CN1921193A - Conductive polymer modified fuel cell catalyst using conductive ceramics as carrier and its preparation - Google Patents
Conductive polymer modified fuel cell catalyst using conductive ceramics as carrier and its preparation Download PDFInfo
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Abstract
The invention relates to a fuel battery catalyst decorated with conductive polymer and carried by conductive ceramic. Wherein, its carrier conductive ceramic or metal catalyst particles are decorated by conducive polymer; compared with traditional carbon carried catalyst; the catalyst uses conductive ceramic as carrier, with better chemical stability; and it uses conductive polymer as adhesive to improve the combine force between the metal particles and conductive ceramic; in addition, the conductive polymer is used as protector to avoid grouping the catalyst particles. The preparation of catalyst comprises that preparing the nanometer platinum or platinum alloy colloid whose protector is polymer; preparing the carrier conductive ceramic decorated by conductive polymer; loading catalyst metal particles on the surface. And the catalyst can be prepared into fuel battery chip CCM, with better electric output property.
Description
Technical field
The present invention relates to a kind of catalyst, particularly be applied to the catalyst of fuel cell, be characterized in that the conductivity ceramics carrier of catalyst or noble metal catalyst particulate modified by conducting polymer.The invention still further relates to this kind Preparation of catalysts method.
Background technology
Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell is called for short PEMFC) is as a kind of novel energy source device, have plurality of advantages such as working temperature is low, pollution-free, specific power big, startup is rapid, more and more be subjected to people's attention, become the focus that countries in the world are competitively studied.Normally used catalyst is the alloy of precious metal platinum or platinum in fuel cell.But platinum is as a kind of scarce resource, and its price is very expensive.Therefore need to improve the utilance of platinum, reduce the consumption of platinum, to reach the purpose that reduces the fuel cell cost.People generally adopt carbon black as catalyst carrier at present, and this is because carbon black has higher specific surface area and has good electrical conductivity and preferable pore structure, the Dispersion of Particles of the metal platinum that helps improving.Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences (CN1165092C) adopts the deadman as chloroplatinic acid such as ammonium chloride, potassium chloride, made platinum grain in the active carbon hole with lip-deep equally distributed Pt/C catalyst.Physical Chemistry Technology Inst., Chinese Academy of Sciences (CN1677729A) adopts colloid method at first to prepare PtO
xColloid carries out the Pt/C catalyst that vapour phase reduction is prepared uniform particle diameter, high degree of dispersion then.University of Science ﹠ Technology, Beijing (CN1243390C) carries out preliminary treatment with the high alkalinity solution that contains the inferior stannic acid of weak reductant to carbon black support earlier, and the black carbon surface active site is evenly distributed; Joined then that reduce deposition obtains the PtRu/C catalyst in chloroplatinic acid and the ruthenic chloride mixed solution.But the utilance of Pt can be very not high among Pt/C, the PtM/C of above method preparation, important reasons is the micropore that a large amount of platinum or platinum alloy particulate enter into carbon surface, because this part platinum or the platinum alloy that are buried can not contact with proton conductor, therefore be difficult to form more three-phase reaction interface, thereby reduced the utilance of platinum.In addition, because platinum or platinum alloy directly link to each other with carbon, in preparation membrane electrode process, proton exchange resins can not enter into the position between platinum or platinum alloy and the carbon.This has reduced the phase reaction district on the one hand, owing to lack cementation, the bond strength between platinum or platinum alloy and the carbon is not high on the other hand.In PEMFC,, thereby make the durability of carbon black be subjected to weakening in addition owing to the work under bad environment of catalyst.And the existence of platinum can quicken the aging of carbon, from and cause coming off of platinum, this also will reduce the durability of catalyst greatly.
