CN103050714A - Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst - Google Patents
Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst Download PDFInfo
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Abstract
The invention relates to a nano carbon doped electrocatalyst for a fuel cell, and application of the nano carbon doped electrocatalyst. The electrocatalyst is prepared by adopting the steps of: complexing a nitrogen-containing and/or boron-containing organic precursor and a transition metal salt to form a composite; adding nano carbon as a carrier, and heating and reacting a mixture by adopting a microwave radiation method; and after the reaction is complete, filtering and drying, placing a product obtained after the reaction in an inert atmosphere and/or reducing atmosphere, and treating at a high temperature of 500-1500 DEG C to obtain the nano carbon doped electrocatalyst. The nano carbon doped electrocatalyst is very low in cost, high in activity and stability and excellent in anti-poisoning capacity.
Description
Technical field
The present invention relates to the fuel-cell catalyst field, specifically a kind of fuel cell base metal eelctro-catalyst and preparation and application.
Background technology
Fuel cell is a kind of chemical energy that will be stored in fuel and the oxidant directly changes into electric energy by electrode reaction electrochemical appliance.Because the advantages such as it has energy conversion efficiency height, environmental friendliness, noise is low, startup is fast, being considered to one of the cleaning of 21 century first-selection, efficient generation technology, is the new energy technology that is hopeful to provide in a large number electric power after wind-force, waterpower and solar energy.Greatly develop " energy shortage " and " environmental pollution " this two hang-up that fuel cell technology faces solving the present world, realize that energy variation is significant.Through effort for many years, fuel cell has successfully carried out demonstrating running in fields such as electric automobile, Household hot chp system, dispersion electric power station systems.But the problems such as cost is high, stability and poor durability have seriously hindered its industrialization process.
Eelctro-catalyst is one of critical material of PEMFC and DMFC, is one of key factor of the output performance, life-span and the cost that affect fuel cell.At present, the eelctro-catalyst that generally uses in fuel cell is that Pt is catalyst based.But because the Pt resource scarcity is expensive, cause holding at high price of eelctro-catalyst.In addition, catalyst based catalytic activity, stability and the anti-impurity NO of Pt
x, SO
xDeng and the ability that poisons of methyl alcohol still can not satisfy the practical requirement of fuel cell.Therefore, the novel non-noble metal catalyst that cheap, active and the stable and antitoxin voltinism of exploitation can be high is most important.
Be the low-cost eelctro-catalyst that exploitation has actual application prospect, the research institution of countries in the world and enterprise all drop into the research that substantial contribution carries out non-platinum catalyst, and obtain considerable progress.Yet, the combination property of existing non-platinum catalyst, especially the problem such as its low power density and long-time running poor stability causes these materials still can not satisfy the requirement of above-mentioned electrocatalyst for fuel cell.But because the advantage on its resource and the cost makes it still have good researching value.
In recent years, many results of study show carries out trace element (N, B, Se etc.) doping or modification in the materials such as semi-conducting material and carbon, changed physics, chemistry and the thermodynamic (al) character of material, thereby made it have excellent electro catalytic activity.Wherein the most noticeable result of study is: hydrogen reduction catalytic activity, stability and the selectivity of reporting on " science " magazine that the orthotropic N of mixing carbon nano-pipe array was listed in the alkaline medium in 2009 all are higher than business-like Pt/C catalyst.After this result delivers, caused namely widely and paid close attention to that the research of dopen Nano C catalyst has become one of research emphasis of present fuel cell electro-catalyst.Because doped nano material, especially the research that is used as fuel-cell catalyst of doping carbon material is in the stage at the early-stage, research report both domestic and external is also less, although this material has preferably hydrogen reduction under alkali condition active, it is catalyst based that the power density of the fuel cell that this type of catalyst is assembled still is lower than traditional Pt.
Chinese patent CN200880012148.X adopts and to contain nitro and contain amino aromatic and the slaine metal-containing polymer that pyrolysis forms under the inert atmosphere cell catalyst that acts as a fuel.This patent only limits to the nanocarbon catalyst that nitro contains amino aromatic preparation.The preparation method of CN200810020833.9 employing phosphorus-ordered mesoporous carbon complex and this compound are as the fuel-cell catalyst of carrier.The doping of P has improved the performance of mesoporous carbon, when such catalyst performance still well below the Pt/C catalyst.
