CN1674329A - Electric catalyst with compound conducing high polymer modification one-dimensional nano carbon as carrier and preparation - Google Patents
Electric catalyst with compound conducing high polymer modification one-dimensional nano carbon as carrier and preparation Download PDFInfo
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- CN1674329A CN1674329A CNA2005100182867A CN200510018286A CN1674329A CN 1674329 A CN1674329 A CN 1674329A CN A2005100182867 A CNA2005100182867 A CN A2005100182867A CN 200510018286 A CN200510018286 A CN 200510018286A CN 1674329 A CN1674329 A CN 1674329A
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Abstract
An electro-catalyst is featured as using one - dimensional nanocarbon modified by composite conduction high polymer in large Pi bond structure as carrier. Its preparing process includes preparing one - dimensional carbon modified by composite conduction high polymer first and then loading Pt or Pt alloy on its surface. The average metal particle diameter of electro - catalyst is less than or equal to 5 nm and power density of single cell prepared by electro - catalyst is 0.42-0.50 W / 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 adopts the composite conducting high polymer modification one-dimensional nano carbon.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.Therefore 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 takes place carbon black easily, has promoted the loss of platinum or platinum alloy particles or 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 nanofibres CNFs) etc., has and the similar structure of crystalline graphite carbon nano-fiber, therefore 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 reported in literature 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 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 and metallics such as Pt are carried on unidimensional nanocarbon surface, the particle diameter that the eelctro-catalyst of preparation also exists 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.
Some scholars study the electric conductivity that improves conduction high polymer.Wang Junxiang etc. (New Chemical Materials, 2004,32,1,31-34) report as adding material, has prepared the composite conducting polyaniline with the nano silver particles of high conductivity, and electric conductivity is improved preferably.People such as Ma Yalu (polymer material science and engineering, 2001,17,5,165-171) by adding TiO
2, Al
2O
3Deng metal oxide, prepare the composite conducting polyaniline with sol-gel process, make the electric conductivity of polyaniline obtain bigger raising.Therefore can form the composite conducting high polymer by in the matrix of high polymer, mixing nano conducting powders, reach the purpose of the conductivity that strengthens high polymer.
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 particularly used in proton exchange membrane fuel cell eelctro-catalyst of a kind of fuel cell; Another object of the present invention provides the preparation method of this kind eelctro-catalyst.
Fuel cell electro-catalyst of the present invention, the carrier that it is characterized in that Pt in the eelctro-catalyst or Pt alloy is the one-dimensional nano carbon of composite conducting high polymer modification, and described composite conducting high polymer is formed by containing big π bond structure conductive polymer polymer matrix material and conductive filling material.
Employing contains big π bond structure conduction high polymer modification one-dimensional nano carbon as carrier, mainly be to utilize pi-pi bond between conduction high polymer matrix and the 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 are 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, and the controllability of the dispersiveness of metallic and particle diameter is improved also.For increasing the conductivity of conduction high polymer, the present invention is compound with conduction high polymer and conductive filling material, has prepared the composite conducting high polymer with high conductivity feature.
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.
It is of the present invention that to contain big π bond structure conductive polymer high polymer be in polyaniline, polypyrrole, polythiophene, polyacetylene, poly-phenylene vinylene (ppv) support, polyacetylene, polyphenyl, polyphenylacetylene, poly(ethylene oxide) and the PPOX any; Described conductive filling material is that carbon is any in filler, siliceous filler, metallic stuffing and the metal oxide; Carbon is that filler is carbon black or the graphite superfine powder of particle diameter≤100nm, and siliceous filler is SiC or the MoSi of particle diameter≤100nm
2, metallic stuffing is the superfine powder of Au, Ag, Cu, Cr, Ni, Fe, Co, Al, Mo, Mn, Ti, W or the Sn of particle diameter≤100nm, metal oxide filler is ZnO, the Al of particle diameter≤100nm
2O
3, TiO
2, NiO, CuO, BaPbO
3, LaCrO
3, LaMnO
3Or SrPbO
3Superfine powder.