Report is also arranged now with the act as a fuel catalyst carrier of battery of carbon nano-tube (CNT).CNT has carbonization structure, therefore has conductivity and chemical stability preferably; Simultaneously, tube-surface micropore development degree is low, and most of platinum grain can be exposed to tube-surface, has improved the utilance of platinum; CNT has the feature that tubular structure and one dimension extend, and the mechanical strength height can form a kind of inierpeneirating network structure of uniqueness in Catalytic Layer, the not only intensity of Catalytic Layer raising, and also conductive capability also is enhanced; In addition, it also has good thermal conductivity.But should see that also the CNT surface is inertia, lack active sites, therefore influence the even dispersion of metallic catalyst.Northern Transportation University (CN1414726A) utilization photocatalysis in-situ chemical reduction precipitation method has synthesized CNT and has carried the platinum electrode catalyst, but does not fundamentally solve the agglomeration traits of CNT.The method of Zhejiang University (CN1424150A) utilization carry out microwave radiation heating in the carbon nano tube surface load platinum-ruthenium alloy catalysts, but they have but destroyed the chemical stability of CNT to the surface treatment of CNT.Xiamen University (CN1559686A) is though solved the agglomeration traits of CNT to a certain extent, and they also exist same problem to the surface treatment of CNT.
If pottery has reasonable resist chemical performance usually, therefore as catalyst carrier, can have corrosion resistance preferably.But pottery is non-conductive usually, therefore will can not make up the electron channel of catalyst layer with it as catalyst carrier.For this reason, the present invention adopts the conductivity ceramics cell catalyst carrier that acts as a fuel, and conducting polymer modified in addition.Compare with background technology, the present invention has the following advantages: 1) possess excellent conducting performance and corrosion resistance; 2) the conductivity ceramics surface micropore is few, and the noble metal catalyst particle can be anchored on carrier surface, thereby improves the utilization ratio of catalyst; 3) conducting polymer can improve adhesion between catalyst metal particles and carrier conductive ceramic as binding agent, and the reunion that stops catalyst granules; 4) conducting polymer itself is exactly an electric conductor, and under acid condition good stability.
At present, Shang Weiyou uses conducting polymer modified conductivity ceramics or conducting polymer modified catalyst metal particles, and is the relevant report of the fuel-cell catalyst of carrier with the conductivity ceramics.
Summary of the invention
The object of the invention provides a kind of catalyst that is applied to fuel cell.Catalyst possesses excellent conducting performance and corrosion resistance, and the bond strength between noble metal catalyst particle and carrier is good and do not reunite, and under acid condition the good stability of catalyst.The present invention also provides this kind Preparation of catalysts method.
The catalyst of a kind of fuel cell of the present invention is a noble metal catalyst, and characteristics are that carrier is a conductivity ceramics, and noble metal catalyst particle or conductivity ceramics carrier are modified by conducting polymer.
Conductivity ceramics carrier of the present invention is TiSi
2, TiB
2, TiC, TiO
2, ZrO
2, SiC, PbTiO
3, Ti
3SiC
2, BaPbO
3, LaCrO
3, TiC/Si
3N
4Or TiAl/TiB
2, particle diameter is 10～200 nanometers.
Conducting polymer of the present invention is any in polyaniline, polysulfones resin, polypyrrole, polythiophene, polyacetylene, poly-phenylene vinylene (ppv) support, polyacetylene, polyphenyl, polyphenylacetylene, PPOX and the poly(ethylene oxide).
Noble metal catalyst of the present invention is precious metal simple substance or precious metal alloys,
Precious metal alloys are M
xN
yOr M
xN
yO
zWherein M, N, O are respectively the arbitrary metallic element among Pt, Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga and the Mo, M, N, O three are different, but has a kind of noble metal platinum that is at least, x, y and z are respectively the natural number in 0～100, and x+y=100 or x+y+z=100;
Precious metal simple substance is any one among Pt, Ru, Pd, Rh, Ir and the Os.
A kind of preparation method of catalyst of the present invention prepares conducting polymer modified noble metal catalyst particle earlier, then it is loaded on the conductivity ceramics, and concrete preparation process is as follows:
Step 1, the conducting polymer monomer is dissolved in the alcohol solution, adds the catalyst precursor salting liquid, at N
2, He or Ar protection fully stirs down; pH=8～13 that keep solution in the course of reaction; 90～100 ℃ of reflux 20～60 minutes, prepare the platinum or the platinum alloy colloid of polymer monomer protection, the mass ratio of conducting polymer monomer and noble metal platinum is 0.1～100: 1.
