CN101462712A - Modified carbonized base material, and preparation method and use thereof - Google Patents
Modified carbonized base material, and preparation method and use thereof Download PDFInfo
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- CN101462712A CN101462712A CNA2007103005100A CN200710300510A CN101462712A CN 101462712 A CN101462712 A CN 101462712A CN A2007103005100 A CNA2007103005100 A CN A2007103005100A CN 200710300510 A CN200710300510 A CN 200710300510A CN 101462712 A CN101462712 A CN 101462712A
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Abstract
The invention provides a method for modifying a carbonized base material and the modified carbonized base material obtained by the method. The method comprises that: a mixture containing hydrophobic macromolecule and carbon material is applied to the carbonized base material without hydrophobic treatment, thereby modifying the carbonized base material by a relatively simplified procedure and providing the modified carbonized base material with good electrical conductivity, air permeability and hydrophobicity; moreover, the base material is suitable to be used as a material for a gas diffusion layer in an electrode of a fuel cell.
Description
Technical field
The present invention system is about a kind of method for modifying of carbide base material, especially in regard to a kind of method for modifying that can be used as the gas diffusion layers of fuel cell electrode; And gained modified carbonized base material and its purposes.
Background technology
In recent years, because factors such as energy shortage and global greenhouse effects, hydrogen attracts much attention for the development of the fuel cell (fuel cell) of system; Not only lid fuel cell rechargeable battery nothing but uses up the problem of promptly losing in the environmental protection that is caused, and also can exempt the shortcoming that traditional rechargeable battery need carry out charging procedure consuming time.In addition, the discharge of fuel cell (for example water) does not also have harm to environment.
In various fuel cells, Proton Exchange Membrane Fuel Cells (proton exchangemembrane fuel cell, PEMFC) and direct methanol fuel cell (direct methanolfuel cell, DMFC) because of operating at low temperatures, can produce high current density again, so be widely used in the power unit of vehicle, combined generating system and all kinds of 3C Product (as notebook computer, mobile phone etc.).
With PEMFC is example, the primary member of its each monocell comprise mea (membrane-electrode assembly, MEA) and have a bipolar plates (bipolar plates) of gas flow.Generally speaking, MEA system by a proton exchange membrane (being generally a polymeric membrane) as ionogen, lay respectively at these proton exchange membrane both sides two catalyst layers, and place two gas diffusion layers (can be described as " electric pole gaseous diffusion layer " in addition) in these two catalyst layers outsides to be formed respectively.
At present, mostly to adopt porousness carbon paper or carbon cloth be the material of the gas diffusion layers of electrode for PEMFC and DMFC.This diffusion layer is except the passage that can make reactant gases and pass through and move as power supply, because it has the effect of auxiliary water management (water management), the water that event can make in the catalyzed reaction and be produced is got rid of smoothly, hinder the transmission of gas to avoid water flooding, and then influence fuel cell performance.Therefore, the water management capabilities of gas diffusion layers is one of electrical important factor of decision fuel cell.
Influence fuel cell performance for fear of water flooding, can on the carbon back material of gas diffusion layers, do hydrophobic treatment usually, unnecessary water can easily be discharged, to prolong fuel battery service life.Moreover because present carbon cloth and the carbon paper surface irregularity that uses, this can have influence on the reaction and the efficient of catalyst on the catalyst layer; Be with, except hydrophobic treatment, also be necessary smooth processing is carried out on the surface of carbon cloth or carbon paper.
People such as Taniguchi are at United States Patent (USP) the 6th, 083, disclose in No. 638, with fibrous carbon base material (fibrous carbon substrate) earlier after fluoride resin (fluororesin) carries out hydrophobic treatment, 360 ℃ of oven dry down; Then use hydrophobic polymer (hydrophobicpolymer) and hydrophilic macromolecule (hydrophilic polymer) to handle again, and on the carbon back material, produce hydrophobicity and hydrophilic passage.
United States Patent (USP) the 5th, 561, then disclose earlier on carbon cloth or carbon paper that (polytetrafluoroethylene PTFE) carries out hydrophobic treatment, and then in the mixture that is coated with last layer PTFE and carbon on the carbon cloth of PTFE hydrophobic treatment or carbon paper with tetrafluoroethylene for No. 000.
People such as Gorman are the 5th, 561, No. 000 disclosed technology of teaching Modified American patent in WO0 0/54350 then, further handles United States Patent (USP) the 5th, 561, and No. 000 prepared carbon cloth or carbon paper change it and be the hydrophilic works of tool.
