following table four, wherein embodiment 2 is to use the end modified rubber of ethene of the present invention and styrene as the copolymer (being the VTBN-Styrene copolymer) of the crosslinking agent composite finished product as the bond (binder) of graphite powder, and comparative example 2 is ordinary rubber to be strengthened vinyl ester group resin mix with graphite; And comparative example 3 is only general vinyl ester group resin directly to be mixed with graphite merely.By the result of table four as can be known, the finished product flexibility that embodiment 2 makes is obviously better than comparative example 2 and comparative example 3, the electrical conductivity part is also preferable, shows that conductive composite material of the present invention has better characteristic than general electric conducting material really, is a kind of bendable and high conductivity composite material.
Table four
| Characteristic | Embodiment 2 | Comparative example 2 | Comparative example 3 |
| Flexibility (%) | 32％ | 6.2％ | 1.5％ |
| Heat resisting temperature (℃) | 200 | 200 | 200 |
| Electrical conductivity (S/cm) | 155 | 152 | 148 |
| Corrosion stability (μ A/cm 2) (in the aqueous sulfuric acid of 0.5M) | <1 | <1 | <1 |
| Proportion | 1.57 | 1.65 | 1.62 |
| Air-tightness | Good | Good | Good |
Claims (18)
1, a kind of conducing composite material, this conducing composite material comprises:
The copolymer of 5-40 weight %; And
The conductive filler of 60-95 weight %;
Wherein, described copolymer is selected from: terminal ethene is modified the copolymer of rubber-styrene, terminal ethene is modified the copolymer of rubber-styrene-divinylbenzene or the copolymer of styrene-divinylbenzene.
2, conducing composite material as claimed in claim 1, wherein said conductive filler comprise graphite powder, carbon fiber, expanded graphite, carbon black, coke, CNT (carbon nano-tube) or its composition.
3, conducing composite material as claimed in claim 1, wherein said conductive filler are the mixture of the expanded graphite of the carbon fiber of graphite powder, 30%-5% of 65%-90% and 5%-10%.
4, conducing composite material as claimed in claim 1, the copolymer that wherein said terminal ethene is modified rubber-styrene is to be formed by following ingredients combined polymerization in the presence of free radical starting agent:
The terminal ethene of 1-90 weight % is modified rubber; And
The styrene of 10-99 weight %.
5, conducing composite material as claimed in claim 1, the copolymer that wherein said terminal ethene is modified rubber-styrene-divinylbenzene is to be formed by following ingredients combined polymerization in the presence of free radical starting agent:
The terminal ethene of 1-20 weight % is modified rubber;
The styrene of 60-98 weight %; And
The divinylbenzene of 1-20 weight %.
6, conducing composite material as claimed in claim 1, the copolymer of wherein said styrene-divinylbenzene are to be formed by following ingredients combined polymerization in the presence of free radical starting agent:
The styrene of 90-99 weight %; And
The divinylbenzene of 1-10 weight %.
7, conducing composite material as claimed in claim 4, wherein said free radical starting agent comprises t-butyl peroxybenzoate or benzoyl hydroperoxide.
8, conducing composite material as claimed in claim 5, wherein said free radical starting agent comprises t-butyl peroxybenzoate or benzoyl hydroperoxide.
9, conducing composite material as claimed in claim 6, wherein said free radical starting agent comprises t-butyl peroxybenzoate or benzoyl hydroperoxide.
10, conducing composite material as claimed in claim 1, wherein said terminal ethene are modified rubber and are comprised polybutadiene, natural rubber, polyisobutylene, styrene butadiene rubbers, butyl rubber, nitrile rubber, ethylene propylene rubber, polychlorobutadiene, polyvinyl chloride, siloxane polymer, Viton or its combination.
11, conducing composite material as claimed in claim 1, it is to be formed by acrylonitrile and polymerizing butadiene that wherein said terminal ethene is modified rubber.
