CN102110822A - Gas diffusion layer and preparation method and application thereof - Google Patents
Gas diffusion layer and preparation method and application thereof Download PDFInfo
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- CN102110822A CN102110822A CN2009102597529A CN200910259752A CN102110822A CN 102110822 A CN102110822 A CN 102110822A CN 2009102597529 A CN2009102597529 A CN 2009102597529A CN 200910259752 A CN200910259752 A CN 200910259752A CN 102110822 A CN102110822 A CN 102110822A
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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
Abstract
The invention discloses a gas diffusion layer and a preparation method and application thereof. The gas diffusion layer comprises a carbon black layer (2) with the micropore diameter of 30 to 100 microns and/or a carbon fiber layer (1) with the micropore diameter of 50 to 150 microns. The gas diffusion layer can be widely applied to gas diffusion electrodes in fuel cells, electrolytic cells and ultracapacitor electrochemical reaction devices. The invention simultaneously discloses a preparation method of the gas diffusion layer. The gas diffusion layer has a simple, rational and compact structure, overcomes various defects of the prior art, and has the advantages of high air permeability, high drainage, high conductivity, stable catalyst layers and high catalyst utilization rate.
Description
Technical field
The present invention relates to electrochemical reaction appts, particularly, relate to a kind of gas diffusion layers and its production and use.
Background technology
The electrode of fuel cell, electrolytic cell, super capacitor is a kind of gas-diffusion electrode of porous, generally is made up of diffusion layer and catalyst layer.Different diffusion layer materials has very big influence for structure, manufacture craft and the performance of electrode.
Arrive catalyst layer such as fuel gas in Proton Exchange Membrane Fuel Cells through anode diffusion layer, under the effect of catalyst, electrode reaction takes place, promptly
H
2-2H+2e
The electronics that this electrode reaction produces arrives negative electrode by the conduction flow of diffusion layer through external circuit, and hydrogen ion arrives negative electrode under the effect of proton exchange membrane simultaneously.Oxygen generates water by with hydrogen ion and electronics electrode reaction taking place under catalyst action behind the cathode diffusion layer, that is:
1/2O
2+2H+2e-H
2O
There is (temperature and pressure that depends on battery) (Ersoz A in water in the Proton Exchange Membrane Fuel Cells (PEMFC) with gaseous state and liquid state, Olgun H, Ozdogan S.et al., J.Power Sources.2003,118 (1-2): 384-392), dilutional hyponatremia or very few performance to PEMFC all can be brought negative effect (Huang Naike, Wang Shuzhong, power technology, 2003,27 (3): 329-332).
Gas diffusion layers not only plays a part support catalyst layer, stabilized electrodes structure in electrode, also possess the multiple function that gas passage, electron channel and drainage channel are provided for electrode reaction.Select for use high performance gas diffusion layer material to help improving combination property (JAMESL, the ANDREW D.Fuel cell systems explained.England:John Wiley﹠amp of electrode; Sons Ltd., 2000.66-69).Desirable diffusion layer should possess 3 characteristics: air permeability and good, good drainage and good electrical conductivity.General gas diffusion layers is made up of base material and transition zone.In multiple base material, the charcoal fibrous paper has uniform porous matter laminate structure and excellent conductivity, chemical stability and thermal stability, be diffusion layer material (Thomas T O, Glendale, the HiroshiI that is most widely used in the fuel cell, et al., US:3829327,1974. and Teruaki Kitago, Tadaaki Yoshida, US:3998689,1976).Transition zone is known as intermediate layer (Shao Zhigang again, the clothing treasured is honest and clean, Han Ming etc., electrochemistry, 2000,6 (3): 317-323.), its adding has realized reacting gas and the reallocation of product between flow field and Catalytic Layer, for strengthening conductivity, improve electrode performance, battery operation stability and service life and played important function.
