CN1976101A - Method for producing carbon-carrying platinum-based alloy electrode - Google Patents
Method for producing carbon-carrying platinum-based alloy electrode Download PDFInfo
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- CN1976101A CN1976101A CNA2006101022728A CN200610102272A CN1976101A CN 1976101 A CN1976101 A CN 1976101A CN A2006101022728 A CNA2006101022728 A CN A2006101022728A CN 200610102272 A CN200610102272 A CN 200610102272A CN 1976101 A CN1976101 A CN 1976101A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 44
- 239000000956 alloy Substances 0.000 title claims abstract description 24
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 72
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000004070 electrodeposition Methods 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 33
- -1 salt compound Chemical class 0.000 claims abstract description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 239000004744 fabric Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 18
- 230000010355 oscillation Effects 0.000 claims description 17
- 239000010953 base metal Substances 0.000 claims description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000976 ink Substances 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 31
- 239000002245 particle Substances 0.000 abstract description 11
- 239000000446 fuel Substances 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000010411 electrocatalyst Substances 0.000 abstract description 2
- 239000011149 active material Substances 0.000 abstract 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 12
- 238000000151 deposition Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 229910052707 ruthenium Inorganic materials 0.000 description 8
- 229920000557 Nafion® Polymers 0.000 description 7
- 239000002923 metal particle Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 241000896524 Sarcophaga par Species 0.000 description 4
- 101000803345 Ustilago maydis (strain 521 / FGSC 9021) Virulence-associated membrane protein 2 Proteins 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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Classifications
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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
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Inert Electrodes (AREA)
Abstract
本发明公开了一种碳载铂基合金电极的制备方法，该工艺方法首先是将碳载体在惰性气体保护下烘烤，与PTFE乳液和异丙醇一起加入到水中，搅拌，超声振荡，并涂覆在碳布或碳纸上；其次将含铂基金属盐化合物活性物前驱体与全氟烷基磺酸聚合物乳液、异丙醇、乙二醇、水和碳载体混合，超声振荡，再次涂覆于碳布或碳纸上，烘干，制成含铂基活性物前驱体的碳载多孔电极；最后将碳载多孔电极作为工作电极置于含有酸溶液的电化学沉积槽中，用脉冲电流进行电化学沉积，洗涤制成碳载铂基合金电极。本发明能够有效调控沉积活性物的粒径大小及分布，提高了贵金属催化剂的利用率，降低了电极的制造成本，简化了碳载活性物电催化剂多孔电极的制备工艺。可应用于燃料电池电极的制备。The invention discloses a method for preparing a carbon-supported platinum-based alloy electrode. The process firstly involves baking the carbon carrier under the protection of an inert gas, adding it to water together with PTFE emulsion and isopropanol, stirring, ultrasonically oscillating, and Coated on carbon cloth or carbon paper; secondly, the precursor of platinum-based metal salt compound active material is mixed with perfluoroalkane sulfonic acid polymer emulsion, isopropanol, ethylene glycol, water and carbon carrier, ultrasonically oscillated, Coated on carbon cloth or carbon paper again, dried to make a carbon-supported porous electrode containing a platinum-based active material precursor; finally, the carbon-supported porous electrode was placed in an electrochemical deposition tank containing an acid solution as a working electrode, Electrochemical deposition is carried out with pulse current, and the carbon-supported platinum-based alloy electrode is made by washing. The invention can effectively regulate the particle size and distribution of the deposited active matter, improve the utilization rate of the noble metal catalyst, reduce the manufacturing cost of the electrode, and simplify the preparation process of the carbon-supported active matter electrocatalyst porous electrode. It can be applied to the preparation of fuel cell electrodes.
Description
Technical field
The present invention relates to the porous electrode preparation of nano metal particles and alloy thereof, relate in particular to the preparation method who on carbon carrier, supports based on the porous electrode of the Proton Exchange Membrane Fuel Cells nano metal particles eelctro-catalyst of platinum, belong to Preparation of Catalyst and porous catalytic electrode fabrication field.
