CN102088093A - Fuel cell catalyst taking conductive ceramic boron carbide as supporter and preparation method thereof - Google Patents
Fuel cell catalyst taking conductive ceramic boron carbide as supporter and preparation method thereof Download PDFInfo
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- CN102088093A CN102088093A CN201110000141XA CN201110000141A CN102088093A CN 102088093 A CN102088093 A CN 102088093A CN 201110000141X A CN201110000141X A CN 201110000141XA CN 201110000141 A CN201110000141 A CN 201110000141A CN 102088093 A CN102088093 A CN 102088093A
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Abstract
The invention discloses a fuel cell catalyst taking conductive ceramic boron carbide as a supporter and a preparation method thereof. Compared with the traditional carbon supporter catalyst, the fuel cell catalyst takes the conductive ceramic boron carbide as the supporter, so that the catalyst has the advantages of higher electrochemical activity area, higher capability on resisting carbon monoxide poisoning and higher oxidation resistance. The preparation method of the catalyst comprises the following steps: preparing a stable nanoparticle platinum or platinum alloy colloid in advance; supporting the nanoparticle platinum or platinum alloy colloid on a boron carbide supporter; and preparing the fuel cell catalyst which takes the boron carbide as the supporter. The prepared catalyst is made into a fuel cell MEA (membrane electrode assembly) which has better electrical output performance and cell stability.
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 used carrier of catalyst is an electrical-conductive nanometer pottery boron carbide.The invention still further relates to this kind Preparation of catalysts method.
Background technology
(Proton Exchange Membrane Fuel Cell PEMFC) starts fast clear energy sources as a kind of high efficiency, environmental friendliness, room temperature to Proton Exchange Membrane Fuel Cells, has become one of research focus of energy field at present.For its research, the focus majority all concentrates on and improves performance, reduces cost and improve on the durability.Wherein, the durability of PEMFC is to hinder its business-like one big bottleneck.This is because catalyst mainly uses is the Pt noble metal catalyst, and the reduction of catalyst activity and the degraded of proton exchange membrane cause PEMFC durability or low major reason of life-span often in the fuel cell operation process.
Under the PEMFC operational environment, especially catalyst base is easy to corrode under the elevated oxygen level of negative electrode, high potential condition, and its chemistry and electrochemical stability are difficult to reach the life requirements of PEMFC.The corrosion of catalyst base can cause serious consequence, mainly shows: the corrosion of catalyst base can cause peeling off between platinum grain and carrier, makes the platinum grain can't electron gain and ineffective; The corrosion of carrier also can cause subsiding of platinum grain, and platinum grain produce to be assembled, and the platinum grain that subsides is easier is subjected to the covering of carrier or covers; The corrosion of carrier also can change the surface state of material, can reduce the hydrophobicity of material usually, increases the gas transfer resistance, simultaneously intermediate product (as CO) also can strong adsorption in the surface of platinum, cause catalyst poisoning.
Patent US2008/003476A1 proposes to add materials such as chloride, iodide, bromide to suppress growing up and dissolving loss of noble metal in noble metal catalyst.Patent ZL200610020008.x proposes to utilize conductivity ceramics to prepare noble metal catalyst as catalyst base.Compare with the conventional carbon carrier, conductivity ceramics possesses good chemistry and electrochemical stability, and the conductivity ceramics smooth surface, and various spaces are less, can improve the utilance of noble metal granule.Patent ZL200610020007.5 utilizes proton superpolymer modified nanometer noble metal microparticles, has improved the adhesion between noble metal and carrier, can effectively prevent peeling off of fine particle of noble metal and carrier, thereby reduces the dissolving and the reunion of noble metal granule.
