CN1208862C - Prepn of electrode for proton exchange film fuel cell - Google Patents
Prepn of electrode for proton exchange film fuel cell Download PDFInfo
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- CN1208862C CN1208862C CNB031276776A CN03127677A CN1208862C CN 1208862 C CN1208862 C CN 1208862C CN B031276776 A CNB031276776 A CN B031276776A CN 03127677 A CN03127677 A CN 03127677A CN 1208862 C CN1208862 C CN 1208862C
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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
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- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention belongs to a method for preparing electrodes of proton exchange membrane fuel batteries. Catalysts, PTFE and lower alcohol are mixed, an ultrasonic generator is used for dispersion and mechanical stirring for 0.5 to 30 minutes, and the mixture is transferred onto carbon paper or carbon cloth by adopting a blade coating method in a mold plate to prepare electrodes of proton exchange membrane fuel batteries. Then, the electrodes are dried at the temperature of 20 to 120 DEG C in vacuum for 2 to 24 hours and are sintered at the temperature of 150 to 350 DEG C under the protection of air or argon for 0.5 to 2 hours, and then, Nafion raw liquor is sprayed to the surfaces of the electrodes. Finally, the electrodes are dried at the temperature of 20 to 120 DEG C in vacuum for 2 to 24 hours. The method can effectively control the thickness of a catalyst layer of an electrode, so that the thickness of the electrode can be reduced greatly and becomes uniform. Besides, the method can be used for the rapid large-scale preparation of electrodes with large areas. The present invention has the advantages of high operability, rapid preparing process, convenient and simple operation, no need for special devices and favorable repeatability.
Description
Technical field
The invention belongs to the preparation method of proton exchange membrane fuel cell electrode.
Background technology
Proton Exchange Membrane Fuel Cells is (with H
2Or methyl alcohol is fuel) owing to have energy conversion efficiency height, noiseless, pollution-free, characteristics and wide application prospect thereof such as flexibility is big, now become one of international research focus.In this class battery, the preparation technology of electrode is one of key issue that influences battery performance, and form, resistance and the electricity that relates to catalyst consumption and effective rate of utilization, electrode such as leads at all many-sides.In fuel cell 30 years of development processes, people have successively studied and have been coated with cream method [Makoto Uchida, J.Electrochem Soc, 142,2 (1995)], casting method [A.C.Ferreira, S.Srinivasan, Extd.Abs.94-1, TheElectrochemical Sociaty, NJ1994], rolling process [E.J.Taylor, J. ElectrochemSoc 139, L45 (1993)], sputtering method [Shinichi Hirano, et al.High performanceproton exchange membrane fuel cells with sputter-diposited Pt layerelectrodes.Electrochimica acta.1997,42 (10): 1587～1593], electrochemical catalysis technology [M.S.Wilson, S.Gottesfeld, J Electrochem Soc, 22,1 (1992), E.J.Taylor, et al.preparation of high-platinum-utilization gas diffusionelectrodes for proton-exchang-membrane furl cells.Journal ofelectrochemical society.1992,139 (5): L45～L46] etc. multiple technology for preparing electrode makes battery performance obtain continuous raising.
Yet more or less all there are some problems in above-mentioned these methods.On the one hand, said method is bigger as the thickness of electrode that is coated with cream method, casting method, rolling process preparation, and the Catalytic Layer inner transmission matter is apart from increase, and electrode produces serious concentration polarization when causing heavy-current discharge, and the resistance of catalyst layer is also bigger.To use a large amount of catalyst simultaneously, reduce the utilance of catalyst.On the other hand, preparation technology's relative complex of methods such as some method such as rolling process, sputtering method, electrochemical catalysis technology needs special equipment, has increased preparation time and expense.Having is exactly except rolling process again, and additive method only is suitable for preparing the electrode of small size, inapplicable for the larger area electrode, as is coated with the electrode of homogeneity cream method, casting method are difficult to guarantee to(for) large electrode; Sputtering method, electrochemical catalysis technology can't meet the demands on instrument for large electrode.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of proton exchange membrane fuel cell electrode.Employing mixes catalyst, ptfe emulsion and lower alcohol such as ethanol, propyl alcohol, isopropyl alcohol, and the method by blade coating in thickness is the template of 0.3-1.0mm prepares proton exchange membrane fuel cell electrode.Template cuts out mid portion by the plastic packaging film with different-thickness, is bonded on the smooth glass plate with double faced adhesive tape to make.The electrode of preparation does not reduce or improves the performance of electrode under the situation of using less catalyst, can prepare the electrode of various areas fast, in a large number.