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 is the one-dimensional nano carbon for preparing the composite conducting high polymer modification 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, the monomer and the conductive filling material that add conduction high polymer then, fully stir, make dispersion liquid, wherein the mass ratio of the monomer of conduction high polymer and conductive filling material is 1: 0.01～1, and 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, wash with alcohol after filtration, make the one-dimensional nano carbon of composite conducting high polymer modification, alcohol is any in methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol, polymerization initiator is made up of oxidant and Bronsted acid two parts, and 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, 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 then, 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 1～30 minute make eelctro-catalyst of the present invention;
Wherein the mass ratio of alcohol and water is 1～100: 1 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, the Nafion series membranes that evenly is coated on DU PONT company then is (as NRE212, NRE211 etc.) both sides, oven dry makes CCM respectively.CCM yin, yang the two poles of the earth catalyst layer Pt carrying capacity 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 lower.Original method adopts the chemical inert of chemical oxidization method or activation method change unidimensional nanocarbon surface, will destroy the body construction of one-dimensional nano carbon, reduces chemistry, physical stability and the conductivity of material.The present invention has adopted the composite conducting high polymer to come modification one-dimensional nano carbon, utilize the conduction high polymer matrix in the composite conducting thing to combine with the one-dimensional nano carbon pi-pi bond, under the condition of not destroying the 1-dimention nano carbon structure, solved the unstable problem of combining between catalyst granules 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 the metal nanoparticle of formation preferably simultaneously.
3, the composite conducting high polymer of the present invention's employing has higher conductivity, therefore can not reduce the electric conductivity of catalyst.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Get the multi-walled carbon nano-tubes of 0.25g, join in the mixed liquor of 20ml second alcohol and water (mass ratio of second alcohol and water is 1: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～10 minutes, is the nano-Ag particles of 25nm by 1: 1 solid masses than the aniline solution and the average grain diameter that add 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, get the carbon nano-tube that the composite conducting polyaniline is modified.The carbon nano-tube that the composite conducting 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 carbon nano-tube platinum catalyst that the composite conducting polyaniline is modified.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 CCM yin, yang the two poles of the earth catalyst layer 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 ℃.After tested, the electrical property of monocell reaches 0.47W/cm
2(600mA/cm
2).
Embodiment 2
Get the multi-walled carbon nano-tubes of 0.25g, join in the mixed liquor of 20ml second alcohol and water (mass ratio of second alcohol and water is 100: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～10 minutes, is the nano-Ag particles of 25nm by 1: 1 solid masses than the aniline solution and the average grain diameter that add 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 the composite conducting polyaniline is modified.The carbon nano-tube that the composite conducting 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 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 1 minute, but still continue to feed N
2Product is cooled off gradually, make the carbon nano-tube platinum catalyst that the composite conducting polyaniline is modified.Wherein, the particle diameter≤5nm 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 electrical property of monocell reaches 0.44W/cm
2(600mA/cm
2).
Embodiment 3
Get the multi-walled carbon nano-tubes of 0.25g, join in the mixed liquor of 20ml 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 5～10 minutes, (average grain diameter was 30nm than the aniline solution that adds 90wt% and XC-72 conductive carbon black by 1: 1 solid masses, U.S. Cabot company produces), the mass ratio of carbon nano-tube and aniline is 0.6: 1, fully stir, adding ammonium persulfate 2g and concentration is the salpeter solution 20ml of 1mol/l, lasting stirring reaction is 8 hours under 0 ℃, after the filtration,, get the carbon nano-tube that the composite conducting polyaniline is modified with ethanol washing 2～3 times.The carbon nano-tube that the composite conducting 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), 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 stir, feed Ar, 98 ℃ of reflux reacts and are stopped after 8 minutes heating, but still continue to feed Ar product is cooled off gradually, make the carbon nano-tube platinum catalyst that the composite conducting polyaniline is modified.Wherein, the particle diameter≤5nm 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 electrical property of monocell reaches 0.46W/cm
2(600mA/cm
2).