Summary of the invention
The present invention is directed to the problems referred to above, a kind of novel non-noble metal eelctro-catalyst and application thereof are provided, by with after metal and the nitrogenous precursor complexing, form the compound of metal-carbon-hetero-atom presoma by the carry out microwave radiation heating reaction, and by high-temperature roasting, the Nano carbon catalyst of preparation Heteroatom doping.
For achieving the above object, the technical solution used in the present invention is as follows,
A kind of fuel cell dopen Nano carbon eelctro-catalyst, at first with nitrogenous and/or boron organic precursor and transition metal salt complexing formation compound, add again nano-sized carbon as carrier, adopt microwave heating method to mixture heating, reaction, after question response is complete, with its filtration, drying, and the product that will obtain after will reacting obtains dopen Nano carbon non-precious metal catalyst in inert atmosphere and/or lower 500 ℃～1500 ℃ lower high-temperature process of reducing atmosphere; The quality percentage composition of the transition metal in the catalyst (M) is 0.5～20%; The quality percentage composition of nitrogen wherein and/or boron is 0.5～15%; Nanometer Carbon Content wherein is 60-99%.
Its concrete preparation process is,
1) be added drop-wise to transition metal salt solution B nitrogenous and/or boron organic precursor solution A in, stirring 〉=0.5h mixes it, obtains solution C;
2) nano-sized carbon is added in the solution C, mix and obtain mixture D;
3) with mixture D under inert atmosphere, adopt microwave irradiation in 40 ℃ of-150 ℃ of reaction 〉=10s, stops 〉=10s, the process of reaction and stop carries out obtaining mixture E more than the secondary repeatedly; Microwave output power is 500-2000W;
4) will filter after one or two or more kinds the mixed liquor washing in mixture E water, ethanol, the isopropyl alcohol, solid matter vacuumize obtains pressed powder F;
5) processing at least pressed powder F under 500 ℃～1500 ℃ inert atmosphere and/or reducing atmosphere, 0.5h obtains pressed powder G.
Described nitrogenous organic precursor is one or two or more kinds in ethylenediamine, hexamethylene diamine, urea, thiocarbamide, melamine, polyacrylonitrile, pyrroles, the phthalocyanine dye; Described boracic organic precursor is one or two or more kinds in trichlorine borazine, boric acid, Boratex, iron borate and the phenyl boride.
Described nano-sized carbon is one or two or more kinds in carbon black, graphitic carbon, carbon nano-tube, carbosphere, ordered mesopore carbon, Graphene, carbon gel and the carbon fiber.
Described slaine is the soluble metallic salt of one or two or more kinds metallic element in IVB, VB, VIB, VIIB, VIII, IB and the IIB family;
But described soluble metallic salt is nitrate, sulfate, acetate, halide, the acetylacetonate of metal or encircles greatly one or two or more kinds cosolvency salt in complex compound porphyrin compound, the phthalein mountain valley with clumps of trees and bamboo compound;
Vacuumize is carried out under 50～120 ℃.
Described metallic element is one or two or more kinds among Fe, Co, Ni, Mo, Cu, Zn, Ir, V, Cr, Mn, Ti, the W.
Described inert atmosphere is one or two or more kinds in nitrogen, Ar gas, the He gas; Reducing atmosphere is ammonia or CH
3CN atmosphere.
Described solution A and solution B solvent for use are C
1～C
8Monohydric alcohol, C
2～C
8Dihydroxylic alcohols or C
3～C
8It is 0.01M-3M that one or more mixtures in the trihydroxy alcohol, their concentration are respectively concentration, 0.01-3M.
Wherein the mol ratio of metal and Nano carbon is 1 among the transition metal salt solution B: 100-1: 10; The mol ratio of nitrogen element and nano-sized carbon is 1 in the nitrogenous organic precursor solution A: 200-20: 100.
The pressed powder G that obtains also can adopt acid solution as washing, the part metals on the flush away catalyst.