The catalyst that the present invention adopts Proton Exchange Membrane Fuel Cells to use; adding lower alcohol and weight ratio are 10% ptfe emulsion; additional proportion is: catalyst: lower alcohol: ptfe emulsion=10mg: 0.8-8g: 11-67mg; disperse with supersonic generator; add mechanical agitation 0.5-30 minute; scattered mixture is transferred in the template; template thickness is 0.3-1.0mm; pass through blade coating; transfer to equably on carbon paper or the carbon cloth; at 20-120 ℃ of following vacuumize 2-24 hour; under 150-350 ℃ of air or argon shield sintering 0.5-2 hour again, sprayed with the Nafion stoste after the lower alcohol dilution, again in 20-120 ℃ of following vacuumize 2-24 hour on the surface then; polytetrafluoroethylene accounts for 10-40wt% in the catalyst layer that obtains at last, and polymer dielectric Nafion accounts for 5-25wt%.
Because the present invention is at first with catalyst and PTFE emulsion lower alcohol high degree of dispersion, fully stir vibration, blade coating is to supporting layer then, therefore catalyst granules has been distributed in the Catalytic Layer equably, and because cross shear and pressure are longitudinally arranged in the process of blade coating, make that combination closely makes the easier formation network structure of PTFE between the catalyst layer particle, after hot pressing, combine firmly with proton exchange membrane.Have certain thickness template owing to use, the method can also effectively be controlled the thickness of pole catalyze layer, and the thickness of Catalytic Layer is reduced greatly and is very even.This method is applicable to the electrode of the various areas of preparation, and large-area electrode is more suitable for.Experimental result shows, adopts this method to prepare electrode and obtains good performance.
The present invention prepares the method for proton exchange membrane fuel cell electrode and compares and have following advantage with the various fuel cell electrode preparation methods of report in the past: (1) provides a kind of preparation method of broad-area electrode; (2) operability height, preparation process is rapid, and is easy to operation, need not special installation; (3) reduced catalyst amount, the utilance of noble metal improves greatly in the catalyst; (4) has good reappearance.
Embodiment
Embodiment 1: with 40mg
Pt/
C, 40mg
PtRu/
CCatalyst is that ptfe emulsion and the ethanol of 10wt% mixes with concentration respectively, with supersonic generator disperse, mechanical agitation 1 minute simultaneously, scattered mixture is transferred in the template that thickness is 0.3mm, and transferring to area equably by blade coating is 4cm
2Carbon paper on, 30 ℃ of following vacuumize 12 hours, sintering is 6 hours under 250 ℃ of argon shields, the Nafion stoste of surface spraying after with the ethanol dilution in 80 ℃ of following vacuumizes 2 hours, makes anode and negative electrode respectively again.Polytetrafluoroethylene accounts for 30wt% in the catalyst layer that obtains at last, and polymer dielectric Nafion accounts for 15wt%.Assembled battery was tested after this electrode made the electrode/membrane aggregate.Anode adopts methanol solution to make working substance matter, and negative electrode oxygen is as oxidant, and the electrode discharge electric current can reach 0.15A/cm
2, electrode power density can reach 40-60mw/cm
2Than adopting the electrode performance that is coated with the preparation of cream method to exceed 20%.
