CN104600325B - Fuel cell electrode on-step preparation technology - Google Patents
Fuel cell electrode on-step preparation technology Download PDFInfo
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- CN104600325B CN104600325B CN201310532409.3A CN201310532409A CN104600325B CN 104600325 B CN104600325 B CN 104600325B CN 201310532409 A CN201310532409 A CN 201310532409A CN 104600325 B CN104600325 B CN 104600325B
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- 239000000446 fuel Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 238000005516 engineering process Methods 0.000 title description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 210000000170 cell membrane Anatomy 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 claims description 2
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 229940075397 calomel Drugs 0.000 claims 1
- 235000012149 noodles Nutrition 0.000 claims 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims 1
- 229910052939 potassium sulfate Inorganic materials 0.000 claims 1
- 235000011151 potassium sulphates Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000004832 voltammetry Methods 0.000 claims 1
- 210000004027 cell Anatomy 0.000 abstract description 28
- 239000003054 catalyst Substances 0.000 abstract description 22
- 238000003756 stirring Methods 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 229920005597 polymer membrane Polymers 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 239000002322 conducting polymer Substances 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000002048 multi walled nanotube Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 235000001508 sulfur Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The invention provides a fuel cell electrode on-step preparation method, which comprises the following steps: preparing a precursor solution from a carbon carrier, a platinum source, a polymeric monomer and a solvent, and preparing the fuel cell membrane electrode by using a cyclic voltammetry method by adopting a three-electrode system under a stirring condition, wherein the precursor solution is adopted as electrolyte. According to the fuel cell electrode preparation method, the characteristics of the two kinds of substances such as the polymeric monomer and the platinum source capable of respectively generating reactive polymerization and oxidization reaction under positive and negative potentials are reasonably utilized, the preparation of a precious metal catalyst and a polymer membrane can be realized by one step, the preparation method is simple, the conductivity capability of the electrode can be improved, and the service life of the electrode can be prolonged.
Description
Technical field
The present invention relates to field of fuel cell technology, more particularly to a kind of one-step method prepares fuel cell electrode
Technique.
Background technology
Fuel cell be a kind of without burning directly the chemical energy of fuel is changed into by electric energy in electrochemical reaction mode
TRT, be a kind of green energy resource technology." energy shortage " and " ring that fuel cell technology faces to the current world of solution
This two hang-up of border pollution " is significant.It has cleaning, it is considered to be fuel utilization the advantages of efficient and reliable
Optimal path.Energy for carbon-based fuel (such as oil gas, biological fuel processed, alcohols, fuel oil) is changed, fuel cell compared to
Traditional burning/internal combustion engine process has obvious advantage, its efficiency not by Carnot cycle theory the upper limit restricted it is thus also avoided that
The pollution problem that combustion process produces, is the important step to high-efficiency cleaning " low-carbon economy " transition for the fossil energy.Fuel electricity
The output motility in pond is very high, difference according to demand, fuel cell is big to be arrived can be enterprise as distributed energy,
The occasions such as school are powered, little to can be used as the power supply of the portable equipments such as mobile phone, computer.Therefore, fuel cell is as advanced
Novel energy will have very big development；On the other hand, a large amount of uses of fuel cell-powered and fuel cell car, electric motor car,
The continuous pollution of environment can effectively be suppressed, contain global warming simultaneously.
Electrode is the critical component of fuel cell, and its performance is the key factor of impact fuel cell overall performance.In order to
Improve the life-span of fuel cell, reduce the consumption of fuel-cell catalyst noble metal platinum, research worker have studied various electrode knots
Structure.At present no matter cathod catalyst or the anode catalyst of the catalyst used by low-temperature fuel cell, is all to be with platinum metal
Main noble metal catalyst.Platinum metal expensive, and occupy larger proportion in battery cost.This is also to cause to fire
Material battery is still difficult to large-scale promotion and the one of the main reasons of application so far.Additionally, this kind of catalyst is limited by resource,
Especially very limited in the yield of China's platinum metal.Therefore, develop highly active novel membrane electrode, improve the utilization of catalyst
Rate and its consumption of reduction, the direction that always operation of fuel cells person's emphasis is made great efforts.