United States Patent (USP) the 6th, 733, No. 915 exposure utilize porousness carbon cloth or carbon paper as base material, earlier the carbon back material is contained be dipped in carry out hydrophobic treatment in monofluoride polymer (fluorinated polymer) solution after, again in this mixture that on impregnation carbon back material, is coated with last layer fluorochemical polymer and carbon granule, under high temperature, dry afterwards and obtain through upgrading carbon back material.
United States Patent (USP) the 7th, 063 then discloses in No. 913 patents, earlier porousness carbon back material is carried out pre-treatment with hydrophobic polymer (hydrophobic polymer), carries out drying again and obtains the hydrophobic carbon back material of a tool; Then, be coated with the mixture of last layer fluorine-carbon macromolecule (fluorocarbonpolymer) and carbon granule again, heat-treat again at last.
In brief; prior art is in order to obtain the hydrophobic gas diffusion layer; usually can carry out hydrophobic treatment to obtain the hydrophobic carbon back material of tool to the carbon back material earlier; again carry out such as methods such as coating, impregnation or sprinklings this is used the mixture of hydrophobic polymer and carbon granule through the carbon back material of hydrophobic treatment thereafter; then under high temperature, heat-treat, thereby obtain having on the surface hydrophobic gas diffusion layer material of carbon granule layer.
This case the contriver find after deliberation, and can be relatively easy mode provide the hydrophobicity carbide base material, obtain one have desire the modified carbonized base material of electroconductibility, hydrophobicity, ventilation property and planarization.
Summary of the invention
A purpose of the present invention is to provide a kind of method for modifying of carbide base material, comprises: a carbide base material is provided; One mixture that contains hydrophobic polymer and carbon material is provided; This mixture is applied to the one side at least of this carbide base material; And under protection of inert gas, this carbide base material of thermal treatment.
Another object of the present invention is to provide a kind of modified carbonized base material, comprises a carbide base material and a regulating course, and these leveling series of strata in fact directly are positioned on the one side at least of this carbide base material.
Another purpose of the present invention is to provide a kind of fuel cell, and its characteristics are that its at least one electrode contains aforesaid modified carbonized base material.
Description of drawings
Fig. 1 is a kind of structural representation according to modified carbonized base material of the present invention; And
Fig. 2 is a kind of structural representation of mea of the monocell according to fuel cell of the present invention.
Nomenclature is as follows among the figure:
1,1a, 1b carbide base material
2,2a, 2b regulating course
3a, 3b catalyst layer
Proton exchange membrane
5a, 5b bipolar plates
10 modified carbonized base materials
The carbon material
22 hydrophobic polymers
Embodiment
Used carbide base material in the method for modifying of carbide base material of the present invention is to be selected from following group: carbon cloth, carbon paper, and carbon felt.Further it, any material that can be used as the gas diffusion layers in the fuel cell all can be applied to the inventive method, for example the TGP grade carbon paper produced of Toray company, CPW-003 carbon fabric that Textron USA is produced, TCM128 that Le Carboneloraine is produced and TGM 389 carbon fabrics, Panex PW-03 that Zoltek is produced, SigracetGDL 10AA that SGL is produced, Technimat that Lydell is produced, and the Spectracarb produced of Spectracorp etc.Perhaps, (for example select can Science and Technology Co., Ltd. can to choose on the market carbide base material, the carbon cloth of model: FCW1005) or the carbide base material that makes in a known way (for example U.S. patent application case discloses the carbon fiber paper that No. 2006/0214320 institute's exposure method obtained), handle and carbide base material used in the inventive method is provided through high-temperature heat treatment.