As catalyst base, the various spaces of conductivity ceramics smooth surface are less with the conductivity ceramics boron carbide in the present invention, can also improve the utilance of noble metal granule.But compare with background technology, described boron carbide has excellent conducting performance, better chemical stability and antioxygenic property.Boron carbide ceramics and acid, aqueous slkali Fails To Respond, different with other conductivity ceramicss is that boron carbide is to one of the most stable material of acid, all stablizes in all dense or rare acid or aqueous alkali.And, the boron carbide carrier has lower Molecular Adsorption ability than conventional carbon carrier and other conductivity ceramicss, can improve electro-chemical activity, the anti-carbon monoxide poisoning capability of catalyst effectively and improve life of catalyst, this is that other conductivity ceramicss do not have as catalyst base.In addition, the easier realization nanometer of boron carbide.Nano level boron carbide is compared with micron higher level boron carbide particles, can better support the noble metal catalyst particle, improves dispersibility and the carrying capacity of noble metal catalyst on the carrier surface, thereby has greatly improved the electrochemical catalysis activity of catalyst.Carrier of the present invention also is applicable to direct methanol fuel cell (DMFC) and direct aminic acid fuel battery (DFAFC) simultaneously.
Not having at present with conductive nano pottery boron carbide as yet is the relevant report of the catalyst of fuel batter with proton exchange film of carrier.
Summary of the invention
The purpose of this invention is to provide a kind of fuel battery metal catalyst that is applied to, the present invention also provides the preparation method of this kind metallic catalyst.
A kind of fuel battery metal catalyst of the present invention is characterized in that: the carrier of described metallic catalyst is the conductivity ceramics boron carbide, and described conductivity ceramics boron carbide is a hexagonal structure, and particle diameter is 10～100 nanometers.
Conductivity ceramics boron carbide of the present invention and acid, aqueous slkali Fails To Respond have high chemical potential, neutron absorption, wear-resisting and excellent conducting performance.Different with other potteries, boron carbide is to one of the most stable material of acid, all stablizes in all dense or rare acid or aqueous alkali.
Boron carbide carrier of the present invention has lower Molecular Adsorption ability than conventional carbon carrier and other conductivity ceramicss, therefore is that the fuel cell noble metal catalysts of carrier has higher chemical property and anti-carbon monoxide poisoning capability with the boron carbide ceramics.
The metal of metallic catalyst of the present invention is precious metal simple substance or precious metal alloys, and described precious metal simple substance is any one among Pt, Ru, Pd, Rh, Ir, the Os; Described precious metal alloys are MxNy or MxNyOz, wherein 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 each metallic atom ratio in the catalyst, its numerical value is respectively the natural number in 0～100, and x+y=100 or x+y+z=100.
A kind of preparation method of fuel battery metal catalyst of the present invention prepares stable noble metal catalyst particle colloid earlier, it is loaded on the conductivity ceramics boron carbide then, and concrete preparation process is as follows:
Step 1, the presoma salt of the metal of described catalyst is dissolved in deionized water or alcohol or the alcohol solution, at N
2, He or Ar gas shiled fully stir down, keeps pH=9～13 of solution in the course of reaction, 130～160 ℃ of reflux 2～5 hours, prepares stable platinum or platinum alloy colloid;
Step 2, will be in deionized water or alcohol or alcohol solution scattered conductivity ceramics boron carbide join in the platinum or platinum alloy colloidal solution that step 1 makes, continue to stir 8～10 hours, promptly making with the conductivity ceramics boron carbide is the fuel battery metal catalyst of carrier; Prepare with the conductivity ceramics boron carbide is the fuel-cell catalyst 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.
The presoma salt of the metal of catalyst of the present invention is H
2PtCl
6, RuCl
3, PdCl
2, IrCl
3, Co (NO
3)
2In more than one.
The fuel battery metal catalyst of preparation is assembled into monocell, carries out electric performance test:
1, the preparation of fuel cell chip CCM (catalyst coated membrane): with the catalyst adding deionized water of preparation and the full sulfonate resin solution of mass concentration 5%, abundant ultrasonic dispersion is stirred, and the furnishing pasty state is removed the slip bubble under the vacuum.Evenly be coated on then on the poly tetrafluoroethylene, the control coating thickness is 120 microns, dries 3～8 hours naturally under the room temperature, is needed on Nafion@ series membranes (NRE212 or the NRE211 etc.) both sides of DU PONT company then under hot pressing condition, makes CCM.