According to document report, the catalyst carrier of high surface and suitable method for preparing catalyst is selected to be main method
One of.Goodenough et al. have studied pallium-on-carbon very early in document (electrochim. acta, 1987,32 (8))
(pt/c) electrode and the contrast of pure platinum black electrode, test and show that pt/c electrode has with high electric current density.Henceforth, with carbon
Research as fuel-cell catalyst carrier has obtained quick development.In recent years, conducting polymer is due to having specific surface
Long-pending higher, resistance is relatively low and advantage of good stability is gradually used as the carrier of fuel-cell catalyst, such as polythiophene, polyphenyl
Amine, polypyrrole etc..Ren Fangfang reports three in document " the electrocatalysis characteristic research of conducting polymer and noble metal composite "
Plant conducting polymer as the fuel cell electrode preparation method of carrier.Author prepares electrode using two steps, first in glass
On carbon electrode material, conducting polymer support is prepared using electropolymerization mode, then depositing noble metal catalyst.Experimental result table
Bright, the fuel cell electrode of the method preparation has preferable Oxidation to methanol.
Chinese invention patent (201010606384.3) discloses a kind of preparation method of combined electrode of fuel cell.Application
People prepares SWCN ultrathin film using arc discharge method and silk screen print method prepares multi-wall carbon nano-tube film, then
Metallic catalyst is electroplated on combination electrode.The matrix of this method preparation has extra specific surface area and conductive characteristic, fits
Close efficient supported metal catalyst.
Content of the invention
It is an object of the invention to overcoming, existing fuel cell membrane electrode platinum amount is more, conductive capability is poor, complex process
Deng not enough, there is provided the technique that a kind of one-step method prepares fuel cell electrode.Catalysis is had by membrane electrode prepared by the method
Effect preferably, with platinum amount is less and conductive capability is strong feature.
The present invention provides a kind of method that one-step method prepares fuel cell membrane electrode, comprises the following steps: with carbon carrier, platinum
Precursor solution prepared by source, polymerized monomer and solvent, with described precursor solution as electrolyte, using three-electrode system, is stirring
Under the conditions of mixing, prepare fuel cell membrane electrode using cyclic voltammetry.
Carbon carrier, platinum source (in terms of simple substance platinum), the mass ratio 1:0.1 of polymerized monomer three is contained in described precursor solution
～10:1～30, preferably 1:0.2～5:2～15；In terms of simple substance platinum, in precursor solution the concentration range of platinum be 1.0～
15.0mmol/l, preferably 2.0～10mmol/l.
In the preparation method of fuel cell membrane electrode of the present invention, described carbon carrier can for white carbon black, graphite, CNT,
Any one in Graphene, carbon nanocoils, preferably CNT or Graphene.
In the preparation method of fuel cell membrane electrode of the present invention, described carbon carrier is for carrying out at purification during CNT
Reason, described purification treating method can be according to described in document (electroanalysis 2011,23 (8): 1863-1869)
Method carry out.
In the preparation method of fuel cell membrane electrode of the present invention, described platinum source is platinum chloride, in platinum nitrate, chloroplatinic acid
One or more, preferably platinum chloride and/or chloroplatinic acid.
In the preparation method of fuel cell membrane electrode of the present invention, described polymerized monomer can for o-phenylenediamine, p-phenylenediamine,
One or more of resorcinol, hydroquinone, thiophene, aniline, preferably o-phenylenediamine and resorcinol.
In the preparation method of fuel cell membrane electrode of the present invention, described solvent is sodium nitrate, sodium sulfate, sodium chloride, sulfur
Any one in sour potassium solution, preferably sulfuric acid sodium or sodium nitrate.
In the preparation method of fuel cell membrane electrode of the present invention, described working electrode is: graphite flake, platinized platinum, gold plaque, carbon
Any one in paper, nickel foam, preferably carbon paper or nickel foam.
In the preparation method of fuel cell membrane electrode of the present invention, described can be platinum plate electrode, Ti electrode, nickel to electrode
Any one in plate electrode and platinum guaze, preferably platinized platinum or platinum guaze.
In the preparation method of fuel cell membrane electrode of the present invention, described reference electrode can using saturated calomel electrode,
The conventional reference electrode such as Mercurous sulfate electrode or silver/silver chloride electrode.Using different reference electrodes, running voltage is different, can root
According to this reference electrode with respect to standard hydrogen electrode electrode potential convert running voltage.
In the preparation method of fuel cell membrane electrode of the present invention, described cyclic voltammetry operating parameter is, scanning speed 5
～200mv/s, preferably 20～50mv/s, potential range -2.0～3.5v, preferably -1.0～1.5v, the continuous scanning number of turns is 10～
200 circles, preferably 30～100 circles.