Background technology
Fuel cell is efficient, the clean electricity generation system that the contained chemical energy of fuel directly is converted into continuously electric energy by electrochemical reaction.Because (Proton Exchange Membrane FuelCell PEMFC) has advantages such as operating temperature is low, energy density is high, the startup of no burn into is fast, thereby promises to be compact power and Miniature Power Unit most Proton Exchange Membrane Fuel Cells.In PEMFC, Catalytic Layer is the place that electrode carries out electrochemical reaction, and its structure has material impact for the performance of battery.Because electrode reaction is the polyphase electrocatalytic reaction among the PEMFC, every effective active matter particle all should have the passage of transmission electronic, proton, reactant and product simultaneously on the eelctro-catalyst.The active matter particle that lacks above-mentioned any passage all can't carry out electrode reaction continuously.So the utilance of catalyst particle is to influence electrode and battery performance key factor in the PEMFC electrode.Up to now, platinum and platinum base alloy material are considered to the most effective eelctro-catalyst of PEMFC.But,, see that from practical angle utilizing the platinum resource how cost-effectively is vital to the industrialization of solid electrolytic membrane cell because the platinum price is comparatively expensive and resource-constrained.
The utilance of active matter depends on catalyst present position and active matter diameter of particle size on the carrier, has only active matter is placed the valid active matter in threephase region between proton conducting membranes and the carbon carrier.In order to improve the utilance of platinum, reduce cost, now developed multiple PEMFC technology for preparing electrode, mainly contain bond catalysts (or active matter) method and deposition active matter method.The bond catalysts method is also referred to as two step method, promptly prepares eelctro-catalyst earlier, and the back forms porous catalyst layer with adhesive bonds." membrane process " (thin film) is present popular bond catalysts method, as document (S.Litsterl, G.McLean.J.Power Sources, 2004,130:61-76) in the electrode of preparation, active matter efficient only 42%.Deposition active matter method is also referred to as one-step method, promptly directly deposits the method for active component on the porous diffusion layer matrix.Mainly comprise physical deposition method (as sputtering method, vacuum deposition method), electrochemical deposition method etc.Sputtering method, vacuum deposition method manufacturing cost height, application is restricted.Electrochemical deposition method is a kind ofly the nano_scale particle deposit can be positioned the lip-deep short-cut method of arbitrary shape conducting base, has advantages such as deposit contacts with matrix closely, resistance is little, microscopic appearance is controlled, technology is simple.For this reason, people attempt to utilize the method for electro-deposition to prepare small particle diameter noble metal electrocatalyst layer.Thompson etc. (S.D.Thompson, L.R.Jordan, M.Forsyth.Electrochim.Acta, 2001,46:1657-) make Pt (NH by ion-exchange
3)
4 2+Enter Nafion, adopt electro-deposition to make metal particle be deposited on closely black carbon surface of Nafion again, experiment confirm Pt utilance improves a lot.But the metal particle of deposition is even inadequately.(K.H Choi such as Choi, H.S.Kim, T.H.Lee.J.Power Sources, 1998,75:230) in order to improve the uniformity of deposited particles, adopt the pulse electrodeposition method successfully to support 1.5nm diameter Pt particulate in PTFE-carbon black thin layer, but, the catalyst layer Pt utilance of Choi preparation is not high.This is because there be the polarization relatively poor deficiency of metal ion in the matrix surface deposition in existing electrodeposition process.Therefore the eelctro-catalyst active matter of prepared by electrodeposition can not finely enter into the threephase region between proton conducting membranes and the carbon carrier, and the noble metal catalyst utilance is not high.Result of study just at present, noble metal efficient still has bigger room for promotion in the catalyst layer.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of carbon-carrying platinum-based alloy electrode, to solve electrode catalyst particle diameter skewness, polarization difference are brought in the fuel cell the activity and the problem that power is low and cost is high of battery.
The preparation method of carbon-carrying platinum-based alloy electrode of the present invention is achieved through the following technical solutions, this process at first is that carbon carrier is toasted under inert gas shielding, is added to the water with PTFE emulsion and isopropyl alcohol, stirs, sonic oscillation, and be coated on carbon cloth or the carbon paper; Secondly platiniferous Base Metal salt compound active matter presoma is mixed with perfluoro alkyl sulfonic acid polymer emulsion, isopropyl alcohol, ethylene glycol, water and carbon carrier, sonic oscillation, be coated on once more on carbon cloth or the carbon paper, oven dry, the carbon of making platiniferous base active matter presoma carries porous electrode; At last carbon being carried porous electrode and place the electrochemical deposition groove that contains acid solution as work electrode, is to electrode with the Pt electrode, and saturated calomel electrode is a reference electrode, carries out electrochemical deposition with pulse current, and carbon-carrying platinum-based alloy electrode is made in washing.
