CN1221050C - Preparation method of methanol oxidation electrode for direct methanol fuel cell - Google Patents
Preparation method of methanol oxidation electrode for direct methanol fuel cell Download PDFInfo
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- CN1221050C CN1221050C CNB031178235A CN03117823A CN1221050C CN 1221050 C CN1221050 C CN 1221050C CN B031178235 A CNB031178235 A CN B031178235A CN 03117823 A CN03117823 A CN 03117823A CN 1221050 C CN1221050 C CN 1221050C
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 230000003647 oxidation Effects 0.000 title claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 43
- 239000000446 fuel Substances 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 91
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 40
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 18
- 238000004070 electrodeposition Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004744 fabric Substances 0.000 claims abstract description 8
- -1 ruthenium ions Chemical class 0.000 claims abstract description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052755 nonmetal Inorganic materials 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 150000002843 nonmetals Chemical class 0.000 claims 1
- 229920000557 Nafion® Polymers 0.000 abstract description 20
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 13
- 239000012528 membrane Substances 0.000 abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910000929 Ru alloy Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 229910002849 PtRu Inorganic materials 0.000 description 17
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- JIDUBFKLNRRLDT-UHFFFAOYSA-N [Ru].[Pt].[C] Chemical compound [Ru].[Pt].[C] JIDUBFKLNRRLDT-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Inert Electrodes (AREA)
Abstract
一种直接甲醇燃料电池甲醇氧化电极制备方法，涉及直接甲醇燃料电池的电极制备方法。本发明在含铂、钌离子的水溶液中，在Nafion粘接的碳载体粉末的基体碳布或碳纸电极上，用电化学沉积的方法将铂钌合金沉积在与质子交换膜组分接触的碳载体粉末上，经水洗和电化学活化，形成负载金属催化剂铂钌的甲醇氧化电极。本发明具有工艺简单，生产周期短，所制甲醇氧化电极具有贵金属催化剂铂钌利用率高，催化活性高，电极成本低廉等特点。用本发明的甲醇氧化电极制造的直接甲醇燃料电池，广泛应用于电动汽车，便携式电子设备，如摄像机，笔记本电脑，电动玩具等。The invention discloses a method for preparing a methanol oxidation electrode of a direct methanol fuel cell, and relates to an electrode preparation method for a direct methanol fuel cell. In the aqueous solution containing platinum and ruthenium ions, on the base carbon cloth or carbon paper electrode of the carbon carrier powder bonded by Nafion, the platinum-ruthenium alloy is deposited on the surface contacted with the proton exchange membrane components by electrochemical deposition. The carbon carrier powder is washed with water and electrochemically activated to form a methanol oxidation electrode supporting metal catalyst platinum ruthenium. The invention has the advantages of simple process, short production period, and the prepared methanol oxidation electrode has the characteristics of high utilization rate of noble metal catalyst platinum and ruthenium, high catalytic activity, low electrode cost and the like. The direct methanol fuel cell manufactured by the methanol oxidation electrode of the present invention is widely used in electric vehicles, portable electronic equipment, such as video cameras, notebook computers, electric toys and the like.
Description
One technical field
The present invention relates to the methanol oxidation electrode preparation method of direct methanol fuel cell.
Two background technologies
Direct methanol fuel cell (DMFC) is with methyl alcohol (CH
3OH) be the negative reaction material, air is an anode reactant matter.Methyl alcohol oxidation under the catalysis of battery cathode catalyst discharges electronics, carbon dioxide (CO
2) and proton (H
+).CO
2Be discharged in the middle of the atmosphere H
+Arrive anode through proton exchange membrane, electronics drives the load acting through external circuit, also flows to anode, airborne oxygen under the catalysis of anode catalyst, catch the electronics that arrives at through external circuit and with H from exchange membrane
+In conjunction with generating water (H
2O).When a battery produces current, get rid of CO
2And H
2O.With with H
2For the Proton Exchange Membrane Fuel Cells of fuel is compared, be the DMFC of fuel with methyl alcohol, because the fluid characteristics of methyl alcohol is convenient to storage, volumetric specific energy height, become the chemical power source that portable electric appts and electric automobile are praised highly the most.Yet, and H
2-O
2Fuel cell is compared, and the methyl alcohol anodic oxidation speed of DMFC is significantly less than H
2Anodic oxidation speed.Improving the speed of the anode-catalyzed oxidation of methyl alcohol, is the business-like key issue of DMFC.