2, monocell assembling and test: the carbon paper that adopts the polytetrafluoroethylene hydrophobic treatment is as gas diffusion layers, described gas diffusion layers polytetrafluoroethylene content is 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/ excess air factor is 1.5/2.5 (wherein "/" represents the ratio of excess coefficient, down together), and the air back pressure is 0; Anode and cathode humidification, humidification degree are 0～100%; The monocell working temperature is 60～80 ℃, and the humidification temperature is 60～75 ℃.
(2) direct 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.
(3) directly the concentration of aminic acid fuel battery (DFAFC) anode formic acid 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) catalyst possesses excellent conducting performance, high chemical stability and high electrochemical stability;
(2) the various spaces of boron carbide ceramics smooth surface are less, can improve the utilance of noble metal granule.
(3) catalyst has higher anti-carbon monoxide poisoning capability.
(4) catalyst has higher methyl alcohol formic acid oxidation ability.
(4) owing to do not need to add other high molecular polymers in the preparation process, the catalyst building-up process is simple, can carry out large-scale mass production.
Description of drawings:
Fig. 1 is prepared Pt/B
4The transmission electron microscope picture of C catalyst (TEM).
Fig. 2 is prepared Pt/B
4The monocell polarization curve of C catalyst.
Fig. 3 is prepared Pt/B
4C catalyst and traditional commerce Pt/C catalyst anti-carbon monoxide poisoning performance are relatively.
Fig. 4 is prepared Pt
50Ru
50/ B
4C catalyst and conventional carbon carrier catalyst Pt
50Ru
50/ C is at 400mA/cm
2Following battery performance comparison diagram.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
H with 1.4 mg/ml of 150 milliliters pure ethylene glycol solutions and 50 milliliters
2PtCl
66H
2The solution of O mixes, at N
2Protection is fully stirred down and is formed even mixed solution; the sodium hydroxide solution that dropwise splashes into 2 mol then transfers to 9～13 with the pH value of mixed solution; oil bath is heated to 130～160 ℃ to mixed solution afterwards; condensing reflux 2～5 hours; solution colour becomes dark brownly by light yellow gradually, makes stable Pt colloid.The average grain diameter that takes by weighing 280 milligrams is the boron carbide powder of 50 nanometers, joins in 100 milliliters the ethylene glycol solution ultrasonic dispersion 30～60 minutes, then it is joined in the Pt colloidal solution of aforementioned stable, stirs 8～10 hours.After filtration, the alcohol solution washing makes Pt/B
4The C catalyst.Compare active area with carbon carrier catalyst Pt/C and improve 30%, the carbon monoxide oxidizing potential reduces by 0.05 volt, and the oxidation current peak value improves 25%.
The preparation of fuel cell chip CCM: with the catalyst adding deionized water of preparation and the full sulfonate resin solution of mass concentration 5%, abundant ultrasonic dispersion is stirred, and furnishing pasty state slip is removed the slip bubble under the vacuum.Then described slip evenly is coated on the poly tetrafluoroethylene surface, the control coating thickness is 120 microns, naturally dried 3～8 hours under the room temperature, under hot pressing condition, be needed on Nafion@ series membranes (NRE212 or the NRE211 etc.) both sides of DU PONT company then, make CCM.