Described eelctro-catalyst is as the cathod catalyst of fuel cell, and fuel cell comprises negative electrode, anode and the polymer dielectric film between negative electrode and anode, and wherein said negative electrode comprises one or two or more kinds in the described catalyst of claim 1 at least.
Aforesaid dopen Nano C catalyst is used for assembling fuel cell.
Fuel cell according to embodiment of the present invention comprises negative electrode, anode, reaches the dielectric film between negative electrode and anode, and wherein negative electrode comprises a kind of aforesaid dopen Nano C catalyst.Described fuel cell is polymer dielectric film fuel cell (can be Proton Exchange Membrane Fuel Cells (PEMFC) or direct methanol fuel cell (DMFC)).
Compare with existing Catalysts and its preparation method, the present invention has following advantage:
1. the present invention modifies, mixes nano-sized carbon, the compound Nano carbon catalyst of preparation metal-carbon-nitrogen after forming polymer by metal and nitrogenous precursor.The adding of metal has changed microstructure and the edge surface defective of nano-sized carbon; Interaction between hetero-atom and metal and the carbon has improved the active and stable of catalyst;
2. this catalyst preparation process adopts carry out microwave radiation heating, and speed is fast, after the reaction on carrier being evenly distributed of each component, catalyst grain size is little.Compare with other preparation methods that similar catalyst preparation is adopted, preparation technology is simple, flow process is few, easy to operate, environmental friendliness, preparation cost is low and be easy to form the mass production scale;
3. compare with non-precious metal catalyst with traditional Pt/C catalyst, cheap, the aboundresources of base metal of the present invention, nitrogen and charcoal, preparation process is simple, thereby makes the total cost of catalyst very low.Described above-mentioned catalyst shows good catalytic activity and stability when the fuel-cell catalyst, thereby is hopeful to substitute platinum and becomes electrocatalyst for cathode in the polymer dielectric film fuel cell;
4. this catalyst has very high antitoxin voltinism energy.This catalyst is to foreign gas NO
x, SO
xAnd the absorption such as methyl alcohol is more weak, thereby has very high anti-poisoning ability.
Description of drawings
Fig. 1 is the polarization curves of oxygen reduction of the catalyst of embodiment 1 and embodiment 2 preparations;
Electrolyte solution: 0.5M H
2SO
4, sweep speed is: 5mV s
-1Reference electrode: saturated calomel electrode, to electrode: platinum filament; Rotating speed: 1600rpm; Voltage scan range:
Fig. 2 is the cyclic voltammetry curve of the catalyst of embodiment 1 and embodiment 2 preparations;
Electrolyte solution: 0.5M H
2SO
4, sweep speed is: 50mV s
-1Reference electrode: saturated calomel electrode, to electrode: platinum filament;
Fig. 3 is the polarization curves of oxygen reduction of the life test front and back of embodiment 1 employed catalyst;
Electrolyte solution: 0.5M H
2SO
4, sweep speed is: 5mV s
-1Reference electrode: saturated calomel electrode, to electrode: platinum filament;
Fig. 4 is the polarization curves of oxygen reduction of the life test front and back of Comparative Examples 1 employed catalyst.
Electrolyte solution: 0.5M H
2SO
4, sweep speed is: 5mV s
-1Reference electrode: saturated calomel electrode, to electrode: platinum filament.
Embodiment
Aforesaid loaded catalyst is used for negative electrode.Described fuel cell can be polymer dielectric film fuel cell (Proton Exchange Membrane Fuel Cells (PEMFC) or direct methanol fuel cell (DMFC)).
For example, described fuel cell is PEMFC.
Hereinafter, with reference to following examples one or more execution mode of the present invention is described in detail.Yet these embodiment not only limit purpose and the scope of one or more execution mode of the present invention.
Hereinafter, will the preparation method according to the dopen Nano C catalyst of embodiment of the present invention be described in detail.