Embodiment 4
Get the multi-walled carbon nano-tubes of 0.25g, join in the mixed liquor of 20ml 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 5～10 minutes, (average grain diameter was 30nm than the aniline solution that adds 90wt% and XC-72 conductive carbon black by 1: 0.01 solid masses, U.S. Cabot company produces), 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,, get the carbon nano-tube that the composite conducting polyaniline is modified with ethanol washing 2～3 times.The carbon nano-tube that the composite conducting 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), 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 stir, feed Ar, 98 ℃ of reflux reacts and are stopped after 8 minutes heating, but still continue to feed Ar product is cooled off gradually, make the carbon nano-tube platinum catalyst that the composite conducting polyaniline is modified.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 electrical property of monocell reaches 0.43W/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 5～10 minutes, is the nano SiC granule of 20nm by 1: 0.01 solid masses than the pyrroles's solution and the average grain diameter that add 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, get 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 80ml of 0.046mol/l, the mass ratio of pyrroles and platinum is 2: 1, fully stirs, and feeds N
2, reflux is reacted and is stopped heating after 8 minutes, but still continue to feed N
2Product is cooled off gradually, make the carbon nano-tube platinum catalyst of composite conducting polypyrrole modifying.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 electrical property of monocell reaches 0.44W/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 5～10 minutes, is the nano SiC granule of 20nm by 1: 0.01 solid masses than the pyrroles's solution and the average grain diameter that add 95wt%, carbon nano-tube and pyrroles's mass ratio is 0.5: 1, fully stir, adding sodium peroxydisulfate 3.6g and concentration is the hydrochloric acid 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
2Product is cooled off gradually, make the carbon nano-tube platinum catalyst of composite conducting polypyrrole modifying.Wherein, the particle diameter≤6nm of platinum, 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 electrical property of monocell reaches 0.42W/cm
2(600mA/cm
2).
Embodiment 7
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 5～10 minutes, is the nano-Ag particles of 25nm by 1: 0.02 solid masses than the pyrroles's solution and the average grain diameter that add 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), adding Pt concentration 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, 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 carbon nano-tube platinum catalyst of composite conducting polypyrrole modifying.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 electrical property of monocell reaches 0.45W/cm
2(600mA/cm
2).
Embodiment 8
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 5～10 minutes, is the nano-Ag particles of 25nm by 1: 0.2 solid masses than the pyrroles's solution and the average grain diameter that add 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 16g 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, get 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, 90 ℃ of reflux are reacted and are stopped heating after 30 minutes, but still continue to feed N
2Product is cooled off gradually, make the carbon nano-tube platinum catalyst of composite conducting polypyrrole modifying.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 electrical property of monocell reaches 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 1.4: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed after 5～10 minutes, is the nano-Ag particles of 25nm by 1: 0.2 solid masses than the pyrroles's solution and the average grain diameter that add 95wt%, carbon nano-tube and pyrroles's mass ratio is 1: 1, fully stir, adding ammonium persulfate 160g and concentration is the hydrochloric acid solution 1.6l 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 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
2Product is cooled off gradually, make the carbon nano-tube platinum catalyst of composite conducting polypyrrole modifying.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 electrical property of monocell reaches 0.42W/cm
2(600mA/cm
2).
Embodiment 10
Get the carbon nano-fiber of 0.8g, join in the mixed liquor of 20ml 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 5～10 minutes, is the nano-Ag particles of 25nm by 1: 0.2 solid masses than the aniline solution and the average grain diameter that add 90wt%, the mass ratio of carbon nano-tube 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, get the carbon nano-fiber that the composite conducting polyaniline is modified.The carbon nano-fiber that the composite conducting polyaniline that makes 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
2Product is cooled off gradually, make the carbon nano-fiber platinum catalyst of composite conducting polypyrrole modifying.Wherein, the particle diameter≤5nm 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 electrical property of monocell reaches 0.44W/cm
2(600mA/cm
2).