Embodiment 2: with 200mgPt/C, 200mgPtRu/C catalyst is that ptfe emulsion and the isopropyl alcohol of 10wt% mixes with concentration respectively, with supersonic generator disperse, mechanical agitation 2 minutes simultaneously, scattered mixture is transferred in the template that thickness is 0.5mm, and transferring to area equably by blade coating is 50cm
2Carbon paper on, 80 ℃ of following vacuumize 2 hours, 340 ℃ of following heat treatment 1 hour, the surface spraying in 80 ℃ of following vacuumizes 2 hours, makes anode and negative electrode respectively again with the Nafion stoste after the isopropanol.Polytetrafluoroethylene accounts for 20wt% in the catalyst layer that obtains at last, and polymer dielectric Nafion accounts for 20wt%.Assembled battery was tested after this electrode made the electrode/membrane aggregate.Anode adopts methanol solution to make working substance matter, and negative electrode oxygen is as oxidant, and the electrode discharge electric current can reach 0.18A/cm
2, electrode power density can reach 40-72mw/cm
2Than adopting the electrode performance that is coated with the preparation of cream method to exceed 30%.
Embodiment 3: with 300mgPt/C, 300mgPtRu/C catalyst is that ptfe emulsion and the propyl alcohol of 10wt% mixes with concentration respectively, with supersonic generator disperse, mechanical agitation 5 minutes simultaneously, scattered mixture is transferred in the template that thickness is 0.8mm, and transferring to area equably by blade coating is 50cm
2Carbon cloth on, 80 ℃ of following vacuumize 2 hours, 340 ℃ of following heat treatment 1 hour, the surface spraying Nafion stoste after with the propyl alcohol dilution in 80 ℃ of following vacuumizes 2 hours, makes anode and negative electrode respectively again.Polytetrafluoroethylene accounts for 20wt% in the catalyst layer that obtains at last, and polymer dielectric Nafion accounts for 20wt%.Assembled battery was tested after this electrode made the electrode/membrane aggregate.Anode adopts methanol solution to make working substance matter, and negative electrode oxygen is as oxidant, and the electrode discharge electric current can reach 0.16A/cm
2, electrode power density can reach 40-60mw/cm
2Than adopting the electrode performance that is coated with the preparation of cream method to exceed 25%.
Embodiment 4: with 400mgPt/C, 400mgPtRu/C catalyst is that ptfe emulsion and the isopropyl alcohol of 10wt% mixes with concentration respectively, with supersonic generator disperse, mechanical agitation 8 minutes simultaneously, scattered mixture is transferred in the template that thickness is 0.4mm, and transferring to area equably by blade coating is 50cm
2Carbon paper on, 80 ℃ of following vacuumize 3 hours, 340 ℃ of following heat treatment 2 hours, the surface spraying in 80 ℃ of following vacuumizes 3 hours, makes anode and negative electrode respectively again with the Nafion stoste after the isopropanol.Polytetrafluoroethylene accounts for 20wt% in the catalyst layer that obtains at last, and polymer dielectric Nafion accounts for 15wt%.Assembled battery was tested after this electrode made the electrode/membrane aggregate.Anode adopts methanol solution to make working substance matter, and negative electrode oxygen is as oxidant, and the electrode discharge electric current can reach 0.20A/cm
2, electrode power density can reach 40-80mw/cm
2Than adopting the electrode performance that is coated with the preparation of cream method to exceed 30%.
Embodiment 5: except carbon paper is changed into the carbon cloth, all the other are identical with embodiment 4, and the electrode discharge electric current can reach 0.18A/cm
2, electrode power density can reach 40-70mw/cm
2Than adopting the electrode performance that is coated with the preparation of cream method to exceed 25%.