Step 2, platinum or platinum alloy colloid that step 1 is made, add conductivity ceramics at 0～10 ℃, the polymerization initiator that adds polymer monomer again, the mass ratio of conductivity ceramics and conducting polymer monomer is 1～100: 1, stirred 2～8 hours, preparing with the conductivity ceramics is the fuel-cell catalyst of the conducting polymer modified noble metal catalyst particulate of carrier;
The another kind of preparation method of catalyst of the present invention prepares conducting polymer modified conductivity ceramics earlier, and at its area load noble metal catalyst particulate, concrete preparation process is as follows then:
Step 1, conductivity ceramics is dispersed in the alcohol solution, adds the monomer of conducting polymer then, the mass ratio of conductivity ceramics and conducting polymer monomer is 1～100: 1, fully stirs, and makes dispersion liquid;
Step 2, the polymerization initiator of conducting polymer monomer is joined in the made dispersion liquid of step 1, maintain the temperature at 0～10 ℃, react and made the complete polymerization of monomer in 2～8 hours, obtain conducting polymer modified conductivity ceramics;
Step 3, the conducting polymer modified conductivity ceramics that step 2 is prepared are scattered in the alcohol solution, add the presoma salting liquid of platinum or platinum alloy, and the mass ratio of conducting polymer monomer and platinum is 0.1～100: 1, at N
2, He or Ar protection fully stirs down, 90～100 ℃ of reflux 20～60 minutes, makes catalyst of the present invention;
In above-mentioned two kinds of preparation methods, alcohol is 0.5～100: 1 with the mass ratio of water in the described alcohol solution, and alcohol is any in methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol; Described polymerization initiator comprises oxidant and Bronsted acid, and wherein oxidant is any in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, potassium bichromate, sodium dichromate, ammonium dichromate and the hydrogen peroxide; Bronsted acid is any in hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, benzene sulfonic acid, DBSA and the perfluorinated sulfonic resin.
Catalyst precursor salt of the present invention is H
2PtCl
6, RuCl
3, PdCl
2, RhCl
3, IrCl
3, OsCl
3, Fe (NO
3)
3, Cr (NO
3)
3, NiCl
2, Co (NO
3)
2, MnCl
2, CuCl
2, TiCl
3, SnCl
2, VCl
4, Ga (NO
3)
3Or MoCl
5
The eelctro-catalyst of preparation is assembled into monocell, carries out electric performance test:
1, the preparation of fuel cell acp chip CCM (catalyst coated membrane):, fully stir the furnishing pasty state with the eelctro-catalyst adding deionized water of preparation and the perfluor sulfoacid resin solution of mass concentration 5%.Evenly be coated on the Nafion of DU PONT company then
@Series membranes (NRE212 or NRE211 etc.) both sides, oven dry makes CCM respectively.
2, monocell assembling and test: the carbon paper that adopts the polytetrafluoroethylene hydrophobic treatment is as gas diffusion layers, wherein the polytetrafluoroethylene mass concentration 20%～30%, and be compounded with the microporous layers that polytetrafluoroethylene and conductive carbon black particulate are formed in the one side, (calcining 20 minutes 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 corrosion resistant plate.CCM, gas diffusion layers, collector plate, end plate and encapsulant are assembled into monocell.The monocell operating condition is:
(1) Proton Exchange Membrane Fuel Cells (PEMFC): H
2/ air, air back pressure are 0; Anode humidification, humidification degree are 0～100%; The monocell working temperature is 60～80 ℃, and the humidification temperature is 60～75 ℃.
(2) straight methanol fuel cell (DMFC): the concentration of anode methyl alcohol is 2 mol, and flow is 5 ml/min, and negative electrode is an air, and back pressure is 0.