Embodiment 1
Non-precious metal catalyst with Co metal and nitrogen doping.Get 0.13g Co (NO
3)
2.6H
2O is dissolved in the 10ml ethanol, and ultrasonic mixing obtains solution A; To contain the organic precursor hexamethylene diamine that 2.66ml contains N and be dissolved in the 20ml ethanol, ultrasonic mixing obtains solution B; Under constantly stirring, B is dropwise splashed among the A, the A the color of the solution becomes lilac by aubergine, and gradually becomes blue, becomes at last khaki and obtains C; Then with its sealing, after continuing to stir 2h, the XC-72 carbon dust is added among the said mixture C, after ultrasonic the mixing, continue stirring 1h, is that microwave in the 700W microwave reactor stopped 10s in 10 seconds in power output then, repeat microwave and stop process three times, obtain mixture D; With slurry D 60 ℃ of evaporates to dryness in water-bath; 85 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 700 ℃ of lower processing 2 hours in nitrogen atmosphere.
Embodiment 2
Get 0.0694g Co (NO
3)
2Be dissolved in the 10ml alcohol solvent, ultrasonic mixing obtains solution A; The N organic precursor hexamethylene diamine that will contain 0.00143mol is dissolved in the 20ml ethanol, and ultrasonic mixing obtains solution B; Under constantly stirring, B dropwise splashed into obtain C among the A; Then with its sealing, after continuing to stir 2h, the XC-72 carbon dust is added among the said mixture C, after ultrasonic the mixing, continue to stir 1h, be that microwave in the 700W microwave reactor stopped 10s in 10 seconds in power output then, triplicate obtains mixture D; With slurry D 60 ℃ of evaporates to dryness in water-bath; 85 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 700 ℃ of lower processing 2 hours in nitrogen atmosphere.
Embodiment 3
Get 0.402g Fe (NO
3)
3.6H
2O is dissolved in the alcohol solvent, and ultrasonic mixing obtains solution A; The N organic precursor hexamethylene diamine that will contain 0.00357mol is dissolved in the 30ml isopropyl alcohol, and ultrasonic mixing obtains solution B; Under constantly stirring, B is dropwise splashed among the A, obtain C; Then with its sealing, after continuing to stir 2h, 0.39g XC-72 carbon dust is added among the said mixture C, after ultrasonic the mixing, continue to stir 1h, be that microwave in the 700W microwave reactor stopped 10s in 10 seconds in power output then, triplicate obtains mixture D; With slurry D 60 ℃ of evaporates to dryness in water-bath; 85 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 900 ℃ of lower processing 2 hours in nitrogen atmosphere.
Embodiment 4
The auxiliary liquid-phase reduction method preparation of supported catalyst
Get 0.13g Co (NO
3)
2Fe (NO with 0.1804g
3)
3.6H
2O is dissolved in 50ml ethanol and the isopropanol solvent (volume ratio is 3: 2), and ultrasonic mixing obtains solution A; The N organic precursor hexamethylene diamine that will contain 0.00357mol is dissolved in the 5ml ethanol, and ultrasonic mixing obtains solution B; Under constantly stirring, B dropwise splashed into obtain C among the A; Then with its sealing, after continuing to stir 2h, 0.39g XC-72 carbon dust is added among the said mixture C, after ultrasonic the mixing, continue to stir 1h, be that microwave in the 700W microwave reactor stopped 10s in 10 seconds in power output then, triplicate obtains mixture D; With slurry D 60 ℃ of evaporates to dryness in water-bath; 85 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 800 ℃ of lower processing 2 hours in nitrogen atmosphere.
Embodiment 5
Get 0.13g Co (NO
3)
2Fe (NO with 0.1804g
3)
3.6H
2O is dissolved in the 30ml alcohol solvent, and ultrasonic mixing obtains solution A; The N organic precursor hexamethylene diamine that will contain 0.00357mol is dissolved in the ethanol, and ultrasonic mixing obtains solution B; Under constantly stirring, B dropwise splashed into obtain C among the A; Then with its sealing, after continuing to stir 2h, 0.39g XC-72 carbon dust is added among the said mixture C, after ultrasonic the mixing, continue to stir 1h, be that microwave in the 1000W microwave reactor stopped 10s in 10 seconds in power output then, triplicate obtains mixture D; With slurry D 80 ℃ of evaporates to dryness in water-bath; 60～100 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 850 ℃ of lower processing 2 hours in nitrogen atmosphere.