In the inventive method, be directly at least one surface of carbide base material, to use a mixture that contains hydrophobic polymer and carbon material, to form a regulating course in this surface.In this, the hydrophobic polymer that can be used among the present invention is to contain fluorine carbon bond person usually, as long as this fluorine carbon bond can provide the hydrophobicity of being desired.Say it for example, this hydrophobic polymer can be selected from following group: tetrafluoroethylene (polytetrafluoroethylene, PTFE), polyhexafluoropropylene (polyhexafluoropropylene, PHFP), the multipolymer of R 1216 and tetrafluoroethylene (copolymers of hexafluoropropylene and tetrafluoro-ethylene, FEP), the multipolymer of tetrafluoroethylene and perfluoro propyl ethyl ether (copolymers oftetrafluoroethylene and perfluoropropylvinylether, PFA), the multipolymer of tetrafluoroethylene and perfluoro-methyl ethyl ether (copolymers of tetrafluoro-ethylene and perfluoromethylvinylether, MFA), the homopolymer of chlorotrifluoroethylene (homopolymers of chlorotrifluoroethylene, PCTFE), polyvinylidene difluoride (PVDF) (polyvinylidene fluoride, PVDF), fluorinated ethylene propylene (poly (vinylfluoride), PVF), the multipolymer of tetrafluoroethylene and ethene (copolymerof tetrafluoroethylene and ethylene, ETFT), the multipolymer of vinylidene and R 1216 and tetrafluoroethylene (copolymer of vinylidene fluoride, hexafluoro-propylene, and tetrafluoroethylene, THV), and combination; Preferable system is selected from following group: PTFE, FEP, PFA and combination thereof.
According to the present invention, the general system of hydrophobic polymer is used with solution form (as dispersion liquid).Say it for example, can directly use the dispersion liquid that contains hydrophobic polymer that carries out emulsion polymerization reaction gained by monomer; Perhaps, mix hydrophobic polymer powder, solvent, an and interfacial agent and dispersion liquid that contains hydrophobic polymer is provided.At present, the solution product of more existing hydrophobic polymers can be directly used among the present invention on the market; For example, the T30PTFE solution of E.I.Du Pont Company, the NEOFLON FEP ND-20 that Daikin Industries company produces.
Except that hydrophobic polymer, this mixture comprises a carbon material in addition, and it can make the regulating course tool electroconductibility that is formed on this carbide base material, keeps carbide base material inherent conductivity.The carbon material of any suitable form all can be used for the present invention, for example powder carbon material, fibrous carbon material or its combination.Wherein, this carbon material for example can be (but being not limited to): carbon black, graphite, acetylene black or its combination.Say it (but being not limited to) for example, can adopt following powder carbon material: carbon black is (as Cabot company
XC-72, Cabot company
XC-72R, and the N660 of Korea Steel ChemicalCorp.), graphite (electrographite or natural graphite), acetylene black or its combination; Be preferably carbon black.In this, the particle diameter that is used for powder carbon material of the present invention is generally 10 to 200 nanometers, is preferably 15 to 150 nanometers, and the best is 20 to 200 nanometers.In addition, when adopting the carbon material of fibers form, general system employing length is 5 to 200 millimeters short carbon fiber.The consumption system of carbon material decides on actual needs, in the gross weight of hydrophobic polymer and carbon material, is generally 1 to 70 weight %, is preferably 3 to 20 weight %.In an embodiment according to the present invention, be that the carbon material is added in the solution of hydrophobic polymer, after evenly stirring, provide the mixture of being desired that contains hydrophobic polymer and carbon material.
Then, the mixture that in any suitable manner this is contained hydrophobic polymer and carbon material is applied at least one surface of carbide base material.Say it for example, can be selected from following mode and carry out this and use: sprinkling, wire mark, coating, impregnation and combination thereof.Wherein, the amount of application of this mixture system decide on many factors, the mode of for example using, the kind of carbide base material and area size, regulating course desired thickness, reaches solid content in the mixture etc.Say it for example, compared to carbon paper, carbon cloth concave-convex surface degree is bigger, so need bigger amount of application.Generally speaking, the amount of application of mixture is 0.1 to 40 milligram of every square centimeter of carbide base material.In addition, also can optionally this mixture be applied to the two sides of carbide base material, make the two sides of this carbide base material all have an improved properties, further improve the water management capabilities and the battery performance thereof of this carbide base material.When being applied to the two sides of carbide base material, mixture is 0.1 to 40 milligram every square centimeter in the amount of application of each face also as mentioned above.
Afterwards, this carbide base material through using carbon material and hydrophobic polymer is heat-treated under protection of inert gas, form a regulating course on this base material with this mixture of sintering.This heat treated temperature system usually is controlled at the fusing point that is higher than hydrophobic polymer, is preferably 200 to 450 ℃, is more preferred from 250 to 400 ℃; Heat treatment period is not an emphasis of the present invention, is generally 5 to 120 minutes, is preferably 10 to 90 minutes, is more preferred from 20 to 50 minutes.The rare gas element that can be used in the heat treatment step of the present invention can be selected from following group: nitrogen, helium, argon gas and combination thereof, based on considering on the cost, preferable system uses nitrogen.Heat-treat under protection of inert gas according to the present invention, can reduce, and then avoid the reduction of the conductivity of gained modified carbonized base material because of the loss on the weight that oxidation produced of carbon material.