Compare with background technology, catalyst of the present invention is a kind of multi-functional fuel-cell catalyst, has following advantage:
(1) possesses excellent conducting performance and corrosion resistance;
(2) the conductivity ceramics surface micropore is few, and the noble metal catalyst particle can be anchored on carrier surface, thereby improves the utilization ratio of catalyst;
(3) conducting polymer can improve adhesion between catalyst metal particles and carrier conductive ceramic as binding agent;
(4) conducting polymer can also stop the reunion of catalyst particles as protective agent;
(5) conducting polymer itself is exactly an electric conductor, need not remove behind the synthetic catalyst.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
The aniline solution of 4 milliliters of mass concentrations 90% is joined in the mixed solution of 240 milliliters absolute ethyl alcohol and water, the mass ratio of absolute ethyl alcohol and water is 1: 1, adds the H of 4 grams per liters
2PtCl
640 milliliters, adjust pH=8 with NaOH, feed N
290 ℃ of reflux 50 minutes, obtain the platinum colloid that aniline monomer is modified.Get 116 milligrams TiB
2The conductivity ceramics particulate, particle diameter 10～50 nanometers, purity is greater than 95%, join in the mixed solution of 20 milliliters absolute ethyl alcohol and water (mass ratio of absolute ethyl alcohol and water is 1: 1), ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 8 minutes, and it is joined in 5 ± 1 ℃ the platinum colloid, add 2 gram ammonium persulfates again, 20 ml concns are the hydrochloric acid solution of 1 mol, continue down to stir 6 hours at 1 ± 1 ℃, after filtration, alcohol washes and make the Pt/TiB that polyaniline is modified the noble metal catalyst particulate
2Catalyst.The average grain diameter of platinum catalyst is 2.2 nanometers.
The preparation of fuel cell acp chip CCM:, fully stir the furnishing pasty state with the catalyst adding deionized water of preparation and the perfluor sulfoacid resin solution of mass concentration 5%.Evenly be coated on the Nafion of DU PONT company then
@Series membranes NRE211 both sides, oven dry makes CCM.Pt carrying capacity in the Catalytic Layer of CCM yin, yang the two poles of the earth adds up to: 0.46 milligram/centimetre
2
Monocell assembling and test: the carbon paper that adopts the polytetrafluoroethylene hydrophobic treatment is as gas diffusion layers, wherein the polytetrafluoroethylene mass concentration 20%, and be compounded with the microporous layers that polytetrafluoroethylene and conductive carbon black particle are formed in the one side, (calcining 20 minutes 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 corrosion resistant plate.CCM, gas diffusion layers, collector plate, end plate and encapsulant are assembled into monocell.The monocell operating condition is: H
2/ air, air back pressure are 0; Anode 100% humidification; The monocell working temperature is 70 ± 0.5 ℃, and the humidification temperature is 70 ± 0.5 ℃.Test result shows that the electricity output of monocell reaches 0.792 volt/centimetre
2The @300 milliampere/centimetre
2
Embodiment 2
Get 116 milligrams TiB
2The conductivity ceramics particulate, particle diameter 10～50 nanometers, purity is greater than 95%, join in the mixed solution of 20 milliliters absolute ethyl alcohol and water, the mass ratio of absolute ethyl alcohol and water is 1: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 5 minutes, the aniline solution that in mixed solution, adds 4 milliliters of mass concentrations 90% again, fully stir, add 2 gram sodium peroxydisulfates again, 20 ml concns are the hydrochloric acid solution of 1 mol, continue to stir 8 hours down at 1 ± 1 ℃, after filtration, alcohol washes, and makes the conductivity ceramics that polyaniline is modified.It is distributed in the mixed liquor of 240 milliliters of absolute ethyl alcohols and water, and the mass ratio of absolute ethyl alcohol and water is 1: 1, adds the H of 4 grams per liters
2PtCl
640 milliliters, adjust pH=10 with NaOH, feed N
298 ± 2 ℃ of reflux 10 minutes, through the Pt/TiB that cleans, drying obtains polyaniline modified conducting pottery