Embodiment 11
Get the multi-walled carbon nano-tubes of 0.5g, join in the mixed liquor of 20ml 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 5～10 minutes, was the nanometer Al of 30nm by 1: 0.2 solid masses than the aniline solution and the average grain diameter that add 90wt%
20
3Particle, the mass ratio of carbon nano-tube and aniline are 0.6: 1, fully stir, adding ammonium persulfate 4g and concentration is the hydrochloric acid solution 40ml 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 the composite conducting polyaniline is modified.The carbon nano-tube that the composite conducting polyaniline that makes is modified is scattered in the mixed liquor of 310ml second alcohol and water (mass ratio of second alcohol and water is 1.4: 1), adding Pt concentration is the platinum acid chloride solution 55ml 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 carbon nano-tube platinum catalyst that the composite conducting polyaniline is modified.Wherein, platinum grain directly is≤4.5nm, 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 electrical property of monocell reaches 0.44W/cm
2(600mA/cm
2).
Embodiment 12
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 5～10 minutes, is the nano-Ag particles of 25nm by 1: 0.1 solid masses than the pyrroles's solution and the average grain diameter that add 95wt%, carbon nano-tube and pyrroles's mass ratio is 0.5: 1, fully stir, adding ammonium persulfate 3.2g and concentration again 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, get 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 Fe concentration that add Pt concentration respectively and be 0.046mol/l are the FeCl of 0.046mol/l
3Solution 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
2Product is cooled off gradually, and the carbon nano-tube that makes the composite conducting polypyrrole modifying is carried the PtFe alloy catalyst.Wherein, the particle diameter≤8nm of PtFe alloy, average out to 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 electrical property of monocell reaches 0.45W/cm
2(600mA/cm
2).
Embodiment 13
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 5～10 minutes, was the nano-TiO of 20nm by 1: 0.1 solid masses than the pyrroles's solution and the average grain diameter that add 95wt%
2Particle, carbon nano-tube and pyrroles's mass ratio are 0.5: 1, fully stir, adding ammonium persulfate 3.2g and concentration again is the hydrochloric acid solution 32ml of 1mol/l, and lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, get 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 the RuCl of 0.046mol/l
3Solution 84ml, the mass ratio of pyrroles and Pt are 2: 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, the carbon nano-tube that makes the composite conducting polypyrrole modifying is carried the PtRu alloy catalyst.Wherein, the particle diameter≤6nm 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 electrical property of monocell reaches 0.48W/cm
2(600mA/cm
2).
Embodiment 14
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 5～10 minutes, was the nanometer LaCrO of 35nm by 1: 0.1 solid masses than the pyrroles's solution and the average grain diameter that add 95wt%
3Particle, carbon nano-tube and pyrroles's mass ratio are 0.5: 1, fully stir, adding ammonium dichromate 3.2g and concentration is the hydrochloric acid solution 32ml of 1mol/l, and lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, get 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
2Product is cooled off gradually, and the carbon nano-tube that makes the composite conducting polypyrrole modifying is carried Pt
3The Cr alloy catalyst.Wherein, Pt
3Particle diameter≤the 7nm of Cr alloy, 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 electrical property of monocell reaches 0.50W/cm
2(600mA/cm
2).
Embodiment 15
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 5～10 minutes, was the nanometer LaCrO of 35nm by 1: 0.1 solid masses than the pyrroles's solution and the average grain diameter that add 95wt%
3Particle, carbon nano-tube and pyrroles's mass ratio are 0.5: 1, fully stir, adding ammonium dichromate 3.2g and concentration is the hydrochloric acid solution 32ml of 1mol/l, and lasting stirring reaction is 8 hours under 0 ℃, after the filtration, with ethanol washing 2～3 times, get 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 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
2Product is cooled off gradually, and the carbon nano-tube that makes the composite conducting polypyrrole modifying is carried the PtCr alloy catalyst.Wherein, the particle diameter≤7nm of PtCr 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 electrical property of monocell reaches 0.45W/cm
2(600mA/cm
2).