People such as L.R.Jordan (JORDAN L R, SHUKLA A K, BEHRSING T, et al., J.Power Sources, 2000,86:250-254.) powdered carbon is mixed with the polytetrafluoroethylene (PTFE) emulsion, add an amount of solvent, utilize ultrasonic wave that it is uniformly dispersed, it is sprayed on the positive and negative surface of base material equably, the oven dry back is in 300～350 ℃ of about 30min of following sintering, make the PTFE fusion remove surfactant simultaneously, obtain hydrophobic material at last by PTFE bonding charcoal and basilar fibers.The powdered carbon that adds plays the effect that strengthens conductivity on the one hand, is used for filling the macropore between the fiber in the base material on the other hand, makes surfacing and even aperture distribution.The mass ratio of PTFE and carbon black was good between 20: 80 and 50: 50 in the coating liquid, and coating layer thickness is between 0.010～0.254mm, and the content of PTFE is 10%～50%.
In the research of PEMFC diffusion layer, people such as Xu Hongfeng, Tian Ying are coated with the mixture of one deck XC-72R charcoal and polytetrafluoroethylene (PTFE) as regulating course on the carbon paper of crossing through hydrophobic treatment.Shao Zhigang, clothing are precious honest and clean etc. (Shao Zhigang, the clothing treasured is honest and clean, Han Ming etc., electrochemistry, 2000,6 (3): 317-323). and with water or ethanol as solvent, it is 1: 1 solution that carbon black and PTFE are made into mass ratio, mixes the back as regulating course.People such as Chan Lim (LIM C.WANG C Y., Electrochimica Acta, 2004,49 (24): 4149-4156.) studied the influence of PTFE content and thickness of diffusion layer.People such as Giorgi (JORDAN L R, SHUKLA A K, BEHRSING T., Journal of PowerSources.2000.86:250-254.) think the porosity of diffusion layer that increased in the diffusion layer PTFE content influence.People such as L.R.Jordan (KONG C S, KIM D Y, LEE H K, et al., Journal of Power Sources, 2002,108:185-191.) think that the oarse-grained acetylene black of use replaces Vulcan XC 72R charcoal can improve the performance of battery.People such as Chang Sun Kong add pore creating material and improve mass transfer problem in the battery in the PEMFC diffusion layer.
M.Watanabe (the WAT ANABE M. of Japan, US:5137754,1992.) etc. the people invented a kind of new hydrophobic processing method, with mean molecule quantity is that 250000 polyethylene is dissolved in the heptane, be made into a kind of film forming solution, with base material, immerse wherein as the charcoal fibrous paper, treat that heptane volatilization back formation mass fraction on carbon paper is 5% PE coating, then this carbon paper with polyethylene coating is put into stainless steel reactor, at room temperature condition, contain in the fluorine gas atmosphere of 10% argon gas and fluoridize about 30min, the hydrophobic material of obtained performance excellence.The hydrophobicity performance of relatively finding the hydrophobic material that makes than the method for flooding with the PTFE emulsion with this hydrophobic processing method by experiment is better.
After base material made charcoal/PTFE coating, find that aperture does not wherein have hydrophobicity, because those apertures of PTFE molecular proportion are big 10～100 times.Thereby when the spraying noble metal catalyst, can find the phenomenon of osmosis of noble metal, cause the reduction of catalyst utilization, therefore need further make hydrophobic and handle those apertures.V.K.KARL (KARL V K., US:3899354,1975.) uses the benzinum weak solution of 1.5% paraffin wax to handle to the carbon paper after the coating, and baking 30min under 50 ℃ can make the aperture in the coating possess effective hydrophobicity again.Perhaps use the acetone soln of 2.0% cellulose acetate to handle, also can obtain good aperture hydrophobic effect.
Another kind of hydrophobic processing method by the invention of research institute of Japanese Toyota is base material to be exposed to a kind of in plasma treated charcoal fluorine compound gas, makes surface deposition one deck hydrophobic material.Yet this method need design main equipment especially, is not suitable for large-scale production.
In order to simplify production technology, and make the aperture in the base material also obtain hydrophobicity, Gu Jun etc. (Gu Jun, Yu Tao etc., ZL200710019376.7) be made into dispersion liquid with carbon black powders and PTFE or PVDF, base material be placed on to flood in the dispersion liquid then and obtain the better gas diffusion layer.
Though above technical process makes substrate material surface become smooth, can not avoid catalyst to penetrate in the base material fully, because aperture or too big, or too little, cause the moisture that the reacting gas diffusional resistance increases or reaction generates to be difficult to discharge.