2Catalyst.The average grain diameter of platinum catalyst is 2.5 nanometers.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1, adopt the catalyst of present embodiment preparation.Test result shows,
MonocellOutput reaches 0.801 volt/centimetre
2The @300 milliampere/centimetre
2
Embodiment 3
The aniline solution of 4 milliliters of mass concentrations 90% is joined in the mixed liquor of 240 milliliters isopropyl alcohol and water, the mass ratio of isopropyl alcohol and water is 3: 1, adds the H of 4 grams per liters
2PtCl
640 milliliters, the Co (NO of 4 grams per liters
3)
240 milliliters, adjust pH=10 with NaOH, feed N
290～100 ℃ of reflux 30 minutes, obtain the PtCo colloid that aniline monomer is modified.Get 116 milligrams TiC conductivity ceramics particulate, particle diameter 50～100 nanometers, purity is greater than 92%, join in the mixed solution of 20 milliliters isopropyl alcohol and water, the mass ratio of isopropyl alcohol and water is 3: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 10 minutes, it is joined in 5 ± 1 ℃ the platinum colloid, add 2 gram potassium peroxydisulfates again, 10 ml concns are the sulfuric acid solution of 1 mol, continue down to stir 7 hours at 5 ± 1 ℃, after filtration, alcohol washes, and makes the Pt that polyaniline is modified the noble metal catalyst particulate
50Co
50/ TiC catalyst.The average grain diameter of noble metal catalyst is 3 nanometers.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1, adopt the catalyst of present embodiment preparation.Test result shows that the electricity output of monocell reaches 0.784 volt/centimetre
2The @300 milliampere/centimetre
2
Embodiment 4
Get 116 milligrams TiC conductivity ceramics particulate, particle diameter 50～100 nanometers, purity is greater than 92%, join in the mixed solution of 20 milliliters isopropyl alcohol and water, the mass ratio of isopropyl alcohol and water is 3: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 6 minutes, the aniline solution that in mixed solution, adds 4 milliliters of mass concentrations 90% again, fully stir, add 2 gram ammonium persulfates again, 20 ml concns are 1 mol salpeter solution, continue to stir 6 hours down at 1 ± 1 ℃, after filtration, alcohol washes, and makes the conductivity ceramics that polyaniline is modified.It is distributed in the mixed liquor of 240 milliliters isopropyl alcohol and water, and the mass ratio of isopropyl alcohol and water is 3: 1, adds the H of 4 grams per liters
2PtCl
640 milliliters, the IrCl of 4 grams per liters
320 milliliters, the Co (NO of 4 grams per liters
3)
220 milliliters, adjust pH=9 with NaOH, feed N
298 ± 2 ℃ of reflux 20 minutes, through the Pt that cleans, drying obtains polyaniline modified conducting pottery
50Ir
25Co
25/ TiC catalyst.The average grain diameter of noble metal catalyst is 2.8 nanometers.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1, adopt the catalyst of present embodiment preparation.Test result shows that the electricity output of monocell reaches 0.789 volt/centimetre
2The @300 milliampere/centimetre
2
Embodiment 5
Pyrroles's solution of 4 milliliters of mass concentrations 95% joined in 240 milliliters the mixed liquor of first alcohol and water, the mass ratio of first alcohol and water is 100: 1, adds the H of 4 grams per liters
2PtCl
640 milliliters, adjust pH=8 with NaOH, feed Ar 92 ± 2 ℃ of reflux 50 minutes, obtain the platinum colloid that pyrrole monomer is modified.Get 116 milligrams BaPbO
3The conductivity ceramics particulate, particle diameter 100～120 nanometers, purity is greater than 90%, join in 20 milliliters the mixed solution of first alcohol and water, the mass ratio of first alcohol and water is 100: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 10 minutes, it is joined in 4 ± 0.5 ℃ the platinum colloid, add 2 gram sodium peroxydisulfates again, 20 ml concns are the perchloric acid solution of 1 mol, continue down to stir 6 hours at 4 ± 0.5 ℃, after filtration, alcohol washes, and makes the Pt/BaPbO of polypyrrole modifying noble metal catalyst particulate
3Catalyst.The average grain diameter of platinum catalyst is 2 nanometers.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are executed together mutually with example 1, adopt the catalyst of present embodiment preparation.Test result shows that the electricity output of monocell reaches 0.764 volt/centimetre