Hydrophobic polymer after heat treatment can form the reticulated structure thing with said minuscule hole, helps the turnover of gas, and also is beneficial to the unnecessary water of eliminating because of it has hydrophobic property.
According to the inventive method, preferably, lie in before this heat treatment step, carry out a drying step earlier, with remove in the mixture more than moisture content and/or solvent.Say it for example, can adopt to be somebody's turn to do directly to place natural seasoning under the room temperature environment, or be placed in 70 to 150 ℃ the baking oven or be aided with the forced drying mode of hot gas and carry out the removal of this moisture content and/or solvent through the carbide base material that mixture is used.
According to the inventive method, capable of circulationly carry out this mixture step of applying and this drying step optionally 1 to 10 time, to promote the fuel battery performance of gained carbide base material.Afterwards, under protection of inert gas, heat-treat program again.
This case contriver finds, need not as earlier carbide base material being carried out the hydrophobic polymer pre-treatment as the preceding skill, as directly use as the inventive method contain hydrophobic polymer and carbon material mixture on carbide base material, just can give the hydrophobic performance that carbide base material is desired, simplify the upgrading processing procedure of whole carbide base material, reduce preparation cost.Simultaneously, by the modified carbonized base material of method for modifying manufacturing of the present invention, still can represent electroconductibility and the ventilation property of being desired.
The present invention provides a kind of modified carbonized base material in addition, and it comprises a carbide base material and a regulating course, and these leveling series of strata in fact directly are positioned on the one side at least of this carbide base material.In this, so-called " this regulating course in fact directly is positioned on the one side at least of this carbide base material " means between this carbide base material and this regulating course the formed hydrophobic substance layer of pre-treatment of Individual existence not such as Prior Art.About the working conditions of carbide base material, hydrophobic polymer and carbon material, be as indicated above, repeat no more in this.
Fig. 1 is the synoptic diagram that shows an embodiment of modified carbonized base material of the present invention, wherein modified carbonized base material 10 is the regulating course 2 that comprises a carbide base material 1 and be overlying on surface thereof, regulating course 2 is to comprise carbon material 21 and hydrophobic polymer 22, wherein, hydrophobic polymer 22 is the reticulated structure (not illustrating among the figure for simplicity) that is the tiny micropore of tool after thermal treatment.In this, as described above, can all provide regulating course 2 if necessary in the two sides of carbide base material 1.
Modified carbonized base material of the present invention, its surperficial regulating course because of containing the carbon material thus can keep carbide base material electroconductibility, because of contain hydrophobic polymer (reticulated structure that is the tiny micropore of tool) after the thermal treatment die represent desire Gas permeability and its inherent hydrophobicity; Be with, it is the electric pole gaseous diffusion layer material that is specially adapted in the fuel cell.
Therefore, the present invention provides a kind of fuel cell in addition, especially PEMFC and DMFC, and its characteristics are that at least one electrode system of this fuel cell contains modified carbonized base material of the present invention.About the explanation of prior art, the material of each element and structure in the fuel cell are to have in this technical field to know the knowledgeable institute well known usually as described above.Say it for example, can be referring to TaiWan, China patent I272739 number and U.S. Patent Publication 2007/0117005A1 number, its disclosure is all and in herein for your guidance.
Please refer to Fig. 2, it illustrates a primary member synoptic diagram according to PEMFC monocell of the present invention, comprises a mea (MEA) and has bipolar plates 5a, the 5b of gas passage.This mea is by a proton exchange membrane 4, is positioned at catalyst layer 3a, the 3b of these proton exchange membrane 4 both sides and places carbide base material 1a, the 1b in catalyst layer 3a, the 3b outside to be formed respectively, and carbide base material 1a, 1b are respectively at have regulating course 2a, 2b on the surface of catalyst layer 3a, 3b.Wherein, proton exchange membrane 4 can be used the Nafion series product of E.I.Du Pont Company, and catalyst layer 3a, 3b can be palladium or platinum catalyst.In this, also can use the two sides all to be covered with carbide base material 1a, the 1b of regulating course 2a, 2b in the mea of fuel cell.Result as attached embodiment after this case shows, contains the fuel cell of modified carbonized base material of the present invention, is to represent excellent battery performance, as current density.
Now with following embodiment further to illustrate the present invention, wherein, the measuring instrument that is adopted and method are as follows respectively:
(A) Gas permeability method for measurement
Gas permeability measures instrument: Gurley Model 4110, the U.S.