Summary of the invention
The objective of the invention is to,, propose a kind of gas diffusion layers and its production and use, with the advantage that realizes that gas permeability is good, drainage is good, conductivity is good, catalyst layer is stable, catalyst utilization is high at the problems referred to above.
For achieving the above object, the technical solution used in the present invention is:
A kind of gas diffusion layers comprises: micro-pore diameter is that the carbon black layer 2 and/or the micro-pore diameter of 30-100 micron is 50-150 micron carbon fiber layer 1.
Simultaneously, another technical scheme that the present invention adopts is: a kind of application of gas diffusion layers, can be widely used in the gas-diffusion electrode in fuel cell, electrolytic cell, the super capacitor electrochemical reaction appts, described electrode comprises: dielectric film 3, catalyst layer 4, gas diffusion layers 5, pole plate 6, dielectric film 3 both sides order symmetry be provided with catalyst layer 4, gas diffusion layers 5 and pole plate 6.
Simultaneously, another technical scheme that the present invention adopts is: a kind of preparation method of gas diffusion layers, and its preparation process is as follows:
1) carbon fibre material, dispersant and deionized water are configured to uniform sizing material, wherein the consumption of each component is: carbon fibre material is the 5-30wt% of slurry, and dispersant is the 5-30wt% of carbon fibre material; Add the PTFE emulsion in slurry, stirred 0.5-2 hour, wherein the consumption of PTFE emulsion is the 10-50wt% of carbon fibre material; Add viscosity modifier then, the viscosity adjustment of slurry to 1000-30000cps, is promptly obtained the carbon fiber slurry;
2) mixture, deionized water, the dispersant with carbon black powders or carbon black powders and carbon fiber is configured to uniform sizing material, wherein the consumption of each component is: the mixture of carbon black powders or carbon black powders and carbon fiber is the 10-20wt% of slurry, dispersant is the 5-30wt% of carbon fibre material, in slurry, add the PTFE emulsion, stirred 0.5-2 hour, wherein the consumption of PTFE emulsion is the 10-50wt% of the mixture of carbon black powders or carbon black powders and carbon fiber; Add viscosity modifier then, the viscosity adjustment of slurry to 1000-30000cps, is promptly obtained the carbon black slurry;
3) described diffusion layer matrix is put into the PTFE emulsion and flood 0.5-15min, taking-up is dried, and puts into drying box 50-150 ℃ of oven dry, at 300-390 ℃ of sintering 20-60min, obtains being loaded with the diffusion layer matrix of PTFE;
4) utilize the method for silk screen printing, coating, spraying respectively or successively carbon fiber slurry and carbon black slurry to be coated to the diffusion layer matrix that is loaded with PTFE, at 300-390 ℃ of following sintering 20-60min, obtain described gas diffusion layers then.
Further, described dispersant is one or more among XH-1, AEO-9, FC4430, Tween-60, the Triton X-100.
Further, described diffusion layer matrix is a kind of in carbon paper, carbon cloth (model is: TORY, SGL, GORE), stainless (steel) wire, nickel screen, the copper mesh.
Further, described carbon black powders is that acetylene black is or/and active carbon.
Further, described PTFE emulsion is that content is the PTFE emulsion of 10-50wt%.
Further, described viscosity modifier is one or more in polyethylene glycol, ethylene glycol, glycerine, the cellulose.
Beneficial effect:
The invention discloses a kind of diffusion layer and preparation technology thereof who is used for electrochemical reaction appts such as fuel cell, electrolytic cell, super capacitor, micropore distributes more even at electrode surface, cross-sectional direction at electrode has bore diameter gradient, make diffuse layer structure more stable, and help the diffusion of reacting gas and the discharge of moisture, avoid the catalyst material of catalyst layer to penetrate into the bigger diffusion layer in aperture and reduce catalyst utilization simultaneously.