Monocell assembling and test: the carbon paper that adopts the polytetrafluoroethylene hydrophobic treatment is as gas diffusion layers, described gas diffusion layers polytetrafluoroethylene content is 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: H
2/ excess air factor is 1.5/2.5, and the air back pressure is 0; Anode and cathode humidification, humidification degree are 100%; The monocell working temperature is 65 ℃, and the humidification temperature is 65 ℃.Test result shows that the electricity output of monocell reaches 0.671 volt milliampere/centimetre
2
Embodiment 2
The average grain diameter of getting 280 milligrams is the boron carbide powder of 50 nanometers, is distributed to that ultrasonic dispersion was mixed with the boron carbide solution for later use in 30～60 minutes in 100 milliliters the ethylene glycol solution, with the H of 1.4 mg/ml of 150 milliliters ethylene glycol solutions and 50 milliliters
2PtCl
66H
2The solution of O mixes, with above-mentioned boron carbide solution and H
2PtCl
66H
2The solution of O mixes, at N
2Protection is stirred down and was formed even mixed solution in 10～20 minutes; the NaOH solution that dropwise splashes into 2 mol then transfers to 9～13 with the pH value of mixed solution; oil bath is heated to 130～160 ℃ to mixed solution afterwards, and condensing reflux 2～5 hours stops heating and continues to stir 8～10 hours.After filtration, the alcohol solution washing makes Pt/B
4The C catalyst.Compare active area with conventional carbon carrier Pt/C catalyst and improve 21%, the carbon monoxide oxidizing potential reduces by 0.03 volt, and the oxidation current peak value improves 15%.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 0.683 volt milliampere/centimetre
2
Embodiment 3
Take the PdCl of 1.4 mg/ml of concentrated hydrochloric acid configuration
250 milliliters of ethylene glycol with 150 milliliters of solution mix, at N
2Protection is stirred down and was formed even mixed solution in 10～20 minutes; the sodium hydroxide solution that dropwise splashes into 2 mol then transfers to 8～9 with the pH value of mixed solution; the boron carbide powder that to take by weighing 280 milligrams of average grain diameters be 50 nanometers; joined in 100 milliliters the ethylene glycol solution ultrasonic dispersion 30～60 minutes, with itself and PdCl
2Solution mixes, and refluxes 2～3 hours under 80～90 ℃ of conditions, stops heating and continues to stir 8～10 hours, after the filtration, with the alcohol solution washing, makes Pd/B
4The C catalyst.Compare active area with conventional carbon carrier Pd/C catalyst and improve 26%, the carbon monoxide oxidizing potential reduces by 0.043 volt, and the oxidation current peak value improves 17%.
The preparation of fuel cell chip CCM: the full sulfonate resin solution that the catalyst of preparation is added deionized water and mass concentration 5%, abundant ultrasonic dispersion is stirred, furnishing pasty state slip, remove the slip bubble under the vacuum, then slip evenly is coated on the poly tetrafluoroethylene, the control coating thickness is 120 microns, dries 3～8 hours naturally under the room temperature, under hot pressing condition, be needed on Nafion@ series membranes (NRE212 or the NRE211 etc.) both sides of DU PONT company then, make CCM.Anode uses the catalyst of the present invention's preparation, and the palladium carrying capacity is 0.8 milligram/centimetre
2, negative electrode uses Pt/C (carbon the carries platinum) catalyst of JM company, and the platinum carrying capacity is 0.4 milligram/centimetre
2
Monocell assembling and test: the carbon paper that adopts the polytetrafluoroethylene hydrophobic treatment is as gas diffusion layers, the polytetrafluoroethylene mass content is 20%～30% in the gas diffusion layers, 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: the concentration of anode formic acid 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 275 milliwatts/centimetre
2The @300 milliampere/centimetre
2
Embodiment 4
Get the H of 1.4 mg/ml
2PtCl
66H
250 milliliters of ethylene glycol with 150 milliliters of the solution of O mix, at N
2Protection is stirred down and was formed even mixed solution in 10～20 minutes, the sodium hydroxide solution that dropwise splashes into 2 mol then transfers to 9～13 with the pH value of mixed solution, oil bath is heated to 130～160 ℃ to mixed solution afterwards, condensing reflux 2～5 hours, solution colour becomes dark brownly by light yellow gradually, makes stable Pt colloid; Take the PdCl of 1.4 mg/ml of concentrated hydrochloric acid configuration
2Solution joins in the mixed solution for 50 milliliters, continues condensing reflux 1～2 hour, obtains the Pt colloidal solution that stable Pd modifies.The boron carbide powder that to take by weighing 280 milligrams of average grain diameters be 50 nanometers joined in 100 milliliters the ethylene glycol solution ultrasonic dispersion 30～60 minutes, then it was joined in the Pt colloidal solution that stable Pd modifies, and stirred 8～10 hours.After filtering, make Pd-Pt/B with the alcohol solution washing
4The C catalyst.Compare active area with conventional carbon carrier Pd-Pt/C catalyst and improve 29%, the carbon monoxide oxidizing potential reduces by 0.047 volt, and the oxidation current peak value improves 21%.