The platinum ruthenium catalyst (PtRu/C) that with the carbon dust is carrier is the most common and the most effective methanol oxidation catalyst.Chinese patent CN1318873 A discloses a kind of " preparation method of nanometer electrical catalyst for protein exchange film fuel cell ", its preparation method comprises following each step: with the platinum ruthenium halogen compound aqueous solution is raw material, wherein platinum/ruthenium mol ratio is 1: 0.2-1, be dissolved in the beaker with deionized water, bullion content 0.5-10g/l, adding active carbon adsorbs, adjust its pH value 2.5-10.5 with alkaline solution, add redistilled water and be made into suspension, stir, be heated to 50-65 ℃, add the excessive 2.5-5 of relative noble metal molal quantity reducing agent doubly, keep temperature to continue to stir 1 hour with drip-injection method; With liquid filtering, washing was up to wherein there not being Cl when temperature dropped to room temperature
-The time till; 60-80 ℃ of following vacuumize, obtain the carried by active carbon noble metal catalyst PtRu/C of particle diameter 4 ± 0.5 nanometers.
The preparation method of the methanol oxidation electrode of existing DMFC is, with mixture or independent film forming or the brushing of isopropyl alcohol, polytetrafluoroethylene (Teflon) emulsion, perfluoro alkyl sulfonic acid polymer (Nafion) solution and catalyst Pt Ru/C or be printed on the impregnated afflux utmost point of Teflon emulsion (carbon cloth or carbon paper), then with the proton exchange membrane electrolyte, air electrode hot pressing forms " electrode/membrane " assembly together.The H that methyl alcohol generates in the oxidation of negative pole Catalytic Layer
+Must pass mutually via the proton exchange membrane Nafion that mixes in the Catalytic Layer.Therefore, effectively catalyst is that those uninterruptedly are connected to dielectric film along the dielectric film direction by Nafion (ionic conduction phase) in Catalytic Layer, uninterruptedly is connected to the catalyst granules PtRu/C of gas diffusion layers by carbon granules (electron conduction phase) along afflux extreme direction.
The weak point of existing DMFC methanol oxidation electrode preparation method is: in the bonding PtRu/C of Nafion, in film formed of PtRu/C and the Nafion proton, because the mutual agglomeration of PtRu/C powder, part PtRu/C always can not contact with the Nafion proton exchange membrane, thereby becomes spent catalyst.Therefore, the Catalytic Layer of the Proton Exchange Membrane Fuel Cells of the method preparation of the bonding PtRu/C of usefulness Nafion, the utilance of noble metal catalyst PtRu is not high.
Three summary of the invention
The object of the present invention is to provide a kind of direct methanol fuel cell methanol oxidation electrode preparation method.It is simple that the present invention has technology, with short production cycle, noble metal platinum ruthenium catalyst utilance height, characteristics such as with low cost.It is the new method of efficient, the low-cost DMFC methanol oxidation electrode of preparation.
The object of the present invention is achieved like this: a kind of direct methanol fuel cell methanol oxidation electrode preparation method, its principal character is that isopropyl alcohol, carbon carrier powder, polytetrafluoroethylene (Teflon) emulsion, perfluoro alkyl sulfonic acid polymer (Nafion) solution is mixed and made into carbon ink mark mixture, again it is brushed equably or be printed on impregnated carbon cloth of Teflon or the carbon paper, make the non-metal catalyst carbon electrode through heat treated; Then, in the aqueous solution of platiniferous (Pt) and ruthenium (Ru) ion, with the method for electrochemical deposition, with the PtRu alloy deposition with carbon carrier that the proton exchange membrane component contact on, the DMFC methanol oxidation electrode of formation metal supported catalyst PtRu.
The method step of DMFC methanol oxidation electrode preparation is as follows:
The first step: the preparation of base electrode
It is that polytetrafluoroethylene (Teflon) emulsion of 30-60% was soaked 10-30 minute that carbon cloth or carbon paper are placed mass concentration, and taking-up is dried, and under 300-350 ℃ temperature, sintering 1-20 minute, just makes base electrode again.