The preparation method's of carbon-carrying platinum-based alloy electrode of the present invention concrete preparation process follows these steps to carry out:
(1) with carbon carrier under inert gas shielding, and 300 ℃～600 ℃ bakings 1～4 hour, be 10%～60% PTFE emulsion and isopropyl alcohol then with carbon carrier and mass concentration by mass ratio be 100: 5～50: 1～50 to be added to the water, stirred 5～40 minutes, sonic oscillation 5～60 minutes is made prepared Chinese ink shape mixture, and it is coated on carbon paper or the carbon cloth, under 200 ℃～350 ℃ temperature, baking;
(2) be 0.1%～5% perfluoro alkyl sulfonic acid polymer emulsion, isopropyl alcohol, ethylene glycol, water and carbon carrier with platiniferous Base Metal salt compound active matter presoma, mass concentration by mass ratio be 100: 5～50: 1～100: 1～100: 1～100: 20～200 to mix, sonic oscillation 20～50 minutes, make the prepared Chinese ink mixture of platiniferous Base Metal salt compound presoma, be coated on once more on the carbon paper or carbon cloth in the above-mentioned steps (1), its metal active thing coated weight is 0.05～5.00mgcm
-2, and under 30 ℃～90 ℃ temperature, dry, at last 80 ℃～120 ℃ hot pressing 0.2～3 minute, the carbon that obtains platiniferous base active matter presoma carries porous electrode;
(3) carbon with the platiniferous base active matter presoma of preparation in the above-mentioned steps (2) carries porous electrode as work electrode, place the electrochemical deposition groove of acid solution, with the Pt electrode is to electrode, saturated calomel electrode is a reference electrode, and carry out electrochemical deposition with pulse current, make carbon-carrying platinum-based alloy electrode with the distilled water washing.
Carbon carrier described in the preparation method of carbon-carrying platinum-based alloy electrode of the present invention is active carbon, XC-72 carbon black, carbon nano-tube or carbon fiber; Described platinum Base Metal salt compound active matter presoma is (SO
3)
2Pt (NH
3)
4, K
2PtCl
6, H
2PtCl
66H
2O or platinum acetate; Or wherein contain the metal salt compound of Pt and one or more metal salt compounds among Ru, W, Os, Mo, Ni, Sn or the Ir; The ratio of the metal salt compound of described Pt and Ru, W, Os, Mo, Ni, Sn or Ir metal salt compound is 100: 0～100; Described acid solution is hydrochloric acid, sulfuric acid, nitric acid, acetic acid, perchloric acid or phosphoric acid; When described pulse current carried out electrochemical deposition, its pulse negative current current potential was-0.5～0.3V, and pulse positive current current potential is 0.2～0.8V, and pulse current is 0～20mA/cm
2Positive current and 10～200mA/cm
2Negative current, the pulse period is 30～1000ms, negative current and positive current time scale are t
n/ t
p=1: 0.5～10.
The present invention is in the process of preparation carbon-carrying platinum-based alloy electrode, because the active matter presoma is preset in the proton conductor Nafion colloid, solved the directionality problem of electro-deposition, make metallic preferential deposition carbon carrier surface near Nafion, guaranteed that all metal particles that are deposited are positioned conductive carbon carrier and proton conductor joint portion in high proportion, thus make the metallic that deposited efficiently be higher than common membrane electrode preparation method; Simultaneously, by changing the particle size and the particle size distribution of condition regulation and control deposition active matters such as negative current and positive current time scale, pulse period, electrode potential, particle size range is between 2～12nm, improved the utilance of noble metal catalyst, reduce the manufacturing cost of electrode, simplified the preparation technology that carbon carries active matter eelctro-catalyst porous electrode.