The preparation of fuel cell chip CCM: the full sulfonate resin solution that the catalyst of preparation is added deionization who and mass concentration 5%, abundant ultrasonic dispersion is stirred, furnishing pasty state slip, remove the slip bubble under the vacuum, then slip evenly is coated on the poly tetrafluoroethylene, the control coating thickness is 120 microns, dries 3～8 hours naturally under the room temperature, under hot pressing condition, be needed on Nafion@ series membranes (NRE212 or the NRE211 etc.) both sides of DU PONT company then, make CCM.Negative electrode uses the catalyst of the present invention's preparation, and the platinum carrying capacity is 0.4 milligram/centimetre
2, anode uses the Pt/C catalyst of JM company, and the platinum carrying capacity is 0.4 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 content is 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: 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 290 milliwatts/centimetre
2The @400 milliampere/centimetre
2
Embodiment 5
Get 100 milliliters of ethanol 50 ml deionized water and put into the there-necked flask stirring at normal temperature 5 minutes; The gold chloride of measuring 50 milliliter of 1.4 mg/ml adds in the above-mentioned pure water mixed solution, at N
2Protection is stirred down and was formed even mixed solution in 10～20 minutes, dropwise splashes into the NaBH of 2 mol then
4Solution (excessive), solution becomes redness fast, has formed Au colloidal solution; Get the H of 1.4 mg/ml
2PtCl
66H
2The solution of O joins for 50 milliliters and continues in the Au colloidal solution to stir 1～2 hour, forms the Au colloidal solution that stable Pt modifies.The average grain diameter that takes by weighing 280 milligrams is the boron carbide powder of 50 nanometers, joins in 100 milliliters the ethylene glycol solution ultrasonic dispersion 30～60 minutes, then it is joined in the stable PtAu colloidal solution, stirred 8～10 hours, after filtering, with the alcohol solution washing, make Pt-Au/B
4The C catalyst.Compare active area with conventional carbon carrier Pt-Au/C catalyst and improve 25%, the carbon monoxide oxidizing potential reduces by 0.04 volt, and the oxidation current peak value improves 20%.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 0.686 volt milliampere/centimetre
2
Embodiment 6
Get the H of 1.4 mg/ml
2PtCl
66H
2The RuCl of 50 milliliters of the solution of O, 1.4 mg/ml
350 milliliters of ethylene glycol solutions with 150 milliliters of solution mix, at N
2Protection is stirred down and was formed even mixed solution in 10～20 minutes, and the sodium hydroxide solution that dropwise splashes into 2 mol then is adjusted to 8 with the pH value of mixed solution, 100 ℃ of reflux 20 minutes, makes stable PtRu colloid.The boron carbide powder that to take by weighing 280 milligrams of average grain diameters be 50 nanometers, joined in 100 milliliters the ethylene glycol solution ultrasonic dispersion 30～60 minutes, then it is joined in the stable PtRu colloidal solution, the hydrogen peroxide that adds 2 gram 20wt% again, 20 ml concns are the hydrochloric acid solution of 1 mol, continue down to stir 6 hours at 0～10 ℃, after filtering, make Pt with the alcohol solution washing
50Ru
50/ B
4The C catalyst.With conventional carbon carrier Pt
50Ru
50/ C catalyst is compared active area and is improved 27%, and the carbon monoxide oxidizing potential reduces by 0.04 volt, and the oxidation current peak value improves 20%.