Embodiment 6: with 500mgPt/C, 500mgPtRu/C catalyst is that ptfe emulsion and the isopropyl alcohol of 10wt% mixes with concentration respectively, with supersonic generator disperse, mechanical agitation 10 minutes simultaneously, scattered mixture is transferred in the template that thickness is 1.0mm, and transferring to area equably by blade coating is 100cm
2Carbon paper on, 80 ℃ of following vacuumize 2 hours, 340 ℃ of following heat treatment 1 hour, the surface spraying in 80 ℃ of following vacuumizes 2 hours, makes anode and negative electrode respectively again with the Nafion stoste after the isopropanol.Polytetrafluoroethylene accounts for 20wt% in the catalyst layer that obtains at last, and polymer dielectric Nafion accounts for 20wt%.Assembled battery was tested after this electrode made the electrode/membrane aggregate.Anode adopts methanol solution to make working substance matter, and negative electrode oxygen is as oxidant, and the electrode discharge electric current can reach 0.18A/cm
2, electrode power density can reach 40-80mw/cm
2Than adopting the electrode performance that is coated with the preparation of cream method to exceed 30%.
Embodiment 7: with 600mgPt/C, 600mgPtRu/C catalyst is that ptfe emulsion and the isopropyl alcohol of 10wt% mixes with concentration respectively, with supersonic generator disperse, mechanical agitation 5 minutes simultaneously, scattered mixture is transferred in the template that thickness is 0.5mm, and transferring to area equably by blade coating is 100cm
2Carbon paper on, 100 ℃ of following vacuumize 10 hours, 340 ℃ of following heat treatment 2 hours, the surface spraying in 100 ℃ of following vacuumizes 2 hours, makes anode and negative electrode respectively again with the Nafion stoste after the isopropanol.Polytetrafluoroethylene accounts for 30wt% in the catalyst layer that obtains at last, and polymer dielectric Nafion accounts for 20wt%.Assembled battery was tested after this electrode made the electrode/membrane aggregate.Anode adopts methanol solution to make working substance matter, and negative electrode oxygen is as oxidant, and the electrode discharge electric current can reach 0.20A/cm
2, electrode power density can reach 60-80mw/cm
2Than adopting the electrode performance that is coated with the preparation of cream method to exceed 35%.
Embodiment 8: with 800mgPt/C, 800mgPtRu/C catalyst is that ptfe emulsion and the isopropyl alcohol of 10wt% mixes with concentration respectively, with supersonic generator disperse, mechanical agitation 5 minutes simultaneously, scattered mixture is transferred in the template that thickness is 0.6mm, and transferring to area equably by blade coating is 144cm
2Carbon paper on, 100 ℃ of following vacuumize 10 hours, 340 ℃ of following heat treatment 2 hours, the surface spraying in 100 ℃ of following vacuumizes 2 hours, makes anode and negative electrode respectively again with the Nafion stoste after the isopropanol.Polytetrafluoroethylene accounts for 30wt% in the catalyst layer that obtains at last, and polymer dielectric Nafion accounts for 20wt%.Assembled battery was tested after this electrode made the electrode/membrane aggregate.Anode adopts methanol solution to make working substance matter, and negative electrode oxygen is as oxidant, and the electrode discharge electric current can reach 0.20A/cm
2, electrode power density can reach 60-80mw/cm
2Than adopting the electrode performance that is coated with the preparation of cream method to exceed 35%.
Embodiment 9: except carbon paper is changed into the carbon cloth, all the other are identical with embodiment 8, and the electrode discharge electric current can reach 0.18A/cm
2, electrode power density can reach 40-70mw/cm
2Than adopting the electrode performance that is coated with the preparation of cream method to exceed 30%.