2The @300 milliampere/centimetre
2
Embodiment 6
Get 116 milligrams BaPbO
3The conductivity ceramics particulate, particle diameter 100～120 nanometers, purity are greater than 90%, join in 20 milliliters the mixed solution of first alcohol and water, the mass ratio of first alcohol and water is 100: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 5 minutes, added pyrroles's solution of 4 milliliters of mass concentrations 95% again in mixed solution, fully stirred, add 2 gram ammonium persulfates again, continue down to stir 8 hours at 2 ± 1 ℃, after filtration, alcohol washes, and makes the conductivity ceramics of polypyrrole modifying.It is distributed in 240 milliliters the mixed liquor of first alcohol and water, and the mass ratio of first alcohol and water is 100: 1, adds the H of 4 grams per liters
2PtCl
640 milliliters, adjust pH=9 with NaOH, feed Ar 95 ± 1.0 ℃ of reflux 50 minutes, through the Pt/BaPbO that cleans, drying obtains the polypyrrole modifying conductivity ceramics
3Catalyst.The average grain diameter of platinum catalyst is 2 nanometers.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1, adopt the catalyst of present embodiment preparation.Test result shows that the electricity output of monocell reaches 0.781 volt/centimetre
2The @300 milliampere/centimetre
2
Embodiment 7
Pyrroles's solution of 4 milliliters of mass concentrations 95% is joined in the mixed liquor of 240 milliliters absolute ethyl alcohol and water, the mass ratio of absolute ethyl alcohol and water is 2: 1, adds the H of 4 grams per liters
2PtCl
640 milliliters, the RuCl of 4 grams per liters
340 milliliters of solution are adjusted pH=8 with NaOH, feed N
298 ± 2 ℃ of reflux 10 minutes, obtain the PtRu colloid that pyrrole monomer is modified.Get 116 milligrams TiAl/TiB
2The conductivity ceramics particulate, particle diameter 120～150 nanometers, purity is greater than 92%, join in the mixed solution of 20 milliliters absolute ethyl alcohol and water, the mass ratio of absolute ethyl alcohol and water is 2: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 10 minutes, it is joined in 5 ± 0.5 ℃ the PtRu colloid, the hydrogen peroxide that adds 2 grams 20% again, 20 ml concns are the hydrochloric acid solution of 1 mol, continue down to stir 6 hours at 5 ± 0.5 ℃, after filtration, alcohol washes, and makes the Pt of polypyrrole modifying noble metal catalyst particulate
50Ru
50/ TiAl/TiB
2Catalyst.The average grain diameter of metallic catalyst is 2 nanometers.
The preparation of fuel cell acp chip CCM:, fully stir the furnishing pasty state with the eelctro-catalyst adding deionized water of preparation and the perfluor sulfoacid resin solution of mass concentration 5%.Evenly be coated on the Nafion of DU PONT company then
@Series membranes NRE211 both sides, oven dry makes CCM.Anode uses the homemade catalyst of the present invention, and the platinum carrying capacity is 1 milligram/centimetre
2, negative electrode uses the Pt/C catalyst of JM company, and the platinum carrying capacity is 0.6 milligram/centimetre
2
Monocell assembling and test: the carbon paper that adopts the polytetrafluoroethylene hydrophobic treatment is as gas diffusion layers, wherein the polytetrafluoroethylene mass concentration 30%, and be compounded with the microporous layers that polytetrafluoroethylene and conductive carbon black particle are formed in the one side, (calcining 20 minutes 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 corrosion resistant plate.CCM, gas diffusion layers, collector plate, end plate and encapsulant are assembled into monocell.The monocell operating condition is: the concentration of anode methyl alcohol is 2 mol, and flow is 5 ml/min, and negative electrode is an air, and back pressure is 0.Test result shows, the electricity output of monocell reach 265 milliwatts/centimetre
2The @400 milliampere/centimetre
2
Embodiment 8
Get 116 milligrams TiAl/TiB