The preparation of fuel cell chip CCM: the full sulfonate resin solution that the catalyst of preparation is added deionization pasture and water and mass concentration 5%, abundant ultrasonic dispersion is stirred, furnishing pasty state slip, remove the slip bubble under the vacuum, then slip evenly is coated on the poly tetrafluoroethylene, the control coating thickness is 120 microns, dries 3～8 hours naturally under the room temperature, under hot pressing condition, be needed on Nafion@ series membranes (NRE212 or the NRE211 etc.) both sides of DU PONT company then, make CCM.Anode uses the catalyst of the present invention's preparation, 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 0.4 milligram/centimetre
2
Monocell assembling and test: the carbon paper that adopts the polytetrafluoroethylene hydrophobic treatment is as gas diffusion layers, the polytetrafluoroethylene mass content is 20%～30% in the gas diffusion layers, 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: 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 270 milliwatts/centimetre
2The @400 milliampere/centimetre
2
Embodiment 7
Get the H of 1.4 mg/ml
2PtCl
66H
2Co (the NO of 50 milliliters of the solution of O, 1.4 mg/ml
3)
250 milliliters of ethylene glycol solutions with 150 milliliters of solution mix, at N
2Protection is stirred down fully and is formed even mixed solution, and the sodium hydroxide solution that dropwise splashes into 2 mol then is adjusted to 10 with the pH value of mixed solution, 100 ℃ of reflux 40 minutes, makes stable PtCo colloid.Take by weighing 280 milligrams nano silicon carbide boron powder, joined in 100 milliliters the ethylene glycol solution ultrasonic dispersion 30～60 minutes, then it is joined in the stable PtCo colloidal solution, the hydrogen peroxide that adds 2 gram 20wt% again, 20 ml concns are the hydrochloric acid solution of 1 mol, continue down to stir 6 hours at 0～10 ℃, after filtering, make Pt with the alcohol solution washing
50Co
50/ B
4The C catalyst.With conventional carbon carrier Pt
50Co
50/ C catalyst the active area of comparing improves 23%, and the carbon monoxide oxidizing potential reduces by 0.038 volt, oxidation current peak value raising 15%.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 0.671 volt milliampere/centimetre
2
Embodiment 8
Get the H of 1.4 mg/ml
2PtCl
66H
2Co (the NO of 50 milliliters of the solution of O, 1.4 mg/ml
3)
225 milliliters of solution and get the IrCl of 1.4 mg/ml
325 milliliters of ethylene glycol solutions with 150 milliliters of solution mix, at N
2Protection is stirred down and was formed even mixed solution in 10～20 minutes, and the sodium hydroxide solution that dropwise splashes into 2 mol then is adjusted to 9 with the pH value of mixed solution, 100 ℃ of reflux 30 minutes, makes stable PtIrCo colloid.Take by weighing 280 milligrams nano silicon carbide boron powder, joined in 100 milliliters the ethylene glycol solution ultrasonic dispersion 30～60 minutes, then it is joined in the stable PtIrCo colloidal solution, the hydrogen peroxide that adds 2 gram 20wt% again, 20 ml concns are the hydrochloric acid solution of 1 mol, continue down to stir 6 hours at 0～10 ℃, after filtering, make Pt with the alcohol solution washing
50Ir
25Co
50/ B
4The C catalyst.With conventional carbon carrier Pt
50Ir
25Co
50/ C catalyst is compared active area and is improved 22%, and the carbon monoxide oxidizing potential reduces by 0.029 volt, and the oxidation current peak value improves 14%.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 0.692 volt milliampere/centimetre
2
Claims (3)
1. fuel battery metal catalyst, it is characterized in that: the carrier of described metallic catalyst is the conductivity ceramics boron carbide, and described conductivity ceramics boron carbide is a hexagonal structure, and particle diameter is 10～100 nanometers.