Embodiment 6
Get 0.13g Co (NO
3)
2.6H
2Fe (the NO of O and 0.1804g
3)
3.6H
2O is dissolved in the 20ml alcohol solvent, and ultrasonic mixing obtains solution A; The N organic precursor urea that will contain 0.00357mol is dissolved in the 10ml isopropyl alcohol, and ultrasonic mixing obtains solution B; Under constantly stirring, B dropwise splashed into obtain C among the A; Then with its sealing, after continuing to stir 2h, 0.39g XC-72 carbon dust is added among the said mixture C, after ultrasonic the mixing, continue to stir 3h, be that microwave in the 700W microwave reactor stopped 40s in 20 seconds in power output then, triplicate obtains mixture D; With slurry D 60 ℃ of evaporates to dryness in water-bath; 60～100 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 950 ℃ of lower processing 4 hours in nitrogen atmosphere.
Embodiment 7
Get 0.0105g Co (NO
3)
2.6H
2O is dissolved in the 20ml ethanol, and ultrasonic mixing obtains solution A; The N organic precursor dimethyl formamide that will contain 0.00357mol is dissolved in the 20ml ethanol, and ultrasonic mixing obtains solution B; Under constantly stirring, B is dropwise splashed among the A, the A the color of the solution becomes lilac by aubergine, and gradually becomes blue, becomes at last khaki and obtains C; Then with its sealing, after continuing to stir 2h, 0.39g XC-72 carbon dust is added among the said mixture C, after ultrasonic the mixing, continue to stir 1h, be that microwave in the 700W microwave reactor stopped 10s in 10 seconds in power output then, triplicate obtains mixture D; With slurry D 60 ℃ of evaporates to dryness in water-bath; 85 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 1000 ℃ of lower processing 3 hours in nitrogen atmosphere.
Embodiment 8
Get 0.0105g Co (NO
3)
2.6H
2O is dissolved in the 30ml alcohol solvent, and ultrasonic mixing obtains solution A; The N organic precursor nitroaniline that will contain 0.00357mol is dissolved in the 30ml ethanol, and ultrasonic mixing obtains solution B; Under constantly stirring, B is dropwise splashed among the A, obtain C; Then with its sealing, after continuing to stir 2h, the 0.39g carbon nano-tube is added among the said mixture C, after ultrasonic the mixing, continue to stir 1h, be that microwave in the 700W microwave reactor stopped 10s in 10 seconds in power output then, triplicate obtains mixture D; With slurry D 60 ℃ of evaporates to dryness in water-bath; 80 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 700 ℃ of lower processing 2 hours in nitrogen atmosphere.
Embodiment 9
Get 0.0105g Co (NO
3)
2.6H
2O is dissolved in the alcohol solvent, and ultrasonic mixing obtains solution A; To contain in the N organic precursor dimethyl formamide of 0.00357mol, ultrasonic mixing obtains solution B; Under constantly stirring, B dropwise splashed into obtain C among the A; Then with its sealing, after continuing to stir 2h, the 0.39g carbon nano-fiber is added among the said mixture C, after ultrasonic the mixing, continue to stir 1h, be that microwave in the 700W microwave reactor stopped 10s in 10 seconds in power output then, triplicate obtains mixture D; With slurry D 60 ℃ of evaporates to dryness in water-bath; 80 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 700 ℃ of lower processing 2 hours in nitrogen atmosphere.
Embodiment 10
Get being dissolved in the 20ml alcohol solvent of 0.20g ferric acetate, ultrasonic mixing obtains solution A; The N organic precursor melamine that will contain 0.00357mol is dissolved in the water, and ultrasonic mixing obtains solution B; Under constantly stirring, B is dropwise splashed among the A, obtain C; Then with its sealing, after continuing to stir 2h, 0.39g XC-72 carbon dust is added among the said mixture C, after ultrasonic the mixing, continue to stir 1h, be that microwave in the 700W microwave reactor stopped 10s in 10 seconds in power output then, triplicate obtains mixture D; With slurry D 60 ℃ of evaporates to dryness in water-bath; 85 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 900 ℃ of lower processing 2 hours in nitrogen atmosphere.