Compared with prior art, the present invention does not need metal precursor is carried out preliminary treatment, does not need other protective agent and reducing agent, this preparation method to have that simple to operate, controllability is strong, noble metal utilance height yet, and the Preparation of Catalyst cost is lower.
The present invention is as being that the perfluoro alkyl sulfonic acid polymer proton film of Nafion112 or Nafion115 or Nafion117 places with between two cube electrodes of method for preparing with marque, under 200 ℃～250 ℃ temperature, after the hot pressing 1～10 minute, can make the membrane electrode assembly of Proton Exchange Membrane Fuel Cells.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the synthetic catalyst of the embodiment of the invention 2
Fig. 2 is that the EDS of the synthetic catalyst of the embodiment of the invention 2 can spectrogram
Fig. 3 is the transmission electron microscope shape appearance figure of the synthetic catalyst of the embodiment of the invention 2
Embodiment
For illustrating that quantitatively the plated metal particle all has unimpeded electric transmission path, adopt CO absorption coulometry and two kinds of methods of XRD to measure the diameter and the specific surface area data of plated metal particle, go out catalyst activity thing surface current density value by data computation, calculate the metal effective rate of utilization of carrying the thin layer Catalytic Layer with respect to carbon with the ratio that on glass-carbon electrode, carries out the oxidation peak current density value that identical parameters electro-deposition experiment and thin layer cyclic voltammetry scan obtain.
Embodiment 1
(1) with carbon carrier Vulcan XC-72 under inert gas Ar protection, 600 ℃ were toasted 1 hour, be 30% PTFE emulsion and isopropyl alcohol then with Vulcan XC-72 and mass concentration by mass ratio be to be added to the water at 100: 10: 30, the addition of water is convenient to follow-up spreading with made ink-like mixture and is advisable, and stirs sonic oscillation 30 minutes 20 minutes, make the ink-like mixture, and it is coated on the carbon paper, under 280 ℃ temperature, baking;
(2) with the active matter presoma (SO of Pt
3)
2Pt (NH
3)
4, mass concentration is that 2% perfluoro alkyl sulfonic acid polymer (Nafion) emulsion, isopropyl alcohol, ethylene glycol, water and Vulcan XC-72 are 50: 30: 40 by mass ratio: mix at 40: 20: 80, sonic oscillation 20 minutes is made and is contained (SO
3)
2Pt (NH
3)
4The prepared Chinese ink mixture of compound presoma is coated on the carbon paper in the above-mentioned steps (1) once more, and the coated weight of its metal Pt is 1mgcm
-2, and under 50 ℃ temperature, dry, hot pressing 40s under 80 ℃, 50atm at last, the carbon that obtains containing Pt active matter presoma carries porous electrode;
(3) carbon that contains Pt active matter presoma with preparation in the above-mentioned steps (2) carries porous electrode as work electrode, in the electrochemical deposition groove of 1mol/l hydrochloric acid solution, with 312 type Pt electrodes is to electrode, saturated calomel electrode is a reference electrode, under the room temperature, on the product VMP2 of U.S. PAR company multichannel potentiostat, carry out electrochemical deposition with pulse current, impulse waveform is a square wave in the present embodiment, the negative current current potential is～0.2V (vs.SCE), the positive current current potential is an Open Circuit Potential, pulse period is 400ms, and negative current and positive current time scale are t
n/ t
p=1: 3.Then, wash electrode repeatedly, make carbon-carrying platinum-based alloy electrode at last with a large amount of distilled water.Transmission electron microscope and X-ray diffraction chamber are tested the result and are shown that metallic is about 2.9nm, and metal active thing loading is about 1mgcm
-2, the metal effective rate of utilization 83% of catalyst layer.