Description of drawings
Accompanying drawing is used to provide further understanding of the present invention, and constitutes the part of specification, is used from explanation the present invention with embodiments of the invention one, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the generalized section of traditional gas-diffusion electrode;
Fig. 2 has the gas-diffusion electrode generalized section of carbon fiber layer for the present invention;
Fig. 3 has the gas-diffusion electrode generalized section of carbon black layer for the present invention;
Fig. 4 is the gas-diffusion electrode generalized section of the present invention's while carbon-bearing fibrage and carbon black layer.
In conjunction with the accompanying drawings, Reference numeral is as follows in the embodiment of the invention:
The 1-carbon fiber layer; The 2-carbon black layer; The 3-dielectric film; The 4-catalyst layer; The 5-gas diffusion layers; The 6-pole plate.
Embodiment
Below in conjunction with accompanying drawing the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for description and interpretation the present invention, and be not used in qualification the present invention.
Fig. 1 is the generalized section of gas-diffusion electrode in the electrochemical reaction appts such as conventional fuel cell, electrolytic cell, super capacitor.The main of diffusion layer substrate 5 is to electrode interior input reaction medium or to the outside output medium of electrode with effect, and collection the conduct electricity chemical reaction produces or need electric current.Basalis 5 must be the material of electrochemical corrosion resistant and high conduction, mainly is carbon fiber paper, carbon cloth or the antiseptic wire netting of process such as nickel screen, copper mesh, stainless (steel) wire etc.The porosity of basalis 5 generally is 50-90%, and the aperture is the 100-200 micron.Catalyst layer 4 generally is Pt and alloy catalyst thereof in fuel cell, is the zone that electrochemical redox reaction takes place, and the particle diameter of catalyst and carrier thereof is generally the 3-50 micron.Because the bigger gas diffusion layers in catalyst layer next-door neighbour aperture that particle diameter is less, catalyst penetrates into the macropore of basalis easily, causes the loss of catalyst, has reduced the activity of electrochemical reaction.
Fig. 2 has the gas-diffusion electrode generalized section of carbon fiber layer for the present invention.Different with Fig. 1 is to have added carbon fiber layer 1 between basalis 5 and catalyst layer 4.Carbon fiber layer 1 mainly is made up of carbon fiber and high polymer binder, and forming diameter is the micropore of 50-150 micron.The aperture of carbon fiber layer 1 is more smaller than the aperture of basalis, can not influence the transmission of reaction medium in diffusion layer, and can stop the catalyst in the catalyst layer to penetrate into the bigger basalis in aperture.
Fig. 3 is similar for gas-diffusion electrode generalized section and Fig. 2 that the present invention has carbon black layer, has just added carbon black layer 2 between basalis 5 and catalyst layer 4.Carbon black layer 2 mainly is made up of carbon black powders (acetylene black, activated carbon etc.) and high polymer binder, the entering part carbon fiber that perhaps mixes again therein, with obtain high conduction, have a microporous layers that the aperture is the 30-100 micron.The loss of catalyst be can effectively stop like this, but the discharge of moisture in the electrode and the transmission of reaction medium are unfavorable for.
Fig. 4 is the gas-diffusion electrode generalized section of the present invention's while carbon-bearing fibrage and carbon black layer.Different with Fig. 2 and 3 is to have increased carbon black layer 2 between carbon black layer 2 and catalyst layer 4.The aperture is the loss that the carbon black layer 2 of 30-100 micron has effectively stoped catalyst in the catalyst layer 4.Reaction medium arrives catalyst layer 4 from basalis 5 by carbon fiber layer 1, carbon black layer 2, and the aperture is to reduce gradually, has reduced the diffusional resistance of reaction medium, and can guarantee the discharge of moisture in the electrode.
This gas diffusion layers comprises: micro-pore diameter is that the carbon black layer 2 and/or the micro-pore diameter of 30-100 micron is 50-150 micron carbon fiber layer 1.
Simultaneously, another technical scheme that the present invention adopts is: a kind of application of gas diffusion layers, can be widely used in the gas-diffusion electrode in fuel cell, electrolytic cell, the super capacitor electrochemical reaction appts, described electrode comprises: dielectric film 3, catalyst layer 4, gas diffusion layers 5, pole plate 6, dielectric film 3 both sides order symmetry be provided with catalyst layer 4, gas diffusion layers 5 and pole plate 6.