Embodiment 11
Get being dissolved in the 30ml alcohol solvent of 0.20g nickel acetate, ultrasonic mixing obtains solution A; The N organic precursor polyacrylonitrile that will contain 0.00357mol is dissolved in the dimethyl formamide (NMP) of 20ml, and ultrasonic mixing obtains solution B; Under constantly stirring, B is dropwise splashed among the A, obtain C; Then with its sealing, after continuing to stir 2h, the 0.32g carbon aerogels is added among the said mixture C, after ultrasonic the mixing, continue to stir 1h, be that microwave in the 700W microwave reactor stopped 10s in 30 seconds in power output then, triplicate obtains mixture D; With slurry D 60 ℃ of evaporates to dryness in water-bath; 85 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 800 ℃ of lower processing 2 hours in nitrogen atmosphere.
Embodiment 12
Get in the ethanol that is dissolved in 30ml and water mixed solvent (ratio is 1: 3) of 0.0105g ammonium molybdate, ultrasonic mixing obtains solution A; The N organic precursor thiocarbamide that will contain 0.00357mol is dissolved in the 10ml ethanol, and ultrasonic mixing obtains solution B; Under constantly stirring, B is dropwise splashed among the A, obtain C; Then with its sealing, after continuing to stir 2h, the 0.32g carbon aerogels is added among the said mixture C, after ultrasonic the mixing, continue to stir 1h, be that microwave in the 700W microwave reactor stopped 10s in 20 seconds in power output then, triplicate obtains mixture D; With slurry D 60 ℃ of evaporates to dryness in water-bath; 85 ℃ of lower vacuumizes, obtain pressed powder E; With pressed powder E 1000 ℃ of lower processing 3 hours in nitrogen atmosphere.
Comparative Examples 1
Adopt the 20%Pt/C of Johnson-Matthey production as a comparison, the stability of Study of Catalyst.
Application examples 1
Electrode preparation and ORR activity rating
1) electrode preparation
To mix with preparation rotating disk electrode (r.d.e) (RDE) according to nanocarbon catalyst, Nafion (5%) and an amount of solvent (ethanol) of embodiment 1 preparation and form slurry.Nafion is 50 μ l.RDE is formed slurry be coated on the glassy carbon electrode as the RDE substrate, then temperature is being carried out dry run to it when room temperature rises to 30 ℃ gradually, thus preparation RDE.Use RDE as work electrode with evaluate catalysts as described below.
2) ORR activity rating
Estimate as follows the ORR activity: oxygen is dissolved in the electrolyte until electrolyte is saturated, then measuring electric current (sweep speed: 5mV/s, electrode rotary speed: 400rpm) from open circuit voltage (OCV) with the method for negative sense (negative direction) scanning.
3) life assessment
Adopt electrochemical method that eelctro-catalyst is carried out cyclic voltammetry scan from 0-1.05V, the employing accelerated aging test (
AAT) ORR before and after the Study of Catalyst scanning is active.Hydrogen reduction catalytic activity before and after the catalyst test is compared, study its life-span.
Application examples 2-12: electrode preparation and ORR activity rating
Except using the catalyst of catalyst replacement according to preparation example 1 preparation according to preparation example 2-12 preparation, other experiment conditions are identical with application examples 1.
Fig. 1 is the former polarization curve of dopen Nano C catalyst oxidation of embodiment 1 and 2 preparations.
As can be seen from Figure 1, two kinds of catalyst have preferably catalytic activity.Along with the raising of tenor in the catalyst kind, the performance of catalyst improves.
Fig. 2 is the dopen Nano C catalyst scan round curve for embodiment 1 and 2 preparations.From figure can, along with the reduction of tenor in the catalyst, the electric current of catalyst diminishes, active area diminishes, thereby causes performance to reduce.
Fig. 3 and Fig. 4 are respectively the former polarization curve of oxidation of the catalyst life test front and back of embodiment 1 and Comparative Examples 1.
Can find out that from Fig. 3 and 4 catalyst of embodiment 1 preparation has the better stability than Pt/C under this test condition.
Should be understood that illustrative embodiments described herein should be thought only is illustrative and is not used in the restriction purpose.The description of feature or aspect usually should be thought and can be used for other similar characteristics or aspect in other execution mode in each execution mode.