Embodiment 2
(1) with carbon carrier Vulcan XC-72 under inert gas Ar protection, and 300 ℃ of bakings 3 hours, be 60% PTFE emulsion and isopropyl alcohol then with Vulcan XC-72 and mass concentration by mass ratio be to be added to the water at 100: 30: 60, the amount of water is convenient to follow-up spreading with made ink-like mixture and is advisable, and stirs sonic oscillation 50 minutes 40 minutes, make the ink-like mixture, and it is coated on the carbon cloth, under 330 ℃ temperature, baking;
(2) with active matter presoma K
2PtCl
6, RuCl
3, concentration is that 5% perfluoro alkyl sulfonic acid polymer (Nafion) emulsion, isopropyl alcohol, ethylene glycol, water and Vulcan XC-72 are 40: 40: 10 by mass ratio: 70: 60: 50: 100 mixed, sonic oscillation 40 minutes, under 50 ℃ of temperature, placed in the closed container 25 hours, then, add second and go on foot the Vulcan XC-72 that handled, Vulcan XC-72 and K
2PtCl
6, RuCl
3Mass ratio be 100: 40: 40, sonic oscillation 50 minutes is made and is contained Pt, Ru presoma prepared Chinese ink shape mixture, is coated on once more on the carbon cloth in the above-mentioned steps (1), its Pt and Ru washing amount are 2mgcm
-2, and 80 ℃ of oven dry in air atmosphere, at last at 120 ℃ of following hot pressing 90s, the carbon that obtains containing Pt, Ru active matter presoma carries porous electrode;
(3) electrode that contains Pt, Ru active matter presoma for preparing in the above-mentioned steps (2) is as the electro-deposition work electrode, place 1mol/l sulfuric acid solution electrochemical deposition groove, with 312 type Pt electrodes is to electrode, saturated calomel electrode is a reference electrode, under the room temperature, on the product VMP2 (Princeton) of U.S. PAR company multichannel potentiostat, carry out electrochemical deposition with pulse current, pulse electrodeposition negative current current potential is～0.4V (vs.SCE) in the present embodiment, the positive current current potential is 0.4V, and pulse current is 10A/cm
2Positive current and 80mA/cm
2Negative current, the pulse period is 800ms, negative current and positive current time scale are t
n/ t
p=1: 4.After the deposition,, carry the Pt-Ru alloy electrode thereby make carbon with a large amount of pure water cleaning electrode repeatedly.Transmission electron microscope and X-ray diffraction (Fig. 1) result of the test shows that metallic is being about 3.2nm, and the metal loading is 2mgcm
-2, Pt: Ru=1: 1, the metal effective rate of utilization 83% of catalyst layer.
Eelctro-catalyst with embodiment 1 preparation is a negative electrode, eelctro-catalyst with the preparation of this example is an anode, with marque is that the perfluoro alkyl sulfonic acid polymer proton film of Nafion112 places between two cube electrodes, under 230 ℃ of temperature, after the hot pressing 5 minutes, the assembled battery monomer is tested after making the membrane electrode assembly of Proton Exchange Membrane Fuel Cells, anode adopts methanol solution to make working substance matter, negative electrode oxygen is as oxidant, the input concentration of methyl alcohol is 2.5M, and working temperature is 80 ℃, normal pressure, electric current can reach 0.38A/cm under the electrode discharge 0.4V voltage, and electrode power density can reach 125～150mWcm
-2
Embodiment 3
(1) with carbon carrier Vulcan XC-72R under inert gas Ar protection, 400 ℃ were toasted 4 hours, be 20% PTFE emulsion and isopropyl alcohol then with Vulcan XC-72R and mass concentration by mass ratio be to be added to the water at 100: 50: 50, the amount of water is convenient to follow-up spreading with made ink-like mixture and is advisable, and stirs sonic oscillation 60 minutes 10 minutes, make the ink-like mixture, and it is coated on the carbon cloth, under 220 ℃ temperature, baking;
(2) with active matter presoma H
2PtCl
66H
2O, RuCl
3, Na
2WO
4, SnCl
4, concentration is that 0.5% perfluoro alkyl sulfonic acid polymer emulsion, isopropyl alcohol, ethylene glycol, water and Vulcan XC-72R are 30: 20: 10 by mass ratio: 10: 50: 80: mix at 40: 90: 100, sonic oscillation 50 minutes, make the ink-like mixture that contains Pt, Ru, W, four kinds of active matter presomas of Sn, be coated on once more on the carbon carbon cloth in the above-mentioned steps (1), the coated weight of its Pt, Ru, W and Sn metal is 2mgcm
-2, 40 ℃ of oven dry in air atmosphere, at last at 80 ℃ of following hot pressing 150s, the carbon that obtains containing Pt, Ru, W and Sn active matter presoma carries porous electrode;
(3) carbon that contains Pt, Ru, W and Sn active matter presoma with preparation in the above-mentioned steps (2) carries porous electrode as work electrode, place 1mol/l acetum electrochemical deposition groove, with 312 type Pt electrodes is to electrode, saturated calomel electrode is a reference electrode, under the room temperature, on the product VMP2 of U.S. PAR company multichannel potentiostat, carry out electrochemical deposition with pulse current, in the present embodiment pulse electrodeposition negative current current potential be～-0.3V (vs.SCE), the positive current current potential is 0.3V, and pulse current is 15A/cm
2Positive current and 120mA/cm
2Negative current, the pulse period is 500 ms, negative current and positive current time scale are t
n/ t
p=1: 5.After the deposition,, make carbon at last and carry the Pt-Ru-W-Sn alloy electrode with a large amount of pure water cleaning electrode repeatedly.Transmission electron microscope and X-ray diffraction result show that metallic is being about 5.4nm, and metal active thing loading is about 2mgcm
-2, the metal effective rate of utilization 79.2% of catalyst layer.