The principle that the present invention prepares fuel cell membrane electrode is: chloroplatinic acid can be reduced to simple substance platinum under nagative potential,
And polymerized monomer occurs polyreaction under positive potential, carbon carrier can be driven simultaneously to be attached to electrode surface, form Surface coating
The fuel cell membrane electrode of polymer.
Fuel cell membrane electrode preparation method according to the present invention has the advantage that
1st, fuel cell electrode preparation method of the present invention rationally make use of polymerized monomer and this two classes material of platinum source to exist respectively
Positive nagative potential issues the characteristic of raw reactive polymeric reaction and oxidation reaction, can prepare noble metal catalyst by one-step method realization
And polymeric film, preparation method simple it is easy to large-scale promotion application.
2nd, in fuel cell electrode preparation method of the present invention, the addition of conducting polymer enhances the dispersion of catalyst granules
Degree, improves the conductive capability of electrode；Another aspect platinum grain is decreased in course of reaction with the interaction of conducting polymer
The formation of strong adsorbing species, extends the life-span of electrode.
3rd, the electrode being obtained by fuel cell electrode preparation method of the present invention, catalyst granules is less, and carries in carbon
High degree of dispersion on body.Such that it is able to significantly improve the effective surface area of catalyst granules, thus providing substantial amounts of avtive spot, increase
The strong oxidability of electrode.
4th, the carbon carrier adopting in fuel cell electrode preparation method of the present invention can promote electron transmission, increased electrode
Electric conductivity.Both can provide more crystal plane structure being conducive to electrochemical reaction by mutually synergism.
Brief description
Fig. 1 is membrane electrode component transmission electron microscope (tem) picture of preparation in the present invention.
Specific embodiment
With reference to specific embodiment, the present invention is described further, and described embodiment is only used for explaining the present invention,
Rather than limitation of the present invention.
Embodiment 1:
In the present embodiment, with multi-walled carbon nano-tubes as carbon carrier, chloroplatinic acid is platinum source, and o-phenylenediamine and resorcinol are poly-
Close monomer, metabisulfite solution is solvent.With carbon paper as working electrode, it is to electrode with platinum plate electrode, with saturated calomel electrode is
Reference electrode.
In the present embodiment, described multi-walled carbon nano-tubes carries out purification process first.Weigh the multi-walled carbon nano-tubes of 1g, slowly
It is added in 50ml concentrated sulphuric acid and the mixed solution of concentrated nitric acid (concentrated sulphuric acid and concentrated nitric acid volume ratio 3:1), continuous stirring processes 6
Hour, then use the high purity water dilution of 150ml, and centrifugation, repeat dilution and 5 ph values to solution of lock out operation are
6.5, then carry out sucking filtration concentration under 85kpa using vacuum pump sucking filtration system, finally vacuum under conditions of 50 DEG C, 20kpa
It is dried 8 hours, obtain the multi-walled carbon nano-tubes of purification.
Weigh 20mg multi-walled carbon nano-tubes after purification, 40mg chloroplatinic acid, 50mg o-phenylenediamine and 50mg resorcinol to add
Enter in the metabisulfite solution of 20ml 0.02 mol/l to prepare and obtain precursor solution, made with carbon paper in this precursor solution
For working electrode, platinum plate electrode is to electrode, and saturated calomel electrode is reference electrode, prepares fuel cell using cyclic voltammetry
Membrane electrode, scanning speed 50mv/s, potential range -1.0～1.0v, the continuous scanning number of turns is 10 circles, obtains present invention one kind and carries
There is the fuel cell electrode of Pt catalyst granule.
Embodiment 1 is prepared electrode material portions peel off, characterized by transmission electron microscope, see accompanying drawing 1, permissible
See that platinum grain is uniformly dispersed in carbon nano tube surface.It follows that the catalyst of the method preparation is more stable, and active
Site is larger, can improve the performance of electrode.
Embodiment 2:
In the present embodiment, with SWCN as carbon carrier, platinum chloride is platinum source, and aniline is polymerized monomer, sodium nitrate
Solution is solvent.With graphite flake as working electrode, it is to electrode with platinum plate electrode, with saturated calomel electrode as reference electrode.
In the present embodiment, described SWCN carries out purification process first.Weigh the SWCN of 1g, slowly
It is added in 50ml concentrated sulphuric acid and the mixed solution of concentrated nitric acid, continuous stirring processes 6 hours, then use the high purity water of 200ml
Dilution, and centrifugation, repeating dilution and 5 ph values to solution of lock out operation is 6.5, then using vacuum pump sucking filtration system
Carry out sucking filtration concentration under 85kpa, be finally vacuum dried 6 hours under conditions of 50 DEG C, 20kpa, obtain the single wall carbon of purification
Nanotube.
Weigh the SWCN of 30mg purification, 40mg platinum chloride, 100mg aniline are added to 50ml 0.02 mol/l
Sodium nitrate solution in prepare and obtain precursor solution, using graphite flake as working electrode in this precursor solution, platinized platinum electricity
Extremely to electrode, saturated calomel electrode is reference electrode, prepares fuel cell membrane electrode, scanning speed using cyclic voltammetry
20mv/s, potential range -1.0～1.5v, the continuous scanning number of turns is 50 circles, obtains a kind of Pt catalyst granule that is loaded with of the present invention
Fuel cell electrode.
Embodiment 3:
In the present embodiment, with white carbon black as carbon carrier, platinum chloride is platinum source, and thiophene is polymerized monomer, and sodium chloride solution is molten
Agent.With graphite flake as working electrode, it is to electrode with gauze platinum electrode, with saturated calomel electrode as reference electrode.
Weigh the white carbon black of 30mg purification, 80mg platinum chloride, 100mg thiophene are added to the sodium chloride of 50ml 0.02 mol/l
Prepare in solution and obtain precursor solution, using graphite flake as working electrode in this precursor solution, gauze platinum electrode is to electricity
Pole, saturated calomel electrode is reference electrode, prepares fuel cell membrane electrode, scanning speed 100mv/s, electricity using cyclic voltammetry
Position scope -1.0～1.5v, the continuous scanning number of turns is 100 circles, obtains a kind of fuel cell being loaded with Pt catalyst granule of the present invention
Electrode.
Claims (12)
1. one-step method prepare fuel cell membrane electrode method it is characterised in that: with carbon carrier, platinum source, polymerized monomer and solvent
Prepare precursor solution, with described precursor solution as electrolyte, using three-electrode system, under agitation, using circulation
Voltammetry prepares fuel cell membrane electrode, the mass ratio 1 of carbon carrier, platinum source, polymerized monomer three in described precursor solution:
0.1～10:1～30, wherein platinum source is in terms of simple substance platinum；Described carbon carrier is that white carbon black, graphite, CNT, Graphene and carbon are received
Any one in rice noodle；Described platinum source is one or more of platinum chloride, platinum nitrate, chloroplatinic acid；Described polymerized monomer is neighbour
One or more of phenylenediamine, p-phenylenediamine, resorcinol, hydroquinone, thiophene, aniline；Described solvent is sodium nitrate, sulfur
Any one in sour sodium, sodium chloride, potassium sulfate；Described cyclic voltammetry operating parameter is, scanning speed 5～200mv/s, electricity
Position scope -2.0～3.5v, the continuous scanning number of turns is 10～200 circles.
2. method according to claim 1 it is characterised in that: carbon carrier, platinum source, polymerized monomer in described precursor solution
Mass ratio 1:0.2～5:2～15 of three, wherein platinum source is in terms of simple substance platinum.
3. method according to claim 1 it is characterised in that: in terms of simple substance platinum, the concentration range of platinum in precursor solution
For 1.0～15.0mmol/l.
4. method according to claim 1 it is characterised in that: in terms of simple substance platinum, the concentration range of platinum in precursor solution
For 2.0～10.0mmol/l.
5. method according to claim 1 it is characterised in that: described carbon carrier be CNT or Graphene.
6. method according to claim 5 it is characterised in that: carbon carrier is for carrying out purification process during CNT.
7. method according to claim 1 it is characterised in that: described platinum source be platinum chloride and/or chloroplatinic acid.
8. method according to claim 1 it is characterised in that: described polymerized monomer be o-phenylenediamine and resorcinol.
9. method according to claim 1 it is characterised in that: the working electrode in described three-electrode system be graphite
Any one in piece, platinized platinum, gold plaque, carbon paper, nickel foam.
10. method according to claim 1 it is characterised in that: in described three-electrode system to electrode is platinized platinum electricity
Pole, Ti electrode, nickel sheet electrode, any one in platinum guaze.
11. methods according to claim 1 it is characterised in that: the reference electrode in described three-electrode system be saturation
Any one in calomel electrode, Mercurous sulfate electrode, silver/silver chloride electrode.
12. methods according to claim 1 it is characterised in that: described cyclic voltammetry operating parameter is, scanning speed
20～50mv/s, potential range -1.0～1.5v, the continuous scanning number of turns is 30～100 circles.
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