Claims (10)
1. a fuel cell is with dopen Nano carbon eelctro-catalyst, it is characterized in that: by nitrogenous and/or boron organic precursor and transition metal salt complexing are formed compound, add again nano-sized carbon as carrier, adopt microwave heating method to mixture heating, reaction, after question response is complete, with its filtration, drying, and the product that will obtain after will reacting obtains dopen Nano carbon eelctro-catalyst 500 ℃～1500 ℃ high-temperature process under inert atmosphere and/or reducing atmosphere;
Wherein the transition metal quality percentage composition in the catalyst is 0.5～20%; The quality percentage composition of nitrogen and/or boron is 0.5～15%; The nanometer Carbon Content is 60-99%.
2. according to eelctro-catalyst claimed in claim 1, it is characterized in that: its preparation process is as follows,
1) be added drop-wise to transition metal salt solution B nitrogenous and/or boron organic precursor solution A in, stirring 〉=0.5h mixes it, obtains solution C;
2) nano-sized carbon is added in the solution C, mix and obtain mixture D;
3) with mixture D under inert atmosphere, adopt microwave irradiation in 40 ℃ of-150 ℃ of reaction 〉=10s, stops 〉=10s, the process of reaction and stop carries out obtaining mixture E more than the secondary repeatedly;
4) will filter after one or two or more kinds the mixed liquor washing in mixture E water, ethanol, the isopropyl alcohol, solid matter vacuumize obtains pressed powder F;
5) processing at least pressed powder F under 500 ℃～1500 ℃ inert atmosphere and/or reducing atmosphere, 0.5h obtains pressed powder G.
3. according to claim 1 or 2 described eelctro-catalysts, it is characterized in that: described nitrogenous organic precursor is one or two or more kinds in ethylenediamine, hexamethylene diamine, urea, thiocarbamide, melamine, polyacrylonitrile, pyrroles, the phthalocyanine dye; Described boracic organic precursor is one or two or more kinds in trichlorine borazine, boric acid, Boratex, iron borate and the phenyl boride;
Described nano-sized carbon is one or two or more kinds in carbon black, graphitic carbon, carbon nano-tube, carbosphere, ordered mesopore carbon, Graphene, carbon gel and the carbon fiber.
4. according to claim 1 or 2 described eelctro-catalysts, it is characterized in that: described slaine is the soluble metallic salt of one or two or more kinds metallic element in IVB, VB, VIB, VIIB, VIII, IB and the IIB family;
But described soluble metallic salt is nitrate, sulfate, acetate, halide, the acetylacetonate of metal or encircles greatly one or two or more kinds cosolvency salt in complex compound porphyrin compound, the phthalein mountain valley with clumps of trees and bamboo compound.
5. according to the described eelctro-catalyst of claim 4, it is characterized in that:
Described metallic element is one or two or more kinds among Fe, Co, Ni, Mo, Cu, Zn, Ir, V, Cr, Mn, Ti, the W.
6. according to claim 1 or 2 described eelctro-catalysts, it is characterized in that:
Described inert atmosphere is one or two or more kinds in nitrogen, Ar gas or the He gas; Reducing atmosphere is ammonia or CH
3CN atmosphere.
7. according to the described eelctro-catalyst of claim 2, it is characterized in that:
Described solution A and solution B solvent for use are C
1～C
8Monohydric alcohol, C
2～C
8Dihydroxylic alcohols or C
3～C
8In the trihydroxy alcohol one or two or more kinds, concentration are 0.01M-3M.
8. according to the described eelctro-catalyst of claim 2, it is characterized in that:
The mol ratio of metal and nano-sized carbon is 1: 100～1: 10 among the described transition metal salt solution B; The mol ratio of nitrogen element and nano-sized carbon is 1: 200～1: 5 in the nitrogenous organic precursor solution A.
9. according to the described eelctro-catalyst of claim 2, it is characterized in that: described pressed powder G also can adopt the acid solution washing.
10. the application of arbitrary described eelctro-catalyst in fuel cell among the claim 1-9 is characterized in that:
Described eelctro-catalyst is as the cathod catalyst of fuel cell, and fuel cell comprises negative electrode, anode and the polymer dielectric film between negative electrode and anode, and wherein said negative electrode comprises one or two or more kinds in the described catalyst of claim 1 at least.
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