Embodiment 4
(1) with carbon nano-tube under inert gas Ar protection, 400 ℃ were toasted 4 hours, be 20% PTFE emulsion and isopropyl alcohol then with VulcanXC-72 and mass concentration by mass ratio be to be added to the water at 100: 50: 50, stirred 10 minutes, sonic oscillation 60 minutes is made the ink-like mixture, and it is coated on the carbon paper, under 280 ℃ of temperature, toasted 40 minutes;
(2) with active matter presoma K
2PtCl
6, RuCl
3, potassium molybdate, concentration is that 0.5% perfluoro alkyl sulfonic acid polymer (Nafion) emulsion, isopropyl alcohol, ethylene glycol, water and carbon nano-tube are 30: 20: 10 by mass ratio: 10: 50: 80: mix at 40: 90: 100, sonic oscillation 50 minutes, make the ink-like mixture that contains Pt, Ru and Mo metal salt compound presoma, be coated on once more on the carbon paper in the above-mentioned steps (1), the coated weight of its Pt, Ru and Mo metal is 1mgcm
-2, 40 ℃ of oven dry in air atmosphere, at last at 80 ℃ of following hot pressing 150s, the carbon that obtains containing Pt, Ru and Mo active matter presoma carries porous electrode;
(3) carbon that contains Pt, Ru and Mo active matter presoma with preparation in the above-mentioned steps (2) carries porous electrode as work electrode, place 1mol/l perchloric acid solution or phosphoric acid solution electrochemical deposition groove, with 312 type Pt electrodes is to electrode, saturated calomel electrode is a reference electrode, under the room temperature, on the product VMP2 of U.S. PAR company multichannel potentiostat, carry out electrochemical deposition with pulse current, in the present embodiment pulse electrodeposition negative current current potential be～-0.2V (vs.SCE), the positive current current potential is 0.6V, and pulse current is 10A/cm
2Positive current and 50mA/cm
2Negative current, the pulse period is 300ms, negative current and positive current time scale are t
n/ t
p=1: 5.After the deposition,, carry Pt-Ru-Mo alloy porous electrode thereby make carbon nano-tube with a large amount of pure water cleaning electrode repeatedly.Transmission electron microscope and x-ray diffraction experiment result show that metallic is being about 7.8nm, and the active matter loading is about 1mgcm
-2, the metal effective rate of utilization 78% of catalyst layer.
Embodiment 5
The difference of present embodiment and embodiment 3 is: select for use carbon fiber as carbon carrier in step 2, select K for use in step 4
2PtCl
6, RuCl
3, sodium stannate, potassium molybdate be as the active matter presoma.Transmission electron microscope and x-ray diffraction experiment result show that metallic is being about 11.5nm, and metal active thing loading is about 2mgcm
-2, the metal effective rate of utilization 68% of catalyst layer.