2The conductivity ceramics particulate, particle diameter 120～150 nanometers, purity is greater than 92%, join in the mixed solution of 20 milliliters absolute ethyl alcohol and water, the mass ratio of absolute ethyl alcohol and water is 2: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 8～10 minutes, the pyrroles's solution that in mixed solution, adds 4 milliliters of mass concentrations 95% again, fully stir, add 2 gram ammonium persulfates again, 20 ml concns are 1 mol hydrochloric acid solution, continue to stir 6 hours down at 8 ± 0.5 ℃, after filtration, alcohol washes, and makes the conductivity ceramics of polypyrrole modifying.It is distributed in the mixed liquor of 240 milliliters of absolute ethyl alcohols and water, and the mass ratio of absolute ethyl alcohol and water is 2: 1, adds the H of 4 grams per liters
2PtCl
640 milliliters, the RuCl of 4 grams per liters
340 milliliters of solution are adjusted pH=9 with NaOH, feed N
298 ± 2 ℃ of reflux 10 minutes, through the Pt that cleans, drying obtains the polypyrrole modifying conductivity ceramics
50Ru
50/ TiAl/TiB
2Catalyst.The average grain diameter of metallic catalyst is 2 nanometers.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 7, adopt the catalyst of present embodiment preparation.Test result shows that the electricity output of monocell reaches 0.766 volt/centimetre
2The @300 milliampere/centimetre
2
Embodiment 9
The aniline solution of 4 milliliters of mass concentrations 90% is joined in the mixed liquor of 240 milliliters of absolute ethyl alcohols and water, and the mass ratio of absolute ethyl alcohol and water is 1: 1, adds the H of 4 grams per liters
2PtCl
640 milliliters, the RuCl of 4 grams per liters
320 milliliters of solution, the SnCl of 4 grams per liters
320 milliliters of solution are adjusted pH=11 with NaOH, feed He 98 ± 2 ℃ of reflux 20 minutes, obtain the alloy colloid that aniline monomer is modified.Get 116 milligrams TiC/Si
3N
4The conductivity ceramics particulate, particle diameter 150～200 nanometers, purity are greater than 85%, join in the mixed solution of 20 milliliters absolute ethyl alcohol and water, the mass ratio of absolute ethyl alcohol and water is 1: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 10 minutes, and it is joined in 1 ± 1 ℃ the alloy colloid, added 2 gram sodium peroxydisulfates again, 20 ml concns are the hydrochloric acid solution of 1 mol, continue down to stir 6 hours at 6 ± 1 ℃, after filtration, alcohol washes, and makes the Pt that polyaniline is modified the noble metal catalyst particulate
50Ru
25Sn
25/ TiC/Si
3N
4Catalyst.The average grain diameter of alloy catalyst is 2 nanometers.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 7, adopt the catalyst of present embodiment preparation.Test result shows that the electricity output of monocell reaches 0.769 volt/centimetre
2The @300 milliampere/centimetre
2
Embodiment 10
Get 116 milligrams TiC/Si
3N
4The conductivity ceramics particulate, particle diameter 150～200 nanometers, purity is greater than 85%, join in the mixed solution of 20 milliliters absolute ethyl alcohol and water, the mass ratio of absolute ethyl alcohol and water is 1: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 5 minutes, the aniline solution that in mixed solution, adds 4 milliliters of mass concentrations 90% again, fully stir, add 2 gram ammonium persulfates again, 20 ml concns are the hydrochloric acid solution of 1 mol, continue to stir 7 hours down at 6 ± 1 ℃, after filtration, alcohol washes, and makes the conductivity ceramics that polyaniline is modified.It is distributed in the mixed liquor of 240 milliliters of absolute ethyl alcohols and water, and the mass ratio of absolute ethyl alcohol and water is 1: 1, adds the H of 4 grams per liters
2PtCl
640 milliliters, the RuCl of 4 grams per liters
320 milliliters of solution, the SnCl of 4 grams per liters
320 milliliters of solution are adjusted pH=10 with NaOH, feed He 98 ± 2 ℃ of reflux 20 minutes, through the Pt that cleans, drying obtains polyaniline modified conducting pottery
50Ru
25Sn
25/ TiC/Si
3N
4Catalyst.The average grain diameter of alloy catalyst is 2 nanometers.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 7, adopt the catalyst of present embodiment preparation.Test result shows that the electricity output of monocell reaches 0.770 volt/centimetre
2The @300 milliampere/centimetre
2
Claims (6)
1, a kind of fuel cell noble metal catalysts is characterized in that, carrier is a conductivity ceramics, and noble metal granule in the catalyst or conductivity ceramics carrier are modified by conducting polymer.