Second step: preparation carbon ink mark mixture
With carbon carrier powder and mass concentration is that polytetrafluoroethylene (Teflon) emulsion of 10-60%, perfluoro alkyl sulfonic acid polymer (Nafion) solution that mass concentration is 0.1-5% are 100 by mass ratio: 0-50: 1-100 joins in the isopropyl alcohol; the amount of isopropyl alcohol is convenient to follow-up spreading with made carbon ink mark mixture and is advisable; carried out ultrasonic oscillation 5-60 minute, and formed carbon ink mark mixture.
The 3rd step: preparation non-metal catalyst carbon electrode
The carbon ink mark mixture for preparing is brushed equably or is printed on the base electrode for preparing, under 100-300 ℃ temperature, heat 2-30 minute after, be cooled to room temperature, just make the non-metal catalyst carbon electrode.
The 4th step: preparation platinum ruthenium catalyst carbon electrode
With the non-metal catalyst carbon electrode for preparing, placing platiniferous (Pt)/ruthenium (Ru) ion mol ratio is 1: the acid of 0.1-1 (example hydrochloric acid or sulfuric acid etc.) solution electrochemistry dislodger, with inactive, conductive material (as platinized platinum or graphite etc.) is auxiliary electrode, at room temperature, carry out electrochemical deposition with pulse current (as square wave current etc.) for operating current, Pt, Ru are deposited on the non-metal catalyst carbon electrode, form load platinum ruthenium catalyst carbon electrode.Cleaning platinum ruthenium catalyst carbon electrode repeatedly with deionized water again, then, is 0.01-5mol/l sulfuric acid (H in concentration
2SO
4) or perchloric acid (HClO
4) in the solution, in the 1.90V potential range, last at relative standard's hydrogen electrode-0.05 with linear potential method for scanning activated electrode repeatedly, from sulfuric acid or perchloric acid solution, take out electrode, clean repeatedly with deionized water again, just make platinum ruthenium catalyst carbon electrode.
In electrochemical deposition process, the deposition of platinum ruthenium (claiming load capacity again) can pass through to regulate platinum ruthenium ion concentration, pulse current size in the platinum ruthenium ion aqueous solution, and electrodeposition time is controlled.
In the process of preparation platinum ruthenium catalyst carbon electrode, on the matrix carbon electrode, brush equably or print in the mixture of forming by carbon carrier powder, Teflon emulsion, Nafion solution and isopropyl alcohol, to the carbon carrier powder of the carbon granule inside of Nafion polymer parcel, owing to can not contact with the aqueous solution of platiniferous ruthenium ion.Thereby, not with the direct contacted carbon carrier of Nafion on, the electrochemical deposition of platinum ruthenium ion will do not had, this has just guaranteed that all PtRu that are deposited always are deposited on the direct contacted carbon carrier with Nafion, thereby make the PtRu that is deposited be effective catalyst, the utilance height of noble metal catalyst PtRu, and then reduced the cost of electrode.
With model is that 112 or 115 or 117 perfluoro alkyl sulfonic acid polymer (Nafion) film places with between the methanol oxidation platinum ruthenium carbon electrode of method for preparing and the traditional hydrogen reduction platinum carbon electrode, under 200-250 ℃ of temperature, after hot pressing 1-10 minute, taking-up is cooled to room temperature, just makes " electrode/membrane " assembly of DMFC.
After the present invention adopts technique scheme, the utilization ratio height of noble metal catalyst PtRu, prepared platinum ruthenium catalyst carbon electrode cost is low.Adopt the platinum ruthenium catalyst carbon electrode of the present invention's preparation to can be applicable to direct methanol fuel cell.Direct methanol fuel cell with the present invention makes is widely used in electric automobile, various spacecrafts, and portable electric appts, as video camera, notebook computer, electronic toy etc.
Four description of drawings
Fig. 1 is at 0.5mol/l H
2SO
4With 0.5mol/l CH
3In the OH solution, under the room temperature, electrode potential is constant in 0.6 volt of relative standard's hydrogen electrode current potential, and the load capacity of catalyst platinum ruthenium is 0.20mg/cm
2The time, methanol oxidation current density-time graph on the different electrodes.
Curve 1 is in the electrochemical deposition solution, and platinum/ruthenium mol ratio is 1: 0 o'clock, the methanol oxidation current density-time graph of the methanol oxidation electrode of preparation.
Curve 2 is in the electrochemical deposition solution, and platinum/ruthenium mol ratio is 1: 0.1 o'clock, the methanol oxidation current density-time graph of the methanol oxidation electrode of preparation.