Simultaneously, another technical scheme that the present invention adopts is: a kind of preparation method of gas diffusion layers, and its preparation process is as follows:
1) carbon fibre material, dispersant and deionized water are configured to uniform sizing material, wherein the consumption of each component is: carbon fibre material is the 5-30wt% of slurry, and dispersant is the 5-30wt% of carbon fibre material; Add the PTFE emulsion in slurry, stirred 0.5-2 hour, wherein the consumption of PTFE emulsion is the 1050wt% of carbon fibre material; Add viscosity modifier then, the viscosity adjustment of slurry to 1000-30000cps, is promptly obtained the carbon fiber slurry;
2) mixture, deionized water, the dispersant with carbon black powders or carbon black powders and carbon fiber is configured to uniform sizing material, wherein the consumption of each component is: the mixture of carbon black powders or carbon black powders and carbon fiber is the 10-20wt% of slurry, dispersant is the 5-30wt% of carbon fibre material, in slurry, add the PTFE emulsion, stirred 0.5-2 hour, wherein the consumption of PTFE emulsion is the 1050wt% of the mixture of carbon black powders or carbon black powders and carbon fiber; Add viscosity modifier then, the viscosity adjustment of slurry to 1000-30000cps, is promptly obtained the carbon black slurry;
3) described diffusion layer matrix is put into the PTFE emulsion and flood 0.5-15min, taking-up is dried, and puts into drying box 50-150 ℃ of oven dry, at 300-390 ℃ of sintering 20-60min, obtains being loaded with the diffusion layer matrix of PTFE;
4) utilize the method for silk screen printing, coating, spraying respectively or successively carbon fiber slurry and carbon black slurry to be coated to the diffusion layer matrix that is loaded with PTFE, at 300-390 ℃ of following sintering 20-60min, obtain described gas diffusion layers then.
Described dispersant is one or more among XH-1, AEO-9, FC4430, Tween-60, the Triton X-100.Described carbon back is carbon paper or carbon cloth, and model is: TORY, SGL, GORE.Described carbon black powders is that acetylene black is or/and active carbon.Described PTFE emulsion is that content is the PTFE emulsion of 10-50wt%.Described viscosity modifier is one or more in polyethylene glycol, ethylene glycol, glycerine, the cellulose.
Take by weighing 60% PTFE emulsion 60.0080g in the 250mL beaker, add the 60-180g deionized water, magnetic stir bar stir about 15min is uniformly dispersed it.The PTFE solution of 10-30% is poured in the clean culture dish, immerse in the solution cutting out good carbon paper or carbon cloth (clean, dry, weigh) level, put into vacuum drying oven then, regulate vacuum degree to 200Pa, take out carbon paper behind the dipping 1min, blot the solution at carbon paper or carbon cloth edge with filter paper, level is dried (about 6min) then.Again carbon paper or carbon cloth are put into high temperature oven, 70 ℃ of design temperatures, about 6min oven dry is taken out.Again carbon or carbon cloth paper are placed 350 ℃ of sintering 30min of baking oven, the load capacity that makes PTFE is 1-10mg.cm
-2
Take by weighing 3.0g carbon fiber powder with the 50ml beaker.In the 100ml beaker, add the 9ml deionized water, to wherein adding certain density dispersant, as XH-1, AEO 9, FC4430, Tween-60, Triton X-100 etc.Method with ultrasonic cell disruptor disperses is dispensed into the carbon fiber powder in the above-mentioned deionized water.With 1ml distilled water flushing ultrasonic head, the solution of flushing flows in the beaker.Above-mentioned beaker is put into the high-power ultrasonics cleaning machine, guarantee in the tank water with not ing to beaker half highly, ultrasonic agitation 1 hour.Dropwise add 60% PTFE emulsion 0.5-1g in the above-mentioned solution, continue to stir 0.5 hour.In ultra-high frequency ultrasonic wave cleans, a certain amount of thickener such as polyethylene glycol, glycerine etc. are dropwise added in the diffusion layer slurry for preparing, ultrasonic 20min adds a certain amount of isopropyl alcohol in the above-mentioned slurry again, obtains the diffusion layer slurry that viscosity is about 1000-30000cps at last.