2. fuel battery metal catalyst as claimed in claim 1 is characterized in that: the metal of described metallic catalyst is precious metal simple substance or precious metal alloys, and described precious metal simple substance is any one among Pt, Ru, Pd, Rh, Ir, the Os; Described precious metal alloys are MxNy or MxNyOz, wherein 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 each metallic atom ratio in the catalyst, its numerical value is respectively the natural number in 0～100, and x+y=100 or x+y+z=100.
3. the described fuel battery metal Preparation of catalysts of claim 1 method is characterized in that preparation process is:
Step 1, the presoma salt of the metal of described catalyst is dissolved in deionized water or alcohol or the alcohol solution, at N
2, He or Ar gas shiled fully stir down, keeps pH=9～13 of solution in the course of reaction, 130～160 ℃ of reflux 2～5 hours, prepares stable platinum or platinum alloy colloid;
Step 2, will be in deionized water or alcohol or alcohol solution scattered conductivity ceramics boron carbide, join in the platinum or platinum alloy colloidal solution that step 1 makes, stirred 8～10 hours, promptly making with the conductivity ceramics boron carbide is the fuel battery metal catalyst of carrier;
Wherein, alcohol is 0.5～100: 1 with the mass ratio of water in the described alcohol solution, and described alcohol is any in methyl alcohol, ethanol, normal propyl alcohol and the isopropyl alcohol; The presoma salt of the metal of described catalyst is H
2PtCl
6, RuCl
3, PdCl
2, IrCl
3, Co (NO
3)
2In more than one.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022522A (en) * | 2012-12-07 | 2013-04-03 | 太原理工大学 | Ternary carbon loaded palladium tin platinum nanoparticle catalyst and preparation method thereof |
| CN103464189A (en) * | 2013-09-13 | 2013-12-25 | 哈尔滨工程大学 | Preparation method of H2O2 electroreduction catalytic material for nickel and cobaltosic oxide loaded on carbon-coated titanium carbide |
| CN107331873A (en) * | 2017-06-15 | 2017-11-07 | 燕山大学 | A kind of transition metal metaborate nanometer bifunctional catalyst and preparation method |
| CN107537517A (en) * | 2016-06-29 | 2018-01-05 | 北京大学 | A kind of alloy colloid and preparation method and application |
| CN107732261A (en) * | 2017-11-08 | 2018-02-23 | 天津工业大学 | A kind of boron carbide carried noble metal Oxygen Electrode Material for chargeable lithium-air battery |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022522A (en) * | 2012-12-07 | 2013-04-03 | 太原理工大学 | Ternary carbon loaded palladium tin platinum nanoparticle catalyst and preparation method thereof |
| CN103022522B (en) * | 2012-12-07 | 2015-01-28 | 太原理工大学 | Ternary carbon loaded palladium tin platinum nanoparticle catalyst and preparation method thereof |
| CN103464189A (en) * | 2013-09-13 | 2013-12-25 | 哈尔滨工程大学 | Preparation method of H2O2 electroreduction catalytic material for nickel and cobaltosic oxide loaded on carbon-coated titanium carbide |
| CN103464189B (en) * | 2013-09-13 | 2015-12-09 | 哈尔滨工程大学 | The H of the coated titanium carbide Supported Co of carbon and cobaltosic oxide 2o 2the preparation method of electroreduction catalysis material |
| CN107537517A (en) * | 2016-06-29 | 2018-01-05 | 北京大学 | A kind of alloy colloid and preparation method and application |
| CN107537517B (en) * | 2016-06-29 | 2020-06-02 | 北京大学 | Alloy colloid and preparation method and application thereof |
| CN107331873A (en) * | 2017-06-15 | 2017-11-07 | 燕山大学 | A kind of transition metal metaborate nanometer bifunctional catalyst and preparation method |
| CN107331873B (en) * | 2017-06-15 | 2019-07-26 | 燕山大学 | A kind of transition metal metaborate nanometer bifunctional catalyst and preparation method |
| CN107732261A (en) * | 2017-11-08 | 2018-02-23 | 天津工业大学 | A kind of boron carbide carried noble metal Oxygen Electrode Material for chargeable lithium-air battery |
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