Claims (7)
1. the preparation method of a carbon-carrying platinum-based alloy electrode is characterized in that at first carbon carrier being toasted under inert gas shielding, is added to the water with PTFE emulsion and isopropyl alcohol, stir, and sonic oscillation, and be coated on carbon cloth or the carbon paper; Secondly platiniferous Base Metal salt compound active matter presoma is mixed with perfluoro alkyl sulfonic acid polymer emulsion, isopropyl alcohol, ethylene glycol, water and carbon carrier, sonic oscillation, be coated on once more on carbon cloth or the carbon paper, oven dry, the carbon of making platiniferous base active matter presoma carries porous electrode; At last carbon being carried porous electrode and place the electrochemical deposition groove that contains acid solution as work electrode, is to electrode with the Pt electrode, and saturated calomel electrode is a reference electrode, carries out electrochemical deposition with pulse current, and carbon-carrying platinum-based alloy electrode is made in washing.
2. the preparation method of carbon-carrying platinum-based alloy electrode according to claim 1 is characterized in that the concrete preparation process of this method follows these steps to carry out:
(1) with carbon carrier under inert gas shielding, and 300 ℃～600 ℃ bakings 1～4 hour, be 10%～60% PTFE emulsion and isopropyl alcohol then with carbon carrier and mass concentration by mass ratio be 100: 5～50: 1～50 to be added to the water, stirred 5～40 minutes, sonic oscillation 5～60 minutes is made prepared Chinese ink shape mixture, and it is coated on carbon paper or the carbon cloth, under 200 ℃～350 ℃ temperature, baking;
(2) be 0.1%～5% perfluoro alkyl sulfonic acid polymer emulsion, isopropyl alcohol, ethylene glycol, water and carbon carrier with platiniferous Base Metal salt compound active matter presoma, mass concentration by mass ratio be 100: 5～50: 1～100: 1～100: 1～100: 20～200 to mix, sonic oscillation 20～50 minutes, make the prepared Chinese ink mixture of platiniferous Base Metal salt compound presoma, be coated on once more on the carbon paper or carbon cloth in the above-mentioned steps (1), its metal active thing coated weight is 0.05～5.00mg cm
-2, and under 30 ℃～90 ℃ temperature, dry, at last 80 ℃～120 ℃ hot pressing 0.2～3 minute, the carbon that obtains platiniferous base active matter presoma carries porous electrode;
(3) carbon with the platiniferous base active matter presoma of preparation in the above-mentioned steps (2) carries porous electrode as work electrode, place the electrochemical deposition groove of acid solution, with the Pt electrode is to electrode, saturated calomel electrode is a reference electrode, and carry out electrochemical deposition with pulse current, make carbon-carrying platinum-based alloy electrode with the distilled water washing.
3. the preparation method of carbon-carrying platinum-based alloy electrode according to claim 2 is characterized in that carbon carrier is active carbon, XC-72 carbon black, carbon nano-tube or carbon fiber.
4. the preparation method of carbon-carrying platinum-based alloy electrode according to claim 2 is characterized in that platinum Base Metal salt compound active matter presoma is (SO
3)
2Pt (NH
3)
4, K
2PtCl
6, H
2PtCl
66H
2O or platinum acetate; Or wherein contain the metal salt compound of Pt and one or more metal salt compounds among Ru, W, Os, Mo, Ni, Sn or the Ir.
5. the preparation method of carbon-carrying platinum-based alloy electrode according to claim 4 is characterized in that the metal salt compound of Pt and the ratio of Ru, W, Os, Mo, Ni, Sn or Ir metal salt compound are 100: 0～100.
6. the preparation method of carbon-carrying platinum-based alloy electrode according to claim 2 is characterized in that acid solution is hydrochloric acid, sulfuric acid, nitric acid, acetic acid, perchloric acid or phosphoric acid.
7. the preparation method of carbon-carrying platinum-based alloy electrode according to claim 2, when it is characterized in that pulse current carries out electrochemical deposition, its pulse negative current current potential is-0.5～0.3V, and pulse positive current current potential is 0.2～0.8V, and pulse current is 0～20mA/cm
2Positive current and 10～200mA/cm
2Negative current, the pulse period is 30～1000ms, negative current and positive current time scale are t
n/ t
p=1: 0.5～10.
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