Curve 3 is in the electrochemical deposition solution, and platinum/ruthenium mol ratio is 1: 0.4 o'clock, the methanol oxidation current density-time graph of the methanol oxidation electrode of preparation.
Curve 4 is in the electrochemical deposition solution, and platinum/ruthenium mol ratio is 1: 1 o'clock, the methanol oxidation current density-time graph of the methanol oxidation electrode of preparation.
Curve 5 is the methanol oxidation current density-time graph according to the methanol oxidation electrode of platinum ruthenium catalyst (its platinum/ruthenium mol ratio is 1: the 1) preparation of CN1318873 A patent preparation.
Five embodiments
Below in conjunction with embodiment, further specify the present invention.
Embodiment 1
The first step: the preparation of base electrode
It is that the 60%Teflon emulsion was soaked 10 minutes that carbon cloth or carbon paper are placed mass concentration, and taking-up is dried, and under 300 ℃ temperature, sintering 10 minutes just makes base electrode again.
Second step: preparation carbon ink mark mixture
With carbon carrier powder (Vulcan XC-72) and mass concentration is that 60%Teflon emulsion and mass concentration be 0.1%Nafion solution by mass ratio are to join in isopropyl alcohol at 100: 1: 30; the amount of isopropyl alcohol is convenient to follow-up spreading with carbon ink mark mixture and is advisable; through ultrasonic oscillation 30 minutes, form carbon ink mark mixture.
The 3rd step: preparation non-metal catalyst carbon electrode
The carbon ink mark mixture for preparing is brushed equably on the base electrode for preparing, made the carbon carrier powder of electrode surface reach 0.8mg/cm
2, under 140 ℃ temperature, heat 5 minutes after, be cooled to room temperature, just make the non-metal catalyst carbon electrode.
The 4th step: preparation platinum ruthenium catalyst carbon electrode
With the non-metal catalyst carbon electrode for preparing, place 1mol/l hydrochloric acid (HCl), 1 * 10
-3Mol/l chloroplatinic acid (H
2PtCl
62H
2O) and 0.1 * 10
-3Mol/l ruthenium trichloride (RuCl
3) solution, be auxiliary electrode with the platinized platinum, with 14mA/cm
2Positive current and 140mA/cm
2The positive negative impulse current of negative current be applied between non-metal catalyst carbon electrode and the platinized platinum auxiliary electrode, positive current makes chloride ion-containing (Cl
-) Pt, Ru complex anion be enriched in the bonding carbon carrier surface of Nafion, negative current makes Pt in the complex anion that is enriched in the bonding carbon carrier surface of Nafion, Ru reduce deposition at carbon surface.According to number of times and the each time that keeps of reversal of determining that in the load capacity of electrode surface Pt, Ru reversal replaces.The number of times that the present embodiment reversal replaces is 20 times, and each 30 seconds time that keeps of reversal, the load capacity of PtRu is 0.20mg/cm
2Then, clean platinum ruthenium catalyst carbon electrode repeatedly, again at 0.1mol/l H with deionized water
2SO
4In the solution, in the 1.50V potential range, scan activated electrode repeatedly with linear potential at relative standard's hydrogen electrode-0.05, in the present embodiment, with the speed of 50mV/s, scan round 10 times.At last, from sulfuric acid solution, take out electrode, clean repeatedly with deionized water again.Just make platinum ruthenium catalyst carbon electrode.
The platinum ruthenium catalyst carbon electrode of above-mentioned preparation is placed 0.5mol/l H
2SO
4With 0.5mol/l CH
3In the OH solution, under the room temperature, be auxiliary electrode with the Pt sheet, electrode potential is constant when 0.6 volt of current potential of relative standard's hydrogen electrode, curve 2 among the methyl alcohol oxidation current density-time graph that records such as Fig. 1.