Embodiment 10: with 1500mgPt/C, 1500mgPtRu/C catalyst is that ptfe emulsion and the isopropyl alcohol of 10wt% mixes with concentration respectively, with supersonic generator disperse, mechanical agitation 10 minutes simultaneously, scattered mixture is transferred in the template that thickness is 1.0mm, and transferring to area equably by blade coating is 225cm
2Carbon paper on, 100 ℃ of following vacuumize 10 hours, 340 ℃ of following heat treatment 2 hours, the surface spraying in 100 ℃ of following vacuumizes 2 hours, makes anode and negative electrode respectively again with the Nafion stoste after the isopropanol.Polytetrafluoroethylene accounts for 30wt% in the catalyst layer that obtains at last, and polymer dielectric Nafion accounts for 20wt%.Assembled battery was tested after this electrode made the electrode/membrane aggregate.Anode adopts methanol solution to make working substance matter, and negative electrode oxygen is as oxidant, and the electrode discharge electric current can reach 0.20A/cm
2, electrode power density can reach 60-80mw/cm
2Than adopting the electrode performance that is coated with the preparation of cream method to exceed 40%.
Claims (1)
1. the preparation method of a proton exchange membrane fuel cell electrode; it is characterized in that adopting the catalyst of Proton Exchange Membrane Fuel Cells use; add ethanol; propyl alcohol or isopropyl alcohol and weight ratio are 10% ptfe emulsion; additional proportion is: catalyst: ethanol; propyl alcohol or isopropyl alcohol: ptfe emulsion=10mg: 0.8-8g: 11-67mg; disperse with supersonic generator; add mechanical agitation 0.5-30 minute; scattered mixture is transferred in the template of 0.3-1.0mm; pass through blade coating; transfer to equably on carbon paper or the carbon cloth; at 20-120 ℃ of following vacuumize 2-24 hour; under 150-350 ℃ of air or argon shield sintering 0.5-2 hour again; spray with the Nafion stoste after the lower alcohol dilution on the surface then; again in 20-120 ℃ of following vacuumize 2-24 hour; polytetrafluoroethylene accounts for 10-40wt% in the catalyst layer that obtains at last, and polymer dielectric Nafion accounts for 5-25wt%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031276776A CN1208862C (en) | 2003-08-13 | 2003-08-13 | Prepn of electrode for proton exchange film fuel cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031276776A CN1208862C (en) | 2003-08-13 | 2003-08-13 | Prepn of electrode for proton exchange film fuel cell |
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| CN1487610A CN1487610A (en) | 2004-04-07 |
| CN1208862C true CN1208862C (en) | 2005-06-29 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345326C (en) * | 2004-05-14 | 2007-10-24 | 武汉理工大学 | Unit combined high temperature proton exchange film fuel cell membrane electrode and preparation |
| CN100353597C (en) * | 2004-08-10 | 2007-12-05 | 长沙丰日电气集团有限公司 | Method for preparing catalytic film of hydrogen air fuel cell |
| CN100524913C (en) * | 2005-04-01 | 2009-08-05 | 清华大学深圳研究生院 | Method for preparing membrane electrode of direct methanol fuel cell |
| JP5274035B2 (en) * | 2007-03-27 | 2013-08-28 | 三洋電機株式会社 | Fuel cell |
| CN101702436B (en) * | 2009-10-26 | 2012-06-27 | 新源动力股份有限公司 | Sizing agent for proton exchange membrane fuel cell electrodes and preparation method thereof |
| CN102593471B (en) * | 2012-03-06 | 2015-02-18 | 中国科学院长春应用化学研究所 | Preparation method of electrode of proton exchange membrane fuel cell and proton exchange membrane fuel cell |
| CN102743960B (en) * | 2012-07-25 | 2015-04-29 | 中国科学院重庆绿色智能技术研究院 | Preparation method of carbon-based combined electrode, electrolytic tank for decarbonization and desulphurization of flue gas and method for decarbonizing and desulphurizing flue gas on the basis of electrolytic tank |
| CN104363380B (en) * | 2014-10-15 | 2017-10-27 | 北京智谷睿拓技术服务有限公司 | IMAQ control method and device |
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