12, conducing composite material as claimed in claim 1, wherein said terminal ethene is modified the weight molecular weight of rubber between 1000-10000.
13, conducing composite material as claimed in claim 12, wherein said terminal ethene is modified the weight molecular weight of rubber between 4500-5500.
14, conducing composite material as claimed in claim 1, this conducing composite material further comprises rheology control agent or release agent.
15, conducing composite material as claimed in claim 14, wherein said rheology control agent are magnesium oxide.
16, conducing composite material as claimed in claim 14, wherein said release agent comprise the plain wax of fluorine, metallic soap, chloroflo, polyethylene, amide waxe, aliphatic acid, fatty alcohol or fatty ester.
17, a kind of electrode, this electrode are made of the described conducing composite material of claim 1.
18, electrode as claimed in claim 17, it is the bipolar plates of Proton Exchange Membrane Fuel Cells.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007101674482A CN101419851B (en) | 2007-10-25 | 2007-10-25 | Conductivity composite material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007101674482A CN101419851B (en) | 2007-10-25 | 2007-10-25 | Conductivity composite material |
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| CN101419851A true CN101419851A (en) | 2009-04-29 |
| CN101419851B CN101419851B (en) | 2012-05-23 |
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| CN2007101674482A Active CN101419851B (en) | 2007-10-25 | 2007-10-25 | Conductivity composite material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012824A (en) * | 2012-12-27 | 2013-04-03 | 复旦大学 | Graphene oxide-polymer hybrid proton exchange membrane and preparation method thereof |
| CN105419673A (en) * | 2015-12-29 | 2016-03-23 | 舜坦（上海）新材料有限公司 | Conductive floor glue |
| CN105598150A (en) * | 2016-03-16 | 2016-05-25 | 江西省环境保护科学研究院 | Electrode system and electric soil remediation method |
| CN109831838A (en) * | 2019-04-03 | 2019-05-31 | 浙江杭州日盛电热制品有限公司 | The electric heating plastic cord or piece and production method being made of far infrared nano material |
| CN113122075A (en) * | 2019-12-31 | 2021-07-16 | 绵阳市中野科技有限公司 | Elastic conductive composite material, preparation method thereof, elastic coating film and electric appliance element |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6436315B2 (en) * | 1999-03-19 | 2002-08-20 | Quantum Composites Inc. | Highly conductive molding compounds for use as fuel cell plates and the resulting products |
| EP1324411A3 (en) * | 2001-12-26 | 2004-12-22 | Mitsubishi Chemical Corporation | Composite material for fuel cell separator molding and production method thereof, and fuel cell separator which uses the composite material and production method thereof |
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2007
- 2007-10-25 CN CN2007101674482A patent/CN101419851B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012824A (en) * | 2012-12-27 | 2013-04-03 | 复旦大学 | Graphene oxide-polymer hybrid proton exchange membrane and preparation method thereof |
| CN103012824B (en) * | 2012-12-27 | 2015-03-04 | 复旦大学 | Graphene oxide-polymer hybrid proton exchange membrane and preparation method thereof |
| CN105419673A (en) * | 2015-12-29 | 2016-03-23 | 舜坦（上海）新材料有限公司 | Conductive floor glue |
| CN105598150A (en) * | 2016-03-16 | 2016-05-25 | 江西省环境保护科学研究院 | Electrode system and electric soil remediation method |
| CN109831838A (en) * | 2019-04-03 | 2019-05-31 | 浙江杭州日盛电热制品有限公司 | The electric heating plastic cord or piece and production method being made of far infrared nano material |
| CN109831838B (en) * | 2019-04-03 | 2024-02-20 | 浙江杭州日盛电热制品有限公司 | Electrothermal plastic wire or sheet made of far infrared nano material and its making process |
| CN113122075A (en) * | 2019-12-31 | 2021-07-16 | 绵阳市中野科技有限公司 | Elastic conductive composite material, preparation method thereof, elastic coating film and electric appliance element |
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| CN101419851B (en) | 2012-05-23 |
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