Embodiment 16
Get the carbon nano-fiber of 0.8g, join in the mixed liquor of 20ml 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 5-10 minute, is the nano-Ag particles of 25nm by 1: 0.25 solid masses than the aniline solution and the average grain diameter that add 90wt%, the mass ratio of carbon nano-tube and aniline is 0.6: 1, fully stir, adding ammonium dichromate 6.2g and concentration again 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, get the carbon nano-fiber that the composite conducting polyaniline is modified.The carbon nano-fiber that the composite conducting polyaniline that makes 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 respectively is the platinum acid chloride solution 83ml of 0.046mol/l, and Cr concentration is the CrCl of 0.046mol/l
3Solution 83ml and Co concentration are the CoCl of 0.046mol/l
2Solution 83ml, the mass ratio of aniline and Pt are 1.8: 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, and the carbon nano-fiber that makes the composite conducting polypyrrole modifying carries the PtCoCr alloy catalyst.Wherein, the particle diameter≤6nm of PtCoCr alloy, 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 electrical property of monocell reaches 0.50W/cm
2(600mA/cm
2).
Embodiment 17
Get the carbon nano-fiber of 0.8g, join in the mixed liquor of 20ml 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 5-10 minute, is the nano-Ag particles of 25nm by 1: 0.25 solid masses than the aniline solution and the average grain diameter that add 90wt%, the mass ratio of carbon nano-tube 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, get the carbon nano-fiber that the composite conducting polyaniline is modified.The carbon nano-fiber that the composite conducting polyaniline that makes 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 respectively is the platinum acid chloride solution 83ml of 0.046mol/l, and Ir concentration is the IrCl of 0.046mol/l
3Solution 83ml and Co concentration are the CoCl of 0.046mol/l
2Solution 83ml, the mass ratio of aniline and Pt are 1.8: 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, and the carbon nano-fiber that makes the composite conducting polypyrrole modifying carries the PtlrCo alloy catalyst.Wherein, the particle diameter≤8nm of PtlrCo 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 electrical property of monocell reaches 0.49W/cm
2(600mA/cm
2).
Claims (7)
1, a kind of fuel cell electro-catalyst, the carrier that it is characterized in that Pt in the eelctro-catalyst or Pt alloy is the one-dimensional nano carbon of composite conducting high polymer modification, and described composite conducting high polymer is formed by containing big π bond structure conductive polymer polymer matrix material and conductive filling material.
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, it is characterized in that described conductive filling material is that carbon is any in filler, siliceous filler, metallic stuffing and the metal oxide, carbon is that filler is carbon black or the graphite superfine powder of particle diameter≤100nm, and siliceous filler is SiC or the MoSi of particle diameter≤100nm
2, metallic stuffing is the superfine powder of Au, Ag, Cu, Cr, Ni, Fe, Co, Al, Mo, Mn, Ti, W or the Sn of particle diameter≤100nm, metal oxide filler is ZnO, the Al of particle diameter≤100nm
2O
3, TiO
2, NiO, CuO, BaPbO
3, LaCrO
3, LaMnO
3Or SrPbO
3Superfine powder.
5, 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.
6, 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, the monomer and the conductive filling material that add conduction high polymer then, fully stir, make dispersion liquid, the monomer of conduction high polymer and the mass ratio of conductive filling material are 1: 0.01～1, and the mass ratio of one-dimensional nano carbon and conduction high polymer monomer is 0.1～10: 1;
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 under 0～10 ℃ the condition, react and made the complete polymerization of monomer in 1～8 hour, wash with alcohol after filtration, make the one-dimensional nano carbon of composite conducting high polymer modification, described alcohol is any in methyl alcohol, ethanol, propyl alcohol, 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 1～30 minute make eelctro-catalyst of the present invention;
Alcohol is 1～100: 1 with the mass ratio of water in the described alcohol solution wherein, and alcohol is any in methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol.
7, 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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