Gas permeability drum capacity: 300cc
Gas permeability drum weight: 5oz
Measure area: 1 square of inch
Test piece is cut into 10 centimeters * 10 centimeters sizes, tests according to ASTM D726-58 standard.
(B) contact angle method for measurement
Contact angle measures instrument: GBX model D-S Instruments, France
Wettability is often with the contact angle Come amount of commenting, and contact angle is meant drop and the tangent line of solid substrate surface point of contact and the angle theta of solid-liquid interface, promptly so-called contact angle.The more little representative wettability of contact angle is good more, and anti-representative wettability is bad.Generally speaking, 0 °＜θ＜90 ° are classified as wetting ability (hydrophilic); θ〉90 ° be classified as hydrophobicity (hydrophobic); θ=0 ° is moistening fully (complete wetting).
It is according to Young ' s Contact Angle equation that contact angle calculates:
θ
1v?cosθ＝θ
sv-θ
s1。
Wherein, θ
1vBe liquid phase-gas phase angle; θ
SvBe solid phase-gas phase angle; θ
S1Be solid phase-liquid phase angle.
(C) battery testing method
The battery testing board:
PD50 Asia Pacific Fuel Cell Technologies, Ltd.
Cell load machine model: Chroma 63103
Test condition:
Anode fuel: hydrogen (99.999%), flow velocity 200c.c./min
Negative electrode fuel: oxygen (industrial), flow velocity 200c.c./min
Anode negative electrode humidification temperature: 40 ℃
Humidifier outlet relative humidity: 90%
Battery testing temperature: 40 ℃
Battery assembling torsion: 40kgf cm
Cell reaction area: 25cm
2
The test piece that thermal treatment is finished is cut into 5 centimeters * 5 centimeters sizes, with itself and U.S. Gore produced through the catalyst coat film (catalyst-coatedmembrane, CCM, model:
Series 5621MESGA, have 35 micron thickness and 45Pt alloy/60Pt), make up with 40kgfcm torsion, bipolar plates adopts the graphite cake of the irrigation canals and ditches of tool paliform (gate-type), utilize stainless steel plate and teflon gasket (Teflon Gasket) to be packaged into the monocell of a test usefulness at last again, test.
(D) surface resistivity testing method
Surface resistivity tester table: Loresta GP Model MCP-T600, Mitubishi chemical company (Mitubishi Chemical Corp.)
Test piece is cut into 5 centimeters * 5 centimeters sizes, tests according to JIS K 7194 standards.
The carbon paper that will disclose No. 2006/0214320 described method produces according to U.S. patent application case lasts 5 minutes in carry out carbonization under the nitrogen protection under 1300 ℃.The thickness of gained carbon paper is 550 microns, and weight is 125g/m
2
Get FEP (getting with the FEP 121A solution of 10 milliliters of E.I.Du Pont Company of the 90 ml deionized water dilution) uniform mixing of 4 gram Vulcan XC-72 (Cabot Corp., Boston Mass.) and concentration 10%, continuously stirring is 5 minutes under the room temperature, obtains a liquid slurry.
Carbon paper is placed on the smooth solid surface, the gained slurry is sprayed on the one side of this carbon paper.Afterwards, the carbon paper after the spraying is placed 70 ℃ dry 15 minutes of roaster; Under 350 ℃, be that protective gas is heat-treated again, obtain once the upgrading carbon paper with nitrogen.
Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and negative electrode through upgrading carbon paper system, and each character system of measurement is as listed in the table 1.
Use raw material and the step identical with embodiment 1, the circulation 5 times of this spraying and drying step is carried out in thought altogether.Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and negative electrode through upgrading carbon paper system, and each character system of measurement is as listed in the table 1.
Embodiment 3
Use raw material and the step identical with embodiment 1, the circulation 10 times of this spraying and drying step is carried out in thought altogether.Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and negative electrode through upgrading carbon paper system, and each character system of measurement is as listed in the table 1.
Comparative example 1
Use raw material and the step identical with embodiment 1, only before the spraying step, earlier carbon paper is contained and be dipped in 3% FEP solution (getting) by the FEP121A solution of the E.I.Du Pont Company of 3 milliliters of 97 milliliters deionized waters dilutions, dried 15 minutes down in 70 ℃ afterwards, then carry out spraying, drying and the heat treatment process of embodiment 1 again.Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and negative electrode through upgrading carbon paper system, and each character system of measurement is as listed in the table 1.