Embodiment 2
Respectively with 1mol/l HCl, 1 * 10
-3Mol/l H
2PtCl
62H
2O; 1mol/l HCl, 1 * 10
-3Mol/l H
2PtCl
62H
2O, 0.4 * 10
-3Mol/l RuCl
3With 1mol/l HCl, 1 * 10
-3Mol/lH
2PtCl
62H
2O, 1 * 10
-3Mol/l RuCl
3Replace electrochemical deposition solution (the 1mol/l HCl, 1 * 10 among the embodiment 1
-3Mol/l H
2PtCl
62H
2O and 0.1 * 10
-3Mol/l RuCl
3), each step of repetition embodiment 1 makes the load capacity of metallic catalyst on platinum or the platinum ruthenium catalyst carbon electrode be 0.20mg/cm
2Prepared platinum or platinum ruthenium catalyst carbon electrode are at 0.5mol/l H
2SO
4And 0.5mol/lCH
2In the OH solution, under the room temperature, be auxiliary electrode with the Pt sheet, electrode potential is constant when 0.6 volt of current potential of relative standard's hydrogen electrode, and the methyl alcohol oxidation current density-time graph that records is respectively as curve among Fig. 11, curve 3 and curve 4.
Contrast test
The first step: the preparation of base electrode
Place 60% polytetrafluoroethylene (Teflon) emulsion to soak 10 minutes carbon cloth or carbon paper, taking-up is dried, and under 300 ℃ temperature, sintering 10 minutes just makes base electrode again.
Second step: preparation platinum ruthenium carbon ink mark mixture
Will be according to the platinum ruthenium C catalyst (20%PtRu/C of CN1267922 A patent preparation; Pt: Ru is 1: 1) and mass concentration be that 60%Teflon emulsion and mass concentration are that 0.1%Nafion solution joins in the isopropyl alcohol by mass ratio at 100: 1: 30; the amount of isopropyl alcohol is convenient to follow-up spreading with made carbon ink mark mixture and is advisable; ultrasonic oscillation 30 minutes forms platinum ruthenium carbon ink mark mixture.
The 3rd step: preparation platinum ruthenium catalyst carbon electrode
The platinum ruthenium carbon ink mark mixture for preparing is brushed equably on the base electrode for preparing, made the load capacity of base electrode surface platinum ruthenium reach 0.2mg/cm
2, correspondingly, the area load amount of catalyst carrier carbon dust is 0.8mg/cm
2, under 140 ℃ temperature, heat 5 minutes after, be cooled to room temperature, just make platinum ruthenium catalyst carbon electrode.
The platinum ruthenium catalyst carbon electrode of above-mentioned preparation is placed 0.5mol/l H
2SO
4With 0.5mol/l CH
3In the OH solution, under the room temperature, be auxiliary electrode with the Pt sheet, electrode potential is constant when 0.6 volt of current potential of relative standard's hydrogen electrode, curve 5 among the methyl alcohol oxidation current density-time graph that records such as Fig. 1.
As shown in Figure 1,, be increased to 1: 0.4 again, continue to be increased to 1: 1, constantly increase with the electric current of the methanol oxidation electrode catalyst oxidation methyl alcohol of the present invention preparation along with platinum ruthenium ion mol ratio in the electrochemical deposition solution was increased to 1: 0.1 from 1: 0.By the methyl alcohol oxidation current density-time graph of the embodiment of the invention and contrast test as can be known: under the room temperature, under 0.6 volt of current potential of relative standard's hydrogen electrode, the identical load amount and the methanol oxidation electrode of identical platinum ruthenium mol ratio, the present invention is than in advance the platinum ruthenium being deposited on the carbon carrier powder, methyl alcohol anodic oxidation catalysis platinum ruthenium electrode with the bonding method preparation of Nafion has bigger output current, the methanol oxidation current density (mA/cm that they are constantly different then
2) contrast as follows:
| Time (second) | 500 | ?1000 | ?1500 | ?2000 | ?2500 |
| The present invention's (curve 4) | 8.9 | ?7.8 | ?7.0 | ?6.4 | ?5.9 |
| CN1267922 A patent (curve 5) | 4.0 | ?3.2 | ?2.9 | ?2.7 | ?2.5 |
Claims (2)
1, a kind of direct methanol fuel cell methanol oxidation electrode preparation method is characterized in that preparation method's step is as follows:
The first step: the preparation of base electrode
It is that the ptfe emulsion of 30-60% soaked 10-30 minute that carbon cloth or carbon paper are placed mass concentration, and taking-up is dried, again under 300-350 ℃ temperature, and sintering 1-20 minute;
Second step: preparation carbon ink mark mixture