This slurry is coated to the surface of above-mentioned treated carbon paper or carbon cloth with the coating or the method for silk screen printing, obtains carbon fiber layer 1 (as shown in Figure 2).Carbon fiber layer 1 carbon fiber loaded amount is 0.5-2mgcm
-2, thickness is the 10-30 micron.
Take by weighing 60% PTFE emulsion 60.0080g in the 250mL beaker, add the 60-180g deionized water, magnetic stir bar stir about 15min is uniformly dispersed it.The PTFE solution of 10-30% is poured in the clean culture dish, immerse in the solution cutting out good carbon paper or carbon cloth (clean, dry, weigh) level, put into vacuum drying oven then, regulate vacuum degree to 200Pa, take out carbon paper behind the dipping 1min, blot the solution at carbon paper or carbon cloth edge with filter paper, level is dried (about 6min) then.Again carbon paper or carbon cloth are put into high temperature oven, 70 ℃ of design temperatures, about 6min oven dry is taken out.Again carbon or carbon cloth paper are placed 350 ℃ of sintering 30min of baking oven, the load capacity that makes PTFE is 1-10mg.cm
-2
Take by weighing 3-20g acetylene black powder or other carbon black with the 200ml beaker,,, powder is stirred into the dough shape with glass rod as XH-1, AEO-9, FC4430, Tween-60, Triton X-100 etc. to wherein adding certain density dispersant.In the 2500ml beaker, adding 200-500ml concentration is the above-mentioned dispersant of 0.5-10%, adds a certain amount of distilled water again.Use the high-shear emulsion machine agitating solution, and divide doughy carbon black 10 times every 2min to add in the above-mentioned beaker.After all adding, continue to shear 30min.Dropwise add 60% PTFE emulsion 0.5-1g in the above-mentioned solution, continue to stir 0.5 hour.In ultra-high frequency ultrasonic wave cleans, a certain amount of thickener such as polyethylene glycol, glycerine etc. are dropwise added in the diffusion layer slurry for preparing, ultrasonic 20min adds a certain amount of isopropyl alcohol in the above-mentioned slurry again, obtains the diffusion layer slurry that viscosity is about 1000-30000cps at last.
This slurry is coated to the surface of above-mentioned treated carbon paper or carbon cloth with the coating or the method for silk screen printing, obtains carbon black layer 2 (as shown in Figure 3).Carbon black layer 2 load capacity are 0.5-2mgcm
-2, thickness is the 10-30 micron.
Method according to embodiment 1 and 2 prepares the diffusion layer slurry, successively the slurry of embodiment 2 and embodiment 1 is coated to the surface (as shown in Figure 4) of treated carbon paper or carbon cloth with the method for coating or silk screen printing.The gross thickness of carbon black layer 2 and carbon fiber layer 1 is the 10-30 micron, and total carbon black and carbon fiber loaded amount are 0.5-2mgcm
-2
It should be noted that at last: the above only is the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a gas diffusion layers is characterized in that, comprising: micro-pore diameter is that the carbon black layer (2) and/or the micro-pore diameter of 30-100 micron is 50-150 micron carbon fiber layer (1).
2. the application of the described gas diffusion layers of claim 1 is characterized in that, can be widely used in the gas-diffusion electrode in fuel cell, electrolytic cell, the super capacitor electrochemical reaction appts.