Table 1
As shown in table 1, the present invention provided under without hydrophobicity pre-treatment situation through the upgrading carbon paper, hydrophobicity that tool is desired still, this can all be presented greater than 90 degree institutes by its contact angle that sprays face.In addition, compared to comparative example 1, what use that the present invention handles through hydrophobicity earlier during in fuel cell, is to represent preferable current density (improving 17%) through upgrading carbon paper (embodiment 1).In addition, the result's demonstration as embodiment 2 and 3 repeatedly sprays and baking step, can the appropriate usefulness that improves fuel cell.
With commercially available carbon cloth (select energy Science and Technology Co., Ltd., model: FCW1005) under nitrogen protection, last 5 minutes 1750 ℃ of thermal treatments.
Get 2 gram Vulcan XC-72 (Cabot companies (Cabot Corp.), Boston Mass.) with 2 gram N660 (Korea S iron and steel chemistry (the Korea Steel Chemical Co. of company limited, Ltd.)) with the FEP of concentration 10% (getting) uniform mixing with the FEP 121A solution of 10 milliliters of E.I.Du Pont Company of 90 ml deionized water dilution, continuously stirring is 5 minutes under room temperature, obtains a liquid slurry.
Carbon cloth is placed on the smooth solid surface, the gained slurry is sprayed on the one side of this carbon cloth.Afterwards, the carbon cloth after the spraying is placed 70 ℃ dry 15 minutes of roaster; Under 350 ℃, be that protective gas is heat-treated again, obtain once the upgrading carbon cloth with nitrogen.
Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and negative electrode through upgrading carbon cloth system, and each character system of measurement is as listed in the table 2.
Comparative example 2
Adopt raw material and the step identical with embodiment 4, only before the spraying step, earlier carbon cloth is contained and be dipped in 3% FEP solution (getting) by the FEP121A solution of the E.I.Du Pont Company of 3 milliliters of 97 milliliters deionized waters dilutions, dried 15 minutes down in 70 ℃ afterwards, then carry out spraying, drying and the heat treatment process of embodiment 4 again.Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and negative electrode through upgrading carbon cloth system, and each character system of measurement is as listed in the table 2.
Comparative example 3
Adopt the material carbon identical to be distributed under the nitrogen protection with embodiment 4; under 1750 ℃, heat-treat and last 5 minutes; then this carbon cloth is contained and be dipped in 3% FEP solution (get), dried 15 minutes down in 70 ℃ afterwards by the FEP 121A solution of the E.I.Du Pont Company of 3 milliliters of 97 milliliters deionized waters dilutions.
Carry out 4 described spraying and drying programs, under 350 ℃, in air ambient, heat-treat afterwards, obtain once the upgrading carbon cloth as embodiment.
Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and negative electrode through upgrading carbon cloth system, and each character system of measurement is as listed in the table 2.
Comparative example 4
Adopt raw material and the step identical with embodiment 4, the thought heat treatment step lies in the air ambient and carries out.Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and negative electrode through upgrading carbon cloth system, and each character system of measurement is as listed in the table 2.
Table 2
As shown in Table 2, compared to comparative example 2 to comparative example 4, the present invention is to represent suitable hydrophobicity through upgrading carbon cloth (embodiment 4), and it can present higher battery performance when being used in fuel cell.In addition, the weight loss through the upgrading carbon cloth of heat-treating gained in air reaches 1.84 weight % (comparative example 3) and 1.60 weight % (comparative example 4), is higher than thermal treatment gained person under the protection of inert gas (embodiment 4,0.76 weight %).
Embodiment 5
Take commercially available carbon paper TGP-H-090 (Toray company) as raw material.
Get 2 gram Vulcan XC-72 (Cabot companies (Cabot Corp.), Boston Mass.) with 2 gram N660 (Korea S iron and steel chemistry (the Korea Steel Chemical Co. of company limited, Ltd.)) with the FEP of concentration 10% (getting) uniform mixing with 90 ml deionized water, the 10 milliliters of FEP121A of E.I.Du Pont Company solution of dilution, continuously stirring is 5 minutes under the room temperature, obtains a liquid slurry.
Carbon paper is placed on the smooth solid surface, the gained slurry is sprayed on the one side of this carbon cloth.Afterwards, the carbon paper after the spraying is placed 70 ℃ dry 15 minutes of roaster; Under 350 ℃, be that protective gas is heat-treated again, obtain once the upgrading carbon paper with nitrogen.
Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and negative electrode through upgrading carbon paper system, and each character system of measurement is as listed in the table 3.
Comparative example 5
Adopt raw material and the step identical with embodiment 5, only before the spraying step, earlier carbon paper is contained and be dipped in 3% FEP solution (getting) by the FEP121A solution of the E.I.Du Pont Company of 3 milliliters of 97 milliliters deionized waters dilutions, dried 15 minutes down in 70 ℃ afterwards, then carry out spraying, drying and the heat treatment process of embodiment 5 again.Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and negative electrode through upgrading carbon paper system, and each character system of measurement is as listed in the table 3.
Table 3
As shown in Table 3, compared to comparative example 5, what the present invention handled through hydrophobicity earlier is to represent suitable hydrophobicity through upgrading carbon paper (embodiment 5), and it can present preferable current density (improving 22%) when being used in fuel cell.
Embodiment 6
With commercially available carbon cloth (select energy Science and Technology Co., Ltd., model: FCW1005), under nitrogen protection, under 1750 ℃, heat-treat again and last 5 minutes.
Get 2 gram Vulcan XC-72 (Cabot Corp., Boston Mass.) with 2 gram N660 (KoreaSteel Chemical Co., Ltd.) with the FEP of concentration 10% (getting) uniform mixing with the FEP 121A solution of 10 milliliters of E.I.Du Pont Company of 90 ml deionized water dilution, continuously stirring is 5 minutes under the room temperature, obtains a liquid slurry.
Carbon cloth is placed on the smooth solid surface, the gained slurry is sprayed on the one side of this carbon cloth.Afterwards, the carbon cloth after the spraying is placed 70 ℃ dry 15 minutes of roaster.Again this slurry is sprayed into the another side of this carbon cloth, and places 70 ℃ dry 15 minutes of roaster again.Then, under 350 ℃, be that protective gas is heat-treated with nitrogen, obtain once the upgrading carbon cloth.
Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for negative electrode and embodiment 4 gained persons system is used for anode through upgrading carbon cloth system, and each character system of measurement is as listed in the table 4.
Embodiment 7
Adopt raw material and the step identical, obtain through the upgrading carbon cloth with embodiment 6.Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and embodiment 4 gained persons system is used for negative electrode through upgrading carbon cloth system, and each character system of measurement is as listed in the table 4.
Embodiment 8
Adopt raw material and the step identical, obtain through the upgrading carbon cloth with embodiment 6.Utilize above-mentioned testing method to carry out every test, wherein in battery performance test, gained is used for anode and negative electrode through upgrading carbon cloth system, and each character system of measurement is as listed in the table 4.
Table 4
| Fuel cell flow density (under the 0.5V) (mA/cm 2) | |
| Embodiment 6 | 1008 |
| Embodiment 7 | 1099 |
| Embodiment 8 | 1110 |
As shown in Table 4, no matter carbide base material is carried out single face upgrading or two-sided upgrading, and no matter the gained modified carbonized base material is used for negative electrode or anode, all can obtain good battery efficiency in fuel cell.
The above embodiments only are used for exemplifying embodiments of the present invention, and explain technical characterictic of the present invention, are not to be used for limiting protection category of the present invention.Any be familiar with this operator can unlabored change or the arrangement of the isotropism scope that all belongs to the present invention and advocated, the scope of the present invention should be as the criterion with following claim.
Claims (22)
1, a kind of method for modifying of carbide base material comprises:
One carbide base material is provided;
One mixture that contains hydrophobic polymer and carbon material is provided;
This mixture is applied to the one side at least of this carbide base material; And
Under protection of inert gas, this carbide base material of thermal treatment.
2, the method for claim 1, wherein this carbide base material system is selected from following group: carbon cloth, carbon paper or carbon felt.
3, the method of claim 1, wherein this hydrophobic polymer system is selected from following group: tetrafluoroethylene (polytetrafluoroethylene, PTFE), polyhexafluoropropylene (polyhexafluoropropylene, PHFP), the multipolymer of R 1216 and tetrafluoroethylene (copolymers of hexafluoropropylene and tetrafluoro-ethylene, FEP), the multipolymer of tetrafluoroethylene and perfluoro propyl ethyl ether (copolymers oftetrafluoroethylene and perfluoropropyl-vinylether, PFA), the multipolymer of tetrafluoroethylene and perfluoro-methyl ethyl ether (copolymers oftetrafluoroethylene and perfluoromethyl-vinylether, MFA), the homopolymer of chlorotrifluoroethylene (homopolymers of chlorotrifluoroethylene, PCTFE), polyvinylidene difluoride (PVDF) (polyvinylidene fluoride, PVDF), fluorinated ethylene propylene (poly (vinylfluoride), PVF), the multipolymer of tetrafluoroethylene and ethene (copolymerof tetrafluoroethylene and ethylene, ETFT), the multipolymer of vinylidene and R 1216 and tetrafluoroethylene (copolymer of vinylidene fluoride andhexafluoropropylene, and tetrafluoroethylene, THV), or its combination.