With carbon carrier powder and mass concentration is that the ptfe emulsion of 10-60% and perfluoro alkyl sulfonic acid polymer solution that mass concentration is 0.1-5% are 100 by mass ratio: 0-50: 1-100 joins in the isopropyl alcohol, the amount of isopropyl alcohol is convenient to follow-up spreading with made carbon ink mark mixture and is advisable, and carries out ultrasonic oscillation 5-60 minute;
The 3rd step: preparation non-metal catalyst carbon electrode
The carbon ink mark mixture for preparing is brushed equably or is printed on the base electrode for preparing, and heating is 2-30 minute under 100-300 ℃ of temperature, is cooled to room temperature;
The 4th step: preparation platinum ruthenium catalyst carbon electrode
With the non-metal catalyst carbon electrode for preparing, placing platiniferous/ruthenium ion mol ratio is 1: the acid solution electrochemical deposition groove of 0.1-1, with the inactive, conductive material is auxiliary electrode, at room temperature, with the pulse current is that operating current carries out electrochemical deposition, the platinum ruthenium is deposited on the non-metal catalyst carbon electrode, clean platinum ruthenium catalyst carbon electrode repeatedly with deionized water again, then, in concentration is in the sulfuric acid or perchloric acid solution of 0.01-5mol/l, carries out linear potential scanning with activated electrode at relative standard's hydrogen electrode-0.05 in 1.90 volts potential range, last, from sulfuric acid or perchloric acid solution, take out electrode, clean repeatedly with deionized water again.
2, according to the described direct methanol fuel cell methanol oxidation of claim 1 electrode preparation method, it is characterized in that:
The first step: the preparation of base electrode
It is that 60% ptfe emulsion soaked 10 minutes that carbon cloth or carbon paper are placed mass concentration, and taking-up is dried, again under 300 ℃ temperature, and sintering 10 minutes;
Second step: preparation carbon ink mark mixture
With carbon carrier powder and mass concentration is that 60% ptfe emulsion and mass concentration are that 0.1% perfluoro alkyl sulfonic acid polymer solution joins in the isopropyl alcohol by mass ratio at 100: 1: 30, the amount of isopropyl alcohol was convenient to follow-up spreading with carbon ink mark mixture and is advisable, through ultrasonic oscillation 30 minutes;
The 3rd step: preparation non-metal catalyst carbon electrode
The carbon ink mark mixture for preparing is brushed equably on the base electrode for preparing, made the carbon carrier powder of electrode surface reach 0.8mg/cm
2, under 140 ℃ temperature, heat after 5 minutes, be cooled to room temperature;
The 4th step: preparation platinum ruthenium catalyst carbon electrode
Non-metal catalyst carbon electrode with preparing places 1mol/l hydrochloric acid, 1 * 10
-3Mol/l chloroplatinic acid and 1 * 10
-3In the mol/l ruthenium trichloride solution, be auxiliary electrode with the platinized platinum, with 14mA/cm
2Positive current and 140mA/cm
2The positive negative impulse current of negative current be applied between non-metal catalyst carbon electrode and the platinized platinum auxiliary electrode, the number of times that reversal replaces is 20 times, each 30 seconds time that keeps of reversal, then, clean platinum ruthenium catalyst carbon electrode repeatedly with deionized water, again at 0.1mol/l H
2SO
4In the solution, to the 1.50V potential range,, last with linear potential scan method scan round 10 times at relative standard's hydrogen electrode-0.05 with activated electrode with the speed of 50mV/s, from sulfuric acid solution, take out electrode, clean repeatedly with deionized water again.
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| CN100427945C (en) * | 2005-12-14 | 2008-10-22 | 中国科学院大连化学物理研究所 | Alcohol Concentration Sensor for Direct Alcohol Fuel Cell System |
| CN100384001C (en) * | 2006-04-28 | 2008-04-23 | 华南理工大学 | Method for preparing fuel cell membrane electrode by direct spraying |
| GB0714460D0 (en) * | 2007-07-25 | 2007-09-05 | Johnson Matthey Plc | Catalyst |
| CN116103693B (en) * | 2022-11-25 | 2023-09-12 | 东莞理工学院 | Hydrogen evolution electrode, preparation method thereof and application thereof in hydrogen production by water electrolysis |
| CN119069721A (en) * | 2024-07-10 | 2024-12-03 | 昆明理工大学 | Preparation method and application of carbon paper-supported icosahedral Pt nanocrystal integrated electrode |
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