3. the preparation method of the described gas diffusion layers of claim 1 is characterized in that, preparation process is as follows:
1) carbon fibre material, dispersant and deionized water are configured to uniform sizing material, wherein the consumption of each component is: carbon fibre material is the 5-30wt% of slurry, and dispersant is the 5-30wt% of carbon fibre material; Add the PTFE emulsion in slurry, stirred 0.5-2 hour, wherein the consumption of PTFE emulsion is the 10-50wt% of carbon fibre material; Add viscosity modifier then, the viscosity adjustment of slurry to 1000-30000cps, is promptly obtained the carbon fiber slurry;
2) mixture, deionized water, the dispersant with carbon black powders or carbon black powders and carbon fiber is configured to uniform sizing material, wherein the consumption of each component is: the mixture of carbon black powders or carbon black powders and carbon fiber is the 10-20wt% of slurry, dispersant is the 5-30wt% of carbon fibre material, in slurry, add the PTFE emulsion, stirred 0.5-2 hour, wherein the consumption of PTFE emulsion is the 10-50wt% of the mixture of carbon black powders or carbon black powders and carbon fiber; Add viscosity modifier then, the viscosity adjustment of slurry to 1000-30000cps, is promptly obtained the carbon black slurry;
3) described diffusion layer matrix is put into the PTFE emulsion and flood 0.5-15min, taking-up is dried, and puts into drying box 50-150 ℃ of oven dry, at 300390 ℃ of sintering 20-60min, obtains being loaded with the diffusion layer matrix of PTFE;
4) utilize the method for silk screen printing, coating, spraying respectively or successively carbon fiber slurry and carbon black slurry to be coated on the diffusion layer matrix that is loaded with PTFE, at 300-390 ℃ of following sintering 20-60min, obtain described gas diffusion layers then.
4. the preparation method of gas diffusion layers according to claim 3 is characterized in that, described dispersant is one or more among XH-1, AEO-9, FC4430, Tween-60, the Triton X-100.
5. the preparation method of gas diffusion layers according to claim 3 is characterized in that, described diffusion layer matrix is a kind of in carbon paper, carbon cloth (model is: TORY, SGL, GORE), stainless (steel) wire, nickel screen, the copper mesh.
6. the preparation method of gas diffusion layers according to claim 3 is characterized in that, described carbon black powders is that acetylene black is or/and active carbon.
7. the preparation method of gas diffusion layers according to claim 3 is characterized in that, described PTFE emulsion is that content is the PTFE emulsion of 10-50wt%.
8. the preparation method of gas diffusion layers according to claim 3 is characterized in that, described viscosity modifier is one or more in polyethylene glycol, ethylene glycol, glycerine, the cellulose.
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| CN102517602A (en) * | 2011-12-29 | 2012-06-27 | 北京化工大学 | Gelatin hole forming method for gas diffusion electrodes |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002110191A (en) * | 2000-09-27 | 2002-04-12 | Toyota Central Res & Dev Lab Inc | Direct methanol fuel cell |
| CN1572040A (en) * | 2001-10-15 | 2005-01-26 | 纳幕尔杜邦公司 | Solid polymer membrane for fuel cell with polyamine imbibed therein for reducing methanol permeability |
| CN1658422A (en) * | 2005-03-23 | 2005-08-24 | 武汉理工大学 | Gas diffusion layer for fuel cell and its preparation method |
| CN1734812A (en) * | 2005-06-08 | 2006-02-15 | 武汉理工大学 | Gas diffusion layer material for fuel cell and preparation method thereof |
| CN101022164A (en) * | 2007-01-19 | 2007-08-22 | 南京大学 | Method for producing fuel battery gas diffusion layer |
| CN101188302A (en) * | 2007-12-07 | 2008-05-28 | 哈尔滨工业大学 | Method for making film electrode component of proton exchange film fuel battery based on vibration method |
-
2009
- 2009-12-25 CN CN200910259752.9A patent/CN102110822B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002110191A (en) * | 2000-09-27 | 2002-04-12 | Toyota Central Res & Dev Lab Inc | Direct methanol fuel cell |
| CN1572040A (en) * | 2001-10-15 | 2005-01-26 | 纳幕尔杜邦公司 | Solid polymer membrane for fuel cell with polyamine imbibed therein for reducing methanol permeability |
| CN1658422A (en) * | 2005-03-23 | 2005-08-24 | 武汉理工大学 | Gas diffusion layer for fuel cell and its preparation method |
| CN1734812A (en) * | 2005-06-08 | 2006-02-15 | 武汉理工大学 | Gas diffusion layer material for fuel cell and preparation method thereof |
| CN101022164A (en) * | 2007-01-19 | 2007-08-22 | 南京大学 | Method for producing fuel battery gas diffusion layer |
| CN101188302A (en) * | 2007-12-07 | 2008-05-28 | 哈尔滨工业大学 | Method for making film electrode component of proton exchange film fuel battery based on vibration method |
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