4, the method for claim 1, wherein this carbon material system comprises powder carbon material, fibrous carbon material or its combination.
5, the method for claim 1, wherein this carbon material system is selected from following group: carbon black, graphite, acetylene black or its combination.
6, the method for claim 1, wherein this to use be to carry out to be selected from following mode: sprinkling, wire mark, coating, impregnation or its combination.
7, the method for claim 1, wherein this mixing system is applied on the two sides of this carbide base material.
8, the method for claim 1, wherein lie in this heat treatment step before, carry out a drying step.
9, method as claimed in claim 8, wherein this drying step lies under 70 to 150 ℃ and carries out.
10, method as claimed in claim 8 wherein is the circulation 1 to 10 time of carrying out this step of applying and this drying step.
11, the method for claim 1, wherein this indifferent gas system is selected from following group: nitrogen, helium, argon gas or its combination.
12, the method for claim 1, wherein this heat treated temperature is the fusing point that is higher than this hydrophobic polymer.
13, method as claimed in claim 12, wherein this thermal treatment lies under 200 to 450 ℃ and lasts 5 to 120 minutes.
14, a kind of modified carbonized base material comprises:
One carbide base material; And
One regulating course in fact directly is positioned on the one side at least of this carbide base material.
15, modified carbonized base material as claimed in claim 14, wherein this carbide base material system is selected from following group: carbon cloth, carbon paper, carbon felt or its combination.
16, modified carbonized base material as claimed in claim 14, wherein these leveling series of strata comprise hydrophobic polymer and carbon material.
17, modified carbonized base material as claimed in claim 16, wherein this hydrophobic polymer system is selected from following group: PTFE, PHFP, FEP, PFA, MFA, PCTFE, PVDF, PVF, ETFT, THV or its combination.
18, modified carbonized base material as claimed in claim 16, wherein this carbon material system comprises powder carbon material, fibrous carbon material or its combination.
19, modified carbonized base material as claimed in claim 16, wherein this carbon material system is selected from following group: carbon black, graphite, acetylene black or its combination.
20, modified carbonized base material as claimed in claim 14, wherein these leveling series of strata in fact directly are positioned on the two sides of this carbide base material.
21, modified carbonized base material as claimed in claim 14 is as the electric pole gaseous diffusion layer in the fuel cell.
22, a kind of fuel cell is characterized in that its at least one electrode system contains just like each described modified carbonized base material in the claim 14 to 21.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2007103005100A CN101462712A (en) | 2007-12-19 | 2007-12-19 | Modified carbonized base material, and preparation method and use thereof |
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| CNA2007103005100A CN101462712A (en) | 2007-12-19 | 2007-12-19 | Modified carbonized base material, and preparation method and use thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269562A (en) * | 2014-07-18 | 2015-01-07 | 台南大学 | Modification of carbon cloth, and application thereof |
| CN107732254A (en) * | 2016-08-10 | 2018-02-23 | Jntg有限公司 | Vanadium oxide reduction flow battery electrode and the vanadium oxide reduction flow battery for including it |
| CN115198562A (en) * | 2022-09-16 | 2022-10-18 | 融科氢能源有限公司 | Carbon paper processing device and method for fuel cell |
-
2007
- 2007-12-19 CN CNA2007103005100A patent/CN101462712A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269562A (en) * | 2014-07-18 | 2015-01-07 | 台南大学 | Modification of carbon cloth, and application thereof |
| CN104269562B (en) * | 2014-07-18 | 2017-01-18 | 台南大学 | Modification of carbon cloth, and application thereof |
| CN107732254A (en) * | 2016-08-10 | 2018-02-23 | Jntg有限公司 | Vanadium oxide reduction flow battery electrode and the vanadium oxide reduction flow battery for including it |
| CN115198562A (en) * | 2022-09-16 | 2022-10-18 | 融科氢能源有限公司 | Carbon paper processing device and method for fuel cell |
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