2, fuel cell noble metal catalysts as claimed in claim 1 is characterized in that, described conductivity ceramics carrier is TiSi
2, TiB
2, TiC, TiO
2, ZrO
2, SiC, PbTiO
3, Ti
3SiC
2, BaPbO
3, LaCrO
3, TiC/Si
3N
4Or TiAl/TiB
2, particle diameter is 10～200 nanometers.
3, fuel cell noble metal catalysts as claimed in claim 1, it is characterized in that described conducting polymer is any in polyaniline, polysulfones resin, polypyrrole, polythiophene, polyacetylene, poly-phenylene vinylene (ppv) support, polyacetylene, polyphenyl, polyphenylacetylene, PPOX and the poly(ethylene oxide).
4, fuel cell noble metal catalysts as claimed in claim 1 is characterized in that, described noble metal catalyst is precious metal simple substance or precious metal alloys,
Precious metal alloys are M
xN
yOr M
xN
yO
zWherein M, N, O are respectively the arbitrary metallic element among Pt, Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga and the Mo, M, N, O three are different, but has a kind of noble metal platinum that is at least, x, y and z are respectively the natural number in 0～100, and x+y=100 or x+y+z=100;
Precious metal simple substance is any one among Pt, Ru, Pd, Rh, Ir and the Os.
5, the preparation technology of the described fuel cell noble metal catalysts of claim 1 is characterized in that, the Preparation of catalysts step of described conducting polymer modified noble metal is:
Step 1, the conducting polymer monomer is dissolved in the alcohol solution, adds the solution of catalyst precursor, at N
2, He or Ar protection fully stirs down, pH=8～13 that keep solution in the course of reaction, 90～100 ℃ of reflux 20～60 minutes, prepare the platinum or the platinum alloy colloid of polymer monomer protection, the mass ratio of conducting polymer monomer and platinum is 0.1～100: 1;
Step 2, platinum or platinum alloy colloid that step 1 is made, add conductivity ceramics at 0～10 ℃, the polymerization initiator that adds polymer monomer again, the mass ratio of conductivity ceramics and conducting polymer monomer is 1～100: 1, stirred 2～8 hours, preparing with the conductivity ceramics is the fuel-cell catalyst of the conducting polymer modified noble metal catalyst particulate of carrier;
Wherein, alcohol is 0.5～100: 1 with the mass ratio of water in the described alcohol solution, and alcohol is any in methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol; Described polymerization initiator comprises oxidant and Bronsted acid, and wherein oxidant is any in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, potassium bichromate, sodium dichromate, ammonium dichromate and the hydrogen peroxide; Bronsted acid is any in hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, benzene sulfonic acid, DBSA and the perfluorinated sulfonic resin.
6, the preparation technology of the described fuel cell noble metal catalysts of claim 1 is characterized in that, the Preparation of catalysts step of described conducting polymer modified conductivity ceramics carrier is:
Step 1, conductivity ceramics is dispersed in the alcohol solution, adds the monomer of conducting polymer then, the mass ratio of conductivity ceramics and conducting polymer monomer is 1～100: 1, fully stirs, and makes dispersion liquid;
Step 2, the polymerization initiator of conducting polymer monomer is joined in the made dispersion liquid of step 1, maintain the temperature at 0～10 ℃, react and made the complete polymerization of monomer in 2～8 hours, obtain conducting polymer modified conductivity ceramics;
Step 3, the conducting polymer modified conductivity ceramics that step 2 is prepared are scattered in the alcohol solution, add the presoma salting liquid of platinum presoma salting liquid or platinum alloy, and the mass ratio of conducting polymer monomer and platinum is 0.1～100: 1, at N
2, He or Ar protection fully stirs down, 90～100 ℃ of reflux 20～60 minutes, makes catalyst of the present invention;
Wherein, alcohol is 0.5～100: 1 with the mass ratio of water in the described alcohol solution, and alcohol is any in methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol; Described polymerization initiator comprises oxidant and Bronsted acid, and wherein oxidant is any in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, potassium bichromate, sodium dichromate, ammonium dichromate and the hydrogen peroxide; Bronsted acid is any in hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, benzene sulfonic acid, DBSA and the perfluorinated sulfonic resin.
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