CN1140002C - Process for preparing electrode carrier catalyst of fuel battery - Google Patents
Process for preparing electrode carrier catalyst of fuel battery Download PDFInfo
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- CN1140002C CN1140002C CNB011296976A CN01129697A CN1140002C CN 1140002 C CN1140002 C CN 1140002C CN B011296976 A CNB011296976 A CN B011296976A CN 01129697 A CN01129697 A CN 01129697A CN 1140002 C CN1140002 C CN 1140002C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 239000000446 fuel Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title description 9
- 239000000243 solution Substances 0.000 claims abstract description 47
- 239000002253 acid Substances 0.000 claims abstract description 25
- 239000010426 asphalt Substances 0.000 claims abstract description 20
- 239000011280 coal tar Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003208 petroleum Substances 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 42
- 239000011324 bead Substances 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 9
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 3
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 136
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract description 2
- 239000008188 pellet Substances 0.000 abstract 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 abstract 1
- 235000019345 sodium thiosulphate Nutrition 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 25
- 238000007254 oxidation reaction Methods 0.000 description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- 239000006229 carbon black Substances 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 9
- 238000006056 electrooxidation reaction Methods 0.000 description 9
- 229920000557 Nafion® Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000010355 oscillation Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000001075 voltammogram Methods 0.000 description 8
- 238000005087 graphitization Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 4
- 229910021385 hard carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229910000929 Ru alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for preparing a supported catalyst used for a fuel battery. Firstly, carbon pellets as an intermediate phase of carbonized or graphited petroleum asphalt or coal tar asphalt are used as carriers and are activated by air or alkali. Secondly, the activated carbon pellets are added into chloroplatinic acid solution or mixed solution of chloroplatinic acid and ruthenium chloride, and sodium thiosulfate solution with equivalent weight to chloroplatinic acid is slowly dripped, or hydrogen peroxide solution with equivalent weight to ruthenium chloride is slowly dripped. Finally, the solution is filtered, and precipitates are washed by deionized water and then are heated to obtain the electrode supported catalyst. The catalyst prepared by the method of the present invention has high methanol catalytic activity.
Description
Invention field the present invention relates to a kind of preparation method of electrode carrier catalyst of fuel battery, belongs to the fuel cell technology field.
Background technology is in Proton Exchange Membrane Fuel Cells and direct methanol fuel cell, the battery electrode catalyst is the critical material in the battery, the performance of catalyst will directly influence the performance of battery, and therefore, electrode catalyst is the emphasis problem of fuel cell research and development always.At present, widely used catalyst is the carried catalyst that carbon carries other alloys such as platinum or platinum ruthenium in fuel cell, in Preparation of catalysts, the carrier of selecting catalyst is crucial, different carriers will directly influence the performance of catalyst, the widely used carrier of people mainly is a carbon black material, as Vulcan-VC72 carbon black (production of Cabot company), acetylene black and other carbon black, when making carried catalyst, carbon black is not done any processing, after the Pt colloid forms, promptly add the particle of carbon black absorption Pt, and form carried catalyst.
Former study shows, utilize act as a fuel catalyst carrier in the battery of carbon black, the difficulty that exists is that carbon black is easily reunited, the result who reunites will make the noble metal catalyst that is loaded on the carbon black be wrapped up by carbon black and can not participate in electrode reaction, thereby reduced the catalytic efficiency of catalyst, carbon black is a kind of soft carbon in addition, fuel cell electrode must be the diffusion electrode of porous, and when virtual electrode is made, must be pressed into high pressure,, often add blowing agent to increase the porosity of catalyst layer although when making electrode, but high pressure must cause the porosity in the electrode to descend, thereby the material diffusion transport in the electrode is obstructed, if therefore use the carrier of hard carbon, even under high pressure as catalyst, can not cause the porosity to descend yet, thereby guarantee that the porosity and reactant on the electrode spread smoothly.
Summary of the invention the objective of the invention is to propose a kind of preparation method of electrode carrier catalyst of fuel battery, use the act as a fuel catalyst carrier of battery of hard carbon, when using hard carbon as carrier, hard carbon also must possess good profile, macroscopical pore is less relatively simultaneously, improves the utilance of catalyst.
The fuel cell that the present invention the proposes preparation method of carried catalyst comprises following each step:
1, select through carbonization or through the mesocarbon bead of graphited petroleum asphalt or coal tar asphalt as carrier, the diameter of bead at 5 microns to 30 micrometer ranges;
2, pitch mesocarbon bead is placed crucible, under 400 ℃-800 ℃ air atmosphere roasting 0.5-2 hour; Or be that NaOH or the KOH solution of 1M-10M mixes with pitch mesocarbon bead and concentration, NaOH in pitch mesocarbon bead quality and the solution or the mass ratio of KOH are 1: 0.1-2, and boiled 1 hour to 3 hours, last water cleans to neutral;
3, the pitch mesocarbon bead of activated processing utilizes different loading process that different catalysts (as platinum, platinum-ruthenium alloys etc.) is loaded;
First method wherein is:
At the mass volume concentrations is the pitch mesocarbon bead that adds in the platinum acid chloride solution of 1g/L-30g/L through above-mentioned (2) step activation processing, and fully stir, the mass ratio of pitch mesocarbon bead and chloroplatinic acid is 1: 0.1-0.35, slowly drip hypo solution with the chloroplatinic acid equivalent, the mass volume concentrations scope of hypo solution is 10g/L-50g/L, and stirred 0.5-3 hour, filter and use washed with de-ionized water then; Products obtained therefrom was heated 1-3 hour down at 300-400 ℃, promptly get electrode carrier catalyst.
Second method is to be in the chloroplatinic acid of 1g/L-30g/L and the ruthenic chloride mixed solution that the mass volume concentrations is 1g/L-30g/L at the mass volume concentrations, slowly adding is the hypo solution of 10g/L-50g/L with the mass volume concentrations of chloroplatinic acid equivalent, and stirs 0.5-3 hour; After question response is finished, adding concentration is the sodium carbonate liquor of 0.1M-1M, the pH value of solution value is adjusted to 4-6, slowly dropping is the hydrogenperoxide steam generator of 35g/L with the concentration of chlorination nail equivalent, after question response is finished, adding is through the pitch mesocarbon bead of above-mentioned (2) step activation processing, the mass ratio of pitch mesocarbon bead and chloroplatinic acid is 1: 0.1-0.35, stirred 0.5-3 hour, filter cleaning-drying, products obtained therefrom was heated 1-3 hour under 300 ℃ of-400 ℃ of temperature, promptly get electrode carrier catalyst.
Utilize the catalyst of method of the present invention preparation, have very high methyl alcohol catalytic activity, compare, the electrochemical oxidation catalytic activity of methyl alcohol has been improved 2 to 5 times with the Vulcan VC-72 carbon black platinum catalyst of U.S. E-Tec company.
Description of drawings
Fig. 1 is the cyclic voltammetry curve of catalyst in 1N H2SO4+1M CH3OH solution among the embodiment one.
Embodiment
Embodiment one
Get the coal tar asphalt mesocarbon bead of 1.13g through graphitization processing, adding 80ml chloroplatinic acid mass volume concentrations is the platinum acid chloride solution of 5 grams per liters, fully stirs.The concentration that slowly splashes into again with the chloroplatinic acid equivalent is the hypo solution of 20 grams per liters, stirs 3 hours, filters and use washed with de-ionized water then, and heating is 3 hours under 300 ℃ of temperature.The heavy amount percentage concentration that gained catalyst 0.5 gram is joined 1 gram du pont company production in 5% the Nafion solution, is starched after 1 hour uniformly with supersonic oscillations, and slurry is coated in 1cm equably
2Graphite flake on, and the oven dry.The gained electrode is carried out the catalyst effect evaluation in the mixed solution of 1M sulfuric acid and 1M methyl alcohol.Accompanying drawing one is the scanning voltammogram that utilizes this catalyst methanol electrooxidation.As can be seen from the figure, this catalyst has obvious catalytic action to methanol oxidation, is the catalytic oxidation peak of methyl alcohol at the peak of 0.8V correspondence, and the peak current of every milligram of platinum catalysis methanol oxidation reaches 140mA.
Embodiment two
Will be through the heat treatment 2 hours in 600 ℃ of following air atmospheres of the coal tar asphalt mesocarbon bead of 2800 ℃ of graphitization processing.Get the coal tar asphalt mesocarbon bead of 1.13g activation processing, adding 80ml chloroplatinic acid mass volume concentrations is the platinum acid chloride solution of 5 grams per liters, fully stirs.The concentration that slowly splashes into again with the chloroplatinic acid equivalent is the hypo solution of 20 grams per liters, stirs 3 hours, filters and use washed with de-ionized water then, and heating is 3 hours under 300 ℃ of temperature.The concentration expressed in percentage by weight that gained catalyst 0.5 gram is joined 1 gram du pont company production in 5% the Nafion solution, is starched after 1 hour uniformly with supersonic oscillations, and slurry is coated in 1cm equably
2Graphite flake on, and the oven dry.The gained electrode is carried out the catalyst effect evaluation in the mixed solution of 1M sulfuric acid and 1M methyl alcohol.From the scanning voltammogram of this catalyst methanol electrooxidation as can be seen, this catalyst has obvious catalytic action to methanol oxidation, at the peak of 0.8V correspondence is the catalytic oxidation peak of methyl alcohol, and the peak current of every milligram of platinum catalysis methanol oxidation reaches 280mA.
Embodiment three
Will be through the heat treatment 2 hours in 750 ℃ of following air atmospheres of the coal tar asphalt mesocarbon bead of 2800 ℃ of graphitization processing.Get the coal tar asphalt mesocarbon bead of 1.13g activation processing, adding 80ml chloroplatinic acid mass volume concentrations is the platinum acid chloride solution of 5 grams per liters, fully stirs.The concentration that slowly splashes into again with the chloroplatinic acid equivalent is the hypo solution of 20 grams per liters, stirs 3 hours, filters and use washed with de-ionized water then, and heating is 3 hours under 300 ℃ of temperature.The concentration expressed in percentage by weight that gained catalyst 0.5 gram is joined 1 gram du pont company production in 5% the Nafion solution, is starched after 1 hour uniformly with supersonic oscillations, and slurry is coated in 1cm equably
2Graphite flake on, and the oven dry.The gained electrode is carried out the catalyst effect evaluation in the mixed solution of 1M sulfuric acid and 1M methyl alcohol.From the scanning voltammogram of this catalyst methanol electrooxidation as can be seen, this catalyst has obvious catalytic action to methanol oxidation, at the peak of 0.8V correspondence is the catalytic oxidation peak of methyl alcohol, and the peak current of every milligram of platinum catalysis methanol oxidation reaches 350mA.
Embodiment four
20 grams are stirred in the KOH of 100ml, 6M solution through the coal tar asphalt mesocarbon bead of 2800 ℃ of graphitization processing boiled 1 hour, use the deionized water cleaning, drying again.Get the coal tar asphalt mesocarbon bead of 1.13g activation processing, adding 80ml chloroplatinic acid mass volume concentrations is the platinum acid chloride solution of 5 grams per liters, fully stirs.The concentration that slowly splashes into equivalent again is the hypo solution of 20 grams per liters, stirs 3 hours, filters and use washed with de-ionized water then, and heating is 3 hours under 300 ℃ of temperature.The concentration expressed in percentage by weight that gained catalyst 0.5 gram is joined 1 gram du pont company production in 5% the Nafion solution, is starched after 1 hour uniformly with supersonic oscillations, and slurry is coated in 1cm equably
2Graphite flake on, and the oven dry.The gained electrode is carried out the catalyst effect evaluation in the mixed solution of 1M sulfuric acid and 1M methyl alcohol.From the scanning voltammogram of this catalyst methanol electrooxidation as can be seen, this catalyst has obvious catalytic action to methanol oxidation, at the peak of 0.8V correspondence is the catalytic oxidation peak of methyl alcohol, and the peak current of every milligram of platinum catalysis methanol oxidation reaches 1250mA.
Embodiment five
20 grams are stirred in the KOH of 100ml, 6M solution through the coal tar asphalt mesocarbon bead of 2800 ℃ of graphitization processing boiled 3 hours, use the deionized water cleaning, drying again.Get the coal tar asphalt mesocarbon bead of 1.13g activation processing, adding 50ml chloroplatinic acid mass volume concentrations is the platinum acid chloride solution of 5 grams per liters, fully stirs.The concentration that slowly splashes into equivalent again is the hypo solution of 20 grams per liters, stirs 3 hours, filters and use washed with de-ionized water then, and heating is 3 hours under 300 ℃ of temperature.The concentration expressed in percentage by weight that gained catalyst 0.5 gram is joined 1 gram du pont company production in 5% the Nafion solution, is starched after 1 hour uniformly with supersonic oscillations, and slurry is coated in 1cm equably
2Graphite flake on, and the oven dry.The gained electrode is carried out the catalyst effect evaluation in the mixed solution of 1M sulfuric acid and 1M methyl alcohol.From the scanning voltammogram of this catalyst methanol electrooxidation as can be seen, this catalyst has obvious catalytic action to methanol oxidation, at the peak of 0.8V correspondence is the catalytic oxidation peak of methyl alcohol, and the peak current of every milligram of platinum catalysis methanol oxidation reaches 1280mA.
Embodiment six
20 grams are added thermal agitation 1 hour through the coal tar asphalt mesocarbon bead of 2800 ℃ of graphitization processing in the NaOH of 100ml, 6M solution, use the deionized water cleaning, drying again.Get the coal tar asphalt mesocarbon bead of 1.13g activation processing, adding 80ml chloroplatinic acid mass volume concentrations is the platinum acid chloride solution of 3 grams per liters, fully stirs.The concentration that slowly splashes into equivalent again is the hypo solution of 20 grams per liters, stirs 3 hours, filters and use washed with de-ionized water then, and heating is 3 hours under 300 ℃ of temperature.The concentration expressed in percentage by weight that gained catalyst 0.5 gram is joined 1 gram du pont company production in 5% the Nafion solution, is starched after 1 hour uniformly with supersonic oscillations, and slurry is coated in 1cm equably
2Graphite flake on, and the oven dry.The gained electrode is carried out the catalyst effect evaluation in the mixed solution of 1M sulfuric acid and 1M methyl alcohol.From the scanning voltammogram of this catalyst methanol electrooxidation as can be seen, this catalyst has obvious catalytic action to methanol oxidation, at the peak of 0.8V correspondence is the catalytic oxidation peak of methyl alcohol, and the peak current of every milligram of platinum catalysis methanol oxidation reaches 820mA.
Embodiment seven
20 grams are added thermal agitation 1 hour through the coal tar asphalt mesocarbon bead of 2800 ℃ of graphitization processing in 100ml NaOH solution, use the deionized water cleaning, drying again.At the mass volume concentrations of chloroplatinic acid is that the mass volume concentrations of the chloroplatinic acid of 5g/L and ruthenic chloride is in the 50ml mixed solution of ruthenic chloride of 5g/L, and the mass volume concentrations that slowly adds with the chloroplatinic acid equivalent is the hypo solution of 20g/L for the solution concentration scope and stirred 3 hours; After question response is finished, adding concentration is the sodium carbonate liquor of 0.5M, the pH value of solution value is controlled at about 5, slowly dropping is the hydrogenperoxide steam generator of 35g/L with the concentration of ruthenic chloride equivalent, after question response is finished, add the activated pitch mesocarbon bead of having handled 1.13 grams, stirred 3 hours, and the filtration cleaning-drying.Products obtained therefrom was heated 3 hours at 300 ℃.The concentration expressed in percentage by weight that gained catalyst 0.5 gram is joined 1 gram du pont company production in 5% the Nafion solution, is starched after 1 hour uniformly with supersonic oscillations, and slurry is coated in 1cm equably
2Graphite flake on, and the oven dry.The gained electrode is carried out the catalyst effect evaluation in the mixed solution of 1M sulfuric acid and 1M methyl alcohol.From the scanning voltammogram of this catalyst methanol electrooxidation as can be seen, this catalyst has obvious catalytic action to methanol oxidation, at the peak of 0.8V correspondence is the catalytic oxidation peak of methyl alcohol, and the peak current of every milligram of platinum catalysis methanol oxidation reaches 1420mA.
Comparative example
As a comparison, utilize Vulcan XC-72 platinum catalyst,, catalyst 0.5g is joined with in the Nafion solution (5%wt) the comparison of its catalysis methanol electrochemistry oxidation performance, starched uniformly after 1 hour with supersonic oscillations, slurry is coated in 1cm equably
2Graphite flake on, and the oven dry.The gained electrode is carried out the catalyst effect evaluation in the mixed solution of 1M sulfuric acid and 1M methyl alcohol.From the scanning voltammogram of this catalyst methanol electrooxidation as can be seen, this catalyst has obvious catalytic action to methanol oxidation, at the peak of 0.8V correspondence is the catalytic oxidation peak of methyl alcohol, and the peak current of every milligram of platinum catalysis methanol oxidation reaches 220mA/cm
2
Claims (2)
1, a kind of fuel cell preparation method of carried catalyst is characterized in that this method comprises following each step:
(1) select through carbonization or through the mesocarbon bead of graphited petroleum asphalt or coal tar asphalt as carrier, the diameter of bead at 5 microns to 30 micrometer ranges;
(2) pitch mesocarbon bead is placed crucible, under 400 ℃-800 ℃ air atmosphere roasting 0.5-2 hour; Or be that NaOH or the KOH solution of 1M-10M mixes with pitch mesocarbon bead and concentration, NaOH in pitch mesocarbon bead quality and the solution or the mass ratio of KOH are 1: 0.1-2, and boiled 1 hour to 3 hours, last water cleans to neutral;
(3) be the pitch mesocarbon bead that adds in the platinum acid chloride solution of 1g/L-30g/L through above-mentioned (2) step activation processing at the mass volume concentrations, and fully stir, the mass ratio of pitch mesocarbon bead and chloroplatinic acid is 1: 0.1-0.35, slowly drip hypo solution with the chloroplatinic acid equivalent, the mass volume concentrations scope of hypo solution is 10g/L-50g/L, and stirred 0.5-3 hour, filter and use washed with de-ionized water then; Products obtained therefrom was heated 1-3 hour down at 300-400 ℃, promptly get electrode carrier catalyst.
2, a kind of fuel cell preparation method of carried catalyst is characterized in that this method comprises following each step:
(1) select through carbonization or through the mesocarbon bead of graphited petroleum asphalt or coal tar asphalt as carrier, the diameter of bead at 5 microns to 30 micrometer ranges;
(2) pitch mesocarbon bead is placed crucible, under 400 ℃-800 ℃ air atmosphere roasting 0.5-2 hour; Or be that NaOH or the KOH solution of 1M-10M mixes with pitch mesocarbon bead and concentration, NaOH in pitch mesocarbon bead quality and the solution or the mass ratio of KOH are 1: 0.1-2, and boiled 1 hour to 3 hours, last water cleans to neutral;
(3) be in the chloroplatinic acid of 1g/L-30g/L and the ruthenic chloride mixed solution that the mass volume concentrations is 1g/L-30g/L at the mass volume concentrations, slowly adding is in the hypo solution of 10g/L-50g/L with the mass volume concentrations of chloroplatinic acid equivalent, and stirs 0.5-3 hour; After question response is finished, adding concentration is the sodium carbonate liquor of 0.1M-1M, the pH value of solution value is adjusted to 4-6, slowly dropping is the hydrogenperoxide steam generator of 35g/L with the concentration of chlorination nail equivalent, after question response is finished, adding is through the pitch mesocarbon bead of above-mentioned (2) step activation processing, the mass ratio of pitch mesocarbon bead and chloroplatinic acid is 1: 0.1-0.35, stirred 0.5-3 hour, filter cleaning-drying, products obtained therefrom was heated 1-3 hour under 300 ℃ of-400 ℃ of temperature, promptly get electrode carrier catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011296976A CN1140002C (en) | 2001-06-29 | 2001-06-29 | Process for preparing electrode carrier catalyst of fuel battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011296976A CN1140002C (en) | 2001-06-29 | 2001-06-29 | Process for preparing electrode carrier catalyst of fuel battery |
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| CN1330423A CN1330423A (en) | 2002-01-09 |
| CN1140002C true CN1140002C (en) | 2004-02-25 |
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| CNB011296976A Expired - Fee Related CN1140002C (en) | 2001-06-29 | 2001-06-29 | Process for preparing electrode carrier catalyst of fuel battery |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2626131A1 (en) * | 2012-02-08 | 2013-08-14 | Studiengesellschaft Kohle mbH | Highly sinter-stable metal nanoparticles supported on mesoporous graphitic particles and their use |
| CN103007958A (en) * | 2012-11-23 | 2013-04-03 | 浙