CN1674330A - Electric catalyst with conducing high polymer modification one-dimensional nano carbon as carrier and producing process - Google Patents
Electric catalyst with conducing high polymer modification one-dimensional nano carbon as carrier and producing process Download PDFInfo
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Abstract
An electro - catalyst uses one - dimensional nanocarbon modified by conduction high polymer in large Pi bond structure as carrier. Its preparing process includes preparing one - dimensional nanocarbon modified by conduction high polymer first and then loading Pt or Pt alloy on its surface. The average particle diameter of electro - catalyst is less than or equal to 5 nm and power density of single cell prepared by electro - catalyst is 0.40 - 0.47 W / cm2 under test condition as H2/ Air and Pt loading capacity in 0.20mg / sq cm and 600 mA / sq.cm.
Description
Technical field
The present invention relates to a kind of eelctro-catalyst that is mainly used in fuel cell field, particularly be applicable to the used in proton exchange membrane fuel cell eelctro-catalyst, be characterized in that the carrier in the eelctro-catalyst is the one-dimensional nano carbon that conduction high polymer is modified.The invention still further relates to the preparation method of this kind eelctro-catalyst.
Background technology
Energy problem and environmental problem develop rapidly with World Economics and more and more show outstanding.By contrast, the fuel cell that adopts hydrogen to act as a fuel does not pollute fully to environment, but also has the advantage of circular regeneration, has therefore excited numerous researchers' interest.Noble metal in the fuel cell electro-catalyst is generally platinum or platinum alloy, and this is because platinum has higher catalytic efficiency; And the carrier in the fuel cell electro-catalyst mostly is carbon black, and this is because carbon black has higher specific surface area, help improving the dispersiveness of metallics such as platinum or platinum alloy, but the utilance of platinum is not high, is usually less than 20%.This is because a large amount of platinum or platinum alloy particles is deposited in the micropore of porous carbon black, can not contact with proton conductor, therefore is unfavorable for forming more phase reactions district.In addition, the chemical stability of carbon black is relatively poor, and the electrochemical environment of fuel battery inside is more abominable, and electrochemical corrosion very easily takes place carbon black, has accelerated the loss of platinum or platinum alloy and grows up; And the mechanical strength of carbon black is not high yet.These have all limited the application of eelctro-catalyst in fuel cell.
Compare with carbon black, one-dimensional nano carbon (One-dimension nano-carbon, ODNC), as carbon nano-tube (Carbon nanotubes, CNTs), carbon nano-fiber (Carbon nanofibres, CNFs) etc., because of having and the similar structure of crystalline graphite, and have higher mechanical strength and chemical stability, and its conductivity also is better than carbon black; In addition, unidimensional nanocarbon surface does not have the loose structure of similar carbon black, in as fuel cell electro-catalyst during the carrier of platinum or platinum alloy, the metallic particles of the overwhelming majority will be attached to the surface of one-dimensional nano carbon, help the formation of three-phase reaction interface, so the service efficiency of catalyst will improve greatly.As seen, one-dimensional nano carbon is one of preferred material of fuel cell electro-catalyst noble metal carrier.
At present, existing both at home and abroad with the report of one-dimensional nano carbon as carrier system high-performance eelctro-catalyst.Shanghai Inst. of Microsystem and Information Technology, Chinese Academy of Sci (CN1404179A) is to multi-walled carbon nano-tubes (Multi-walledcarbon nanutubes, MWCNTs) carry out pre-activated and handle, adopt liquid impregnation method-heat treating process to prepare the Pt/MWCNTs catalyst then.Zhejiang University is scattered in carbon nano-tube slaine many of Pt, Pd or Ru
In unit's alcoholic solution, adopt the method for carry out microwave radiation heating that nano-metal particle is carried on carbon nano tube surface (CN1424149); In addition, also adopt the method for microwave radiation that the Pt-Ru bianry alloy is carried on (CN1424150) above the carbon nano-tube.Northern Transportation University's utilization photocatalysis in-situ chemical reduction precipitation method with the carbon nano tube surface of chloroplatinic acid reduce deposition in the process activation processing, has prepared Pt/CNTs catalyst (CN1418726A) by UV-irradiation.In addition, DU PONT company also successfully with some transition metal Pd, Pt or Cu even load in carbon nano-tube or fullerene surface (WO9510481).Yoshitake etc. (Phisical, 2002,323,124-126) synthesized the Pt/CNTs eelctro-catalyst with colloid method.Lordi etc. (Chem Mater, 2001,13,733～737) use the EG reducing process to make Pt/SWNTs (Single-Walled CarbonNanotubes) catalyst.Hao etc. (Journal of colloid and interface science, 2004,269,26～31) adopt electrochemical deposition method that platinum is deposited on the carbon nano-fiber surface.
But above-mentioned Preparation of catalysts method exists obviously not enough: because one-dimensional nano carbon is high-graphitized, its surface is chemical inertness, so metallic such as Pt is difficult for the surface attached to one-dimensional nano carbon.Though by one-dimensional nano carbon is carried out oxidation or activation, can change its chemical inertness of surface, this method is very easily destroyed the body construction of one-dimensional nano carbon, reduce chemistry, physical stability and the electric conductivity of material.Even metallics such as Pt are carried on unidimensional nanocarbon surface, the particle diameter that the eelctro-catalyst of preparation also can exist metallic is difficult to control, the particle dispersiveness is relatively poor, and a little less than the adhesion between metallic and the one-dimensional nano carbon, metallic problem such as very easily come off.
Carbon nano tube surface is by sp
2The carbon hexatomic ring of hydridization is formed, and belongs to big π bond structure, therefore can close effect by pi-pi bond with the high polymer that contains big π bond structure equally and combine, and forms firm carbon nano-tube-high polymer composite material.J.Michael (Chem.Phys.Lett, 2001,342,265-271) conjugated polymer has been done research and analysis with combining of carbon nano-tube, (Carbon such as X.H.Li, 2003,41,1670-1674.) and (Electrochimica Acta, 2004 such as Y.K.Zhou, 49,257-262) pi-pi bond of p-poly-phenyl amine-carbon nano-tube closes effect and studies.The result shows that the pi-pi bond between conjugated polymer and carbon nano-tube is quite firm, and the composite material of preparation also has mechanical strength preferably.At present, conjugated polymer-carbon nano tube compound material is general only to be studied as reinforcing material, and Shang Weiyou is with the report of its battery electrocatalyst metal carrier that acts as a fuel.
Summary of the invention
An object of the present invention is to provide a kind of fuel cell that is applied to, particularly be applied to the eelctro-catalyst of Proton Exchange Membrane Fuel Cells; Another object of the present invention provides a kind of preparation method of this kind eelctro-catalyst.
The one-dimensional nano carbon that the eelctro-catalyst of fuel cell of the present invention, the carrier that is characterized in Pt in the eelctro-catalyst or Pt alloy adopt the conduction high polymer that contains big π bond structure to modify
The conduction high polymer modification one-dimensional nano carbon that employing contains big π bond structure mainly is to utilize the pi-pi bond of conduction high polymer and one-dimensional nano carbon to close effect the two is combined closely, the metallic that plays simultaneously catalytic action in the catalyst and the adhesion of conduction high polymer also and the enhancing of the adhesion between the one-dimensional nano carbon, thereby solved the problem of metallic and one-dimensional nano carbon poor bonding strength in the catalyst.In addition, the controllability of the dispersiveness of metallic and particle diameter also is improved.
One-dimensional nano carbon of the present invention is carbon nano-tube or carbon nano-fiber, and wherein, carbon nano-tube comprises Single Walled Carbon Nanotube and multi-walled carbon nano-tubes.
Conduction high polymer of the present invention is any in polyaniline, polypyrrole, polythiophene, polyacetylene, poly-phenylene vinylene (ppv) support, polyphenyl, polyphenylacetylene, poly(ethylene oxide) and the PPOX; Wherein polyaniline, polypyrrole and polythiophene comprise their eigenstate and protonic acid doping attitude; Bronsted acid comprises inorganic acid and organic acid two classes, and inorganic acid is any in hydrochloric acid, nitric acid, sulfuric acid and the perchloric acid, and organic acid is any in benzene sulfonic acid, DBSA and the perfluorinated sulfonic resin.
Pt alloy of the present invention is Pt
xM
yOr Pt
3M
xN
y, wherein x, y are respectively and are less than or equal to 3 natural number, and M, N are respectively the arbitrary metallic element among Pd, Ru, Rh, Ir, OS, Fe, Cr, Ni, Co, Mn, Cu, V, Ti, Ga, W, Sn and the Mo, and M and N are different.
The preparation method of eelctro-catalyst of the present invention prepares the one-dimensional nano carbon that conduction high polymer is modified earlier, and then at its area load Pt or Pt alloy, concrete preparation method is:
1st, one-dimensional nano carbon is scattered in the alcohol solution, adds the monomer of conduction high polymer then, fully stir, make dispersion liquid, the mass ratio of one-dimensional nano carbon and conduction high polymer monomer is 0.1～10: 1;
2nd, the polymerization initiator with the conducting polymer monomer joins in the prepared dispersion liquid of step 1, maintain the temperature under 0～10 ℃ the condition, react and made the complete polymerization of monomer in 1～8 hour, after filtration, the alcohol washing makes the one-dimensional nano carbon that conduction high polymer is modified; Polymerization initiator is made up of oxidant and Bronsted acid, wherein alcohol is any in methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol, and oxidant is any in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, potassium bichromate, sodium dichromate, ammonium dichromate and the hydrogen peroxide; Bronsted acid comprises inorganic acid and organic acid two classes, and inorganic acid is any in hydrochloric acid, nitric acid, sulfuric acid and the perchloric acid, and organic acid is any in benzene sulfonic acid, DBSA and the perfluorinated sulfonic resin;
3rd, the conduction high polymer modification one-dimensional nano carbon with step 2 preparation is scattered in alcohol solution, adds the presoma salting liquid of Pt or Pt alloy, and the mass ratio of conduction high polymer monomer and Pt is 0.1～100: 1.Fully stir, at N
2, Ar or He protection down, 90～98 ℃ of reflux 1～30 minute make eelctro-catalyst of the present invention;
Wherein, alcohol is 1～100: 1 with the mass ratio of water in the alcohol solution, and alcohol is any in methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol.
The eelctro-catalyst of preparation is assembled into monocell, carries out electric performance test, test process is as follows:
1, the preparation of fuel cell acp chip CCM (Catalyst coated membrane): the eelctro-catalyst of preparation is fully washed with deionized water or alcohol solution, and mix mutually with perfluor sulfoacid resin solution, fully stir the furnishing pasty state, evenly be coated on Nafion series membranes (as NRE212NRE211 etc.) both sides of DU PONT company then, oven dry makes CCM respectively.The Pt carrying capacity of CCM cathode and anode catalyst layer adds up to 0.1～0.4mg/cm
2
2, monocell assembling and test: the carbon paper that adopts hydrophobic treatment is as gas diffusion layers, polytetrafluoroethylene (PTFE) content 20～50wt% wherein, and the compound microporous layers of being made up of PTFE and conductive carbon black particle of one side (calcining 20min down through 350 ℃), it mainly acts on is to optimize water and gas passage; Collector plate is a graphite cake, has parallel slot in a side; End plate is gold-plated stainless-steel sheet.CCM, gas diffusion layers, collector plate, end plate and encapsulant are assembled into monocell.The monocell operating condition is: H
2/ Air, the air back pressure is a normal pressure; Anode humidification, humidification degree are 0～100%; The monocell working temperature is 60～80 ℃, and the humidification temperature is 60～75 ℃.
Eelctro-catalyst that is carrier with existing one-dimensional nano carbon and preparation method thereof is compared, and the present invention has following advantage:
1, because unidimensional nanocarbon surface has stronger chemical inert, the bond strength between catalyst granules and the one-dimensional nano carbon is not high.Existing method generally adopts the chemical inert of chemical oxidization method or activation method change unidimensional nanocarbon surface, but this will destroy the body construction of one-dimensional nano carbon, reduce chemistry, physical stability and the conductivity of material.The present invention has adopted conduction high polymer to come modification one-dimensional nano carbon, utilize pi-pi bond to close effect, under the situation of not destroying the 1-dimention nano carbon structure, has solved the unstable problem that combines between catalyst metal particles and the one-dimensional nano carbon.
2, also have adhesion preferably between the metal nanoparticle of catalyst and high polymer, metal nanoparticle is scattered in Polymer Surface, the average grain diameter≤5nm of metal nanoparticle preferably simultaneously.
3, the high polymer modification agent of the present invention's employing belongs to the conjugated type polymer, and itself has conductivity, does not therefore need its removal.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Get the 0.25g multi-walled carbon nano-tubes, join in the mixed liquor of 20ml ethanol and water (mass ratio of second alcohol and water is 1: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperses to add the aniline solution of 90wt% after 5～20 minutes, and the mass ratio of carbon nano-tube and aniline is 0.6: 1, fully stir, adding ammonium persulfate 2g and concentration is the hydrochloric acid solution 20ml of 1mol/l, and lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, make the carbon nano-tube that polyaniline is modified.The carbon nano-tube that the polyaniline that makes is modified is scattered in the mixed liquor of 220ml second alcohol and water (mass ratio of second alcohol and water is 1: 1), adding Pt concentration is the platinum acid chloride solution 28ml of 0.046mol/l, the mass ratio of aniline and platinum is 1.7: 1, fully stirs, and feeds N
2, 90 ℃ of reflux are reacted and are stopped heating after 8 minutes, but still continue to feed N
2Product is cooled off gradually, make the amine-modified carbon nano-tube platinum catalyst of conducting polyaniline.Wherein, the particle diameter≤5nm of platinum, average out to 2nm, and better dispersed.
The preparation of fuel cell acp chip CCM (Catalyst coated membrane).Eelctro-catalyst deionized water wash 3-5 time with preparation, and with the perfluor sulfoacid resin solution (other composition is 70wt% isopropyl alcohol, 10wt% ethanol and 15wt% water) of 5wt% by 2: 1～3: 1 solid masses than mixing, fully stir, the furnishing pasty state, be coated on the Nafion NRE211 both sides that DU PONT company produces then, oven dry makes CCM.NRE211 film thickness is 25 μ m, and the Pt carrying capacity of the cathode and anode catalyst layer of CCM adds up to 0.20mg/cm
2
Monocell assembling and test.The carbon paper that adopts hydrophobic treatment is as gas diffusion layers, polytetrafluoroethylene (PTFE) content 30wt% wherein, and the compound microporous layers of being made up of PTFE and conductive carbon black particle of one side (calcining 20min down through 350 ℃), it mainly acts on is to optimize water and gas passage; Collector plate is a graphite cake, has parallel slot in a side; End plate is gold-plated stainless-steel sheet.CCM, gas diffusion layers, collector plate, end plate and encapsulant are assembled into monocell.The monocell operating condition is: H
2/ Air, the air back pressure is a normal pressure; Anode 100% humidification; The monocell working temperature is 70 ℃, and the humidification temperature is 65 ℃.Test result shows that the power density of monocell reaches 0.45W/cm
2(600mA/cm
2).
Embodiment 2
Get the 0.25g multi-walled carbon nano-tubes, join in the mixed liquor of 20ml ethanol and water (mass ratio of second alcohol and water is 100: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperses to add the aniline solution of 90wt% after 5～20 minutes, and the mass ratio of carbon nano-tube and aniline is 0.6: 1, fully stir, adding ammonium persulfate 2g and concentration is the hydrochloric acid solution 20ml of 1mol/l, and lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, make the carbon nano-tube that polyaniline is modified.The carbon nano-tube that the polyaniline that makes is modified is scattered in the mixed liquor of 220ml second alcohol and water (mass ratio of second alcohol and water is 100: 1), adding Pt concentration is platinum acid chloride solution 28 ml of 0.046mol/l, the mass ratio of aniline and platinum is 1.7: 1, fully stirs, and feeds N
2, 90 ℃ of reflux are reacted and are stopped heating after 1 minute, but still continue to feed N
2Product is cooled off gradually, make the amine-modified carbon nano-tube platinum catalyst of conducting polyaniline.Wherein, the particle diameter of platinum≤5, average out to 4nm, and better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell reaches 0.41W/cm
2(600mA/cm
2).
Embodiment 3
Get the multi-walled carbon nano-tubes of 0.75g, join in the mixed liquor of 30ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～20 minutes, the pyrroles's solution that adds 95wt%, carbon nano-tube and pyrroles's mass ratio is 0.5: 1, fully stir, adding ammonium persulfate 3.2g and concentration is the salpeter solution 32ml of 1mol/l, lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, make the carbon nano-tube of polypyrrole modifying.The carbon nano-tube of the polypyrrole modifying that makes is scattered in the mixed liquor of 355ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), adding Pt concentration is the platinum acid chloride solution 84ml of 0.046mol/l, the mass ratio of pyrroles and platinum is 2: 1, fully stirs, and feeds N
2, 90 ℃ of reflux are reacted and are stopped heating after 8 minutes, but still continue to feed N
2, product is cooled off gradually, make the carbon nano-tube modified platinum catalyst of electric polypyrrole.Wherein, the particle diameter≤5nm of platinum, average out to 3nm and better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell reaches 0.42W/cm
2(600mA/cm
2).
Embodiment 4
Get the multi-walled carbon nano-tubes of 0.75g, join in the mixed liquor of 30ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～20 minutes, the pyrroles's solution that adds 95wt%, carbon nano-tube and pyrroles's mass ratio is 0.5: 1, fully stir, adding sodium peroxydisulfate 3.6g and concentration is the salpeter solution 32ml of 1mol/l, lasting stirring reaction is 1 hour under 10 ℃, after the filtration, with ethanol washing 2～3 times, make the carbon nano-tube of polypyrrole modifying.The carbon nano-tube of the polypyrrole modifying that makes is scattered in the mixed liquor of 355ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), adding Pt concentration is the platinum acid chloride solution 84ml of 0.046mol/l, the mass ratio of pyrroles and platinum is 2: 1, fully stirs, and feeds N
2, 90 ℃ of reflux are reacted and are stopped heating after 8 minutes, but still continue to feed N
2, product is cooled off gradually, make the carbon nano-tube modified platinum catalyst of electric polypyrrole.Wherein, the particle diameter≤8nm of platinum, average out to 5nm, better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell reaches 0.40W/cm
2(600mA/cm
2).
Embodiment 5
Get the Single Walled Carbon Nanotube of 0.75g, join in the mixed liquor of 30ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～20 minutes, the pyrroles's solution that adds 95wt%, carbon nano-tube and pyrroles's mass ratio is 0.1: 1, fully stir, (all the other are the 70wt% isopropyl alcohol to the perfluor sulfoacid resin solution of adding ammonium persulfate 16g and 120g 5wt%, 10wt% ethanol and 15wt% water), lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, make the carbon nano-tube of polypyrrole modifying.The carbon nano-tube of the polypyrrole modifying that makes is scattered in the mixed liquor of 355ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), pouring Pt concentration again into is the platinum acid chloride solution 84ml of 0.046mol/l, the mass ratio of pyrroles and platinum is 10: 1, fully stirs, and feeds N
2, 98 ℃ of reflux are reacted and are stopped heating after 8 minutes, but still continue to feed N
2, product is cooled off gradually, make the carbon nano-tube modified platinum catalyst of electric polypyrrole.Wherein, the particle diameter≤5nm of platinum, average out to 3nm and better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell reaches 0.42W/cm
2(600mA/cm
2).
Embodiment 6
Get the Single Walled Carbon Nanotube of 0.75g, join in the mixed liquor of 30ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～20 minutes, the pyrroles's solution that adds 95wt%, carbon nano-tube and pyrroles's mass ratio is 10: 1, fully stir, (all the other are the 70wt% isopropyl alcohol to the perfluor sulfoacid resin solution of adding ammonium persulfate 0.2g and 120g 5wt%, 10wt% ethanol and 15wt% water), lasting stirring reaction is 1 hour under 0 ℃, after the filtration, with ethanol washing 2～3 times, make the carbon nano-tube of polypyrrole modifying.The carbon nano-tube of the polypyrrole modifying that makes is scattered in the mixed liquor of 355ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), adding Pt concentration is the platinum acid chloride solution 84ml of 0.046mol/l, the mass ratio of pyrroles and platinum is 0.1: 1, fully stirs, and feeds N
2, 98 ℃ of reflux are reacted and are stopped heating after 30 minutes, but still continue to feed N
2, product is cooled off gradually, make the carbon nano-tube modified platinum catalyst of electric polypyrrole.Wherein, the particle diameter≤5nm of platinum, average out to 3nm and better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell reaches 0.42W/cm
2(600mA/cm
2).
Embodiment 7
Get the Single Walled Carbon Nanotube of 0.75g, join in the mixed liquor of 30ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～20 minutes, the pyrroles's solution that adds 95wt%, carbon nano-tube and pyrroles's mass ratio is 1: 1, fully stir, adding ammonium persulfate 160g and concentration again is the hydrochloric acid solution 1.6ml of 1mol/l, lasting stirring reaction is 8 hours under 0 ℃, after the filtration,, make the carbon nano-tube of polypyrrole modifying with ethanol washing 2～3 times.The carbon nano-tube of the polypyrrole modifying that makes is scattered in the mixed liquor of 355ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), adding Pt concentration is the platinum acid chloride solution 8.4ml of 0.046mol/l, the mass ratio of pyrroles and platinum is 100: 1, fully stirs, and feeds N
2, 90 ℃ of reflux are reacted and are stopped heating after 8 minutes, but still continue to feed N
2, product is cooled off gradually, make the carbon nano-tube modified platinum catalyst of electric polypyrrole.Wherein, the particle diameter≤4nm of platinum, average out to 2.5nm, and better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell reaches 0.39W/cm
2(600mA/cm
2).
Embodiment 8
Get the carbon nano-fiber of 0.8g, join that (mass ratio of second alcohol and water is 1 .4: 1) in the mixed liquor of 30ml second alcohol and water, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～20 minutes, the aniline solution that adds 90wt%, the mass ratio of carbon nano-fiber and aniline is 0.6: 1, fully stir, adding ammonium persulfate 6.2g and concentration is the hydrochloric acid solution 60ml of 1mol/l, lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, make the carbon nano-fiber that polyaniline is modified.The carbon nano-fiber that the polyaniline of preparation is modified is scattered in the mixed liquor of 395ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), adding Pt concentration is the platinum acid chloride solution 83ml of 0.046mol/l, the mass ratio of aniline and platinum is 1.8: 1, fully stirs, and feeds N
2, 90 ℃ of reflux are reacted and are stopped heating after 8 minutes, but still continue to feed N
2, product is cooled off gradually, make electrically conductive polyaniline decorated nanometer carbon fiber platinum catalyst.Wherein, the particle diameter≤6nm of platinum, average out to 3.5nm, and better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell has reached 0.43W/cm
2(600mA/cm
2).
Embodiment 9
Get the multi-walled carbon nano-tubes of 0.75g, join in the mixed liquor of 30ml second alcohol and water (mass ratio of second alcohol and water is 2: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～20 minutes, the pyrroles's solution that adds 95wt%, carbon nano-tube and pyrroles's mass ratio is 0.5: 1, fully stir, adding ammonium persulfate 3.2g and concentration is the hydrochloric acid solution 32ml of 1mol/l, lasting stirring reaction is 8 hours under 0 ℃, after the filtration,, make the carbon nano-tube of polypyrrole modifying with ethanol washing 2～3 times.The carbon nano-tube of the polypyrrole modifying that makes is scattered in the mixed liquor of 355ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), the platinum acid chloride solution 84ml and the Co concentration that add Pt concentration respectively and be 0.046mol/l are the CoCl of 0.046mol/l
2Solution 84ml, the mass ratio of pyrroles and Pt are 2: 1, fully stir, and feed N
2, 90 ℃ of reflux are reacted and are stopped heating after 8 minutes, but still continue to feed N
2, product is cooled off gradually, make carbon nano-tube modified year PtCo alloy catalyst of electric polypyrrole.Wherein, the particle diameter≤7nm of PtCo alloy, average out to 4nm and better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell reaches 0.45W/cm
2(600mA/cm
2).
Embodiment 10
Get the multi-walled carbon nano-tubes of 0.75g, join in the mixed liquor of 30ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～20 minutes, the pyrroles's solution that adds 95wt%, carbon nano-tube and pyrroles's mass ratio is 0.5: 1, fully stir, adding ammonium dichromate 3.2g and concentration is the hydrochloric acid solution 32ml of 1mol/l, lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, make the carbon nano-tube of polypyrrole modifying.The carbon nano-tube of the polypyrrole modifying that makes is scattered in the mixed liquor of 355ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), the platinum acid chloride solution 84ml and the Cr concentration that add Pt concentration respectively and be 0.046mol/l are the CrCl of 0.046mol/l
3Solution 28ml, the mass ratio of pyrroles and Pt are 2: 1, fully stir, and feed N
2, 90 ℃ of reflux are reacted and are stopped heating after 8 minutes, but still continue to feed N
2, product is cooled off gradually, make carbon nano-tube modified year Pt of electric polypyrrole
3The Cr alloy catalyst.Wherein, Pt
3Particle diameter≤the 6nm of Cr alloy, average out to 4nm, and better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell reaches 0.47W/cm
2(600mA/cm
2).
Embodiment 11
Get the multi-walled carbon nano-tubes of 0.75g, join in the mixed liquor of 30ml second alcohol and water (mass ratio of second alcohol and water is 2: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～20 minutes, the pyrroles's solution that adds 95wt%, carbon nano-tube and pyrroles's mass ratio is 0.5: 1, fully stir, adding ammonium persulfate 3.2g and concentration is the hydrochloric acid solution 32ml of 1mol/l, lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, make the carbon nano-tube of polypyrrole modifying.The carbon nano-tube of the polypyrrole modifying that makes is scattered in the mixed liquor of 355ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), the platinum acid chloride solution 84ml and the Ru concentration that add Pt concentration respectively and be 0.046mol/l are 0.046mol/lRuCl
3Solution 84ml, the mass ratio of pyrroles and platinum are 2: 1, fully stir, and feed Ar, and 90 ℃ of reflux reacts and stopped heating after 8 minutes, but still continue feeding Ar
2, product is cooled off gradually, make carbon nano-tube modified year PtRu alloy catalyst of electric polypyrrole.Wherein, the particle diameter≤7nm of PtRu alloy, average out to 3.5nm, and better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell reaches 0.47W/cm
2(600mA/cm
2).
Embodiment 12
Get the Single Walled Carbon Nanotube of 0.25g, join in the mixed liquor of 20ml ethanol and water (mass ratio of second alcohol and water is 1.4: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～20 minutes, the aniline solution that adds 90wt%, the mass ratio of carbon nano-tube and aniline is 0.6: 1, fully stir, adding ammonium dichromate 2g and concentration is the hydrochloric acid solution 20ml of 1mol/l, lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, make the carbon nano-tube that polyaniline is modified.The carbon nano-tube that the polyaniline that makes is modified is scattered in the mixed liquor of 220ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), and adding Pt concentration respectively is the platinum acid chloride solution 28ml of 0.046mol/l, and Cr concentration is the CrCl of 0.046mol/l
3Solution 28ml and Co concentration are the CoCl of 0.046mol/l
2Solution 28ml, the mass ratio of aniline and platinum are 1.7: 1, fully stir, and feed N
2, 90 ℃ of reflux are reacted and are stopped heating after 8 minutes, but still continue to feed N
2Product is cooled off gradually, make the amine-modified carbon nano-tube of conducting polyaniline and carry the PtCoCr alloy catalyst.Wherein, the particle diameter of PtCoCr alloy≤6, average out to 4.5nm, and better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell reaches 0.46W/cm
2(600mA/cm
2).
Embodiment 13
Get the Single Walled Carbon Nanotube of 0.25g, join in the mixed liquor of 20ml ethanol and water (mass ratio of second alcohol and water is 1.4: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～20 minutes, the aniline solution that adds 90wt%, the mass ratio of carbon nano-tube and aniline is 0.6: 1, fully stir, adding ammonium persulfate 2g and concentration is the hydrochloric acid solution 20ml of 1mol/l, lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, make the carbon nano-tube that polyaniline is modified.The carbon nano-tube that the polyaniline that makes is modified is scattered in the mixed liquor of 220ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), and adding Pt concentration respectively is the platinum acid chloride solution 28ml of 0.046mol/l, and Ir concentration is the IrCl of 0.046mol/l
3Solution 28ml and Co concentration are the CoCl of 0.046mol/l
2Solution 28ml, the mass ratio of aniline and platinum are 1.7: 1, fully stir, feed He, 90 ℃ of reflux reacts and are stopped after 8 minutes heating, but still continue to feed He product is cooled off gradually, make the amine-modified carbon nano-tube of conducting polyaniline and carry the PtlrCo alloy catalyst.Wherein, the particle diameter of PtlrCo alloy≤8, average out to 4.5nm, and better dispersed.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the power density of monocell reaches 0.45W/cm
2(600mA/cm
2).
Claims (6)
1, the one-dimensional nano carbon that a kind of fuel cell electro-catalyst, the carrier that it is characterized in that Pt in the eelctro-catalyst or Pt alloy adopt the conduction high polymer that contains big π bond structure to modify.
2, eelctro-catalyst according to claim 1 is characterized in that described one-dimensional nano carbon is carbon nano-tube or carbon nano-fiber, and wherein, carbon nano-tube comprises Single Walled Carbon Nanotube and multi-walled carbon nano-tubes.
3, eelctro-catalyst according to claim 1 is characterized in that described conduction high polymer is any in polyaniline, polypyrrole, polythiophene, polyacetylene, poly-phenylene vinylene (ppv) support, polyphenyl, polyphenylacetylene, poly(ethylene oxide) and the PPOX.
4, eelctro-catalyst according to claim 1 is characterized in that described Pt alloy is Pt
3M
xOr Pt
3M
xN
y, wherein x, y are respectively and are less than or equal to 3 natural number, and M, N are respectively the arbitrary metallic element among Pd, Ru, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, V, Ti, Ga, W, Sn and the Mo, and M and N are different.
5, the preparation method of the described eelctro-catalyst of claim 1 is characterized in that preparation technology is as follows:
1st, one-dimensional nano carbon is scattered in the alcohol solution, adds the monomer of conduction high polymer then, the mass ratio of one-dimensional nano carbon and conduction high polymer monomer is 0.1～10: 1, fully stirs, and makes dispersion liquid;
2nd, polymerization initiator oxidant and the Bronsted acid with the conducting polymer monomer joins in the prepared dispersion liquid of step 1, maintain the temperature at 0～10 ℃, react and made the complete polymerization of monomer in 1～8 hour, after filtration, the alcohol washing, make the one-dimensional nano carbon that conduction high polymer is modified, alcohol is any in methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol;
3rd, the conduction high polymer modification one-dimensional nano carbon with step 2 preparation is scattered in alcohol solution, adds the presoma salting liquid of Pt or Pt alloy, and the mass ratio of conduction high polymer monomer and Pt is 0.1～100: 1, fully stirs, at N
2, Ar or He protection down, 90～98 ℃ of reflux 5～20 minutes make eelctro-catalyst of the present invention;
Alcohol is 1～100: 1 with the mass ratio of water in the wherein said alcohol solution, and alcohol is any in methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol.
6, the preparation method of eelctro-catalyst according to claim 5, it is characterized in that described polymerization initiator oxidant and Bronsted acid, wherein oxidant is any in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, potassium bichromate, sodium dichromate, ammonium dichromate and the hydrogen peroxide, Bronsted acid comprises inorganic acid and organic acid two classes, inorganic acid is any in hydrochloric acid, nitric acid, sulfuric acid and the perchloric acid, and organic acid is any in benzene sulfonic acid, DBSA and the perfluorinated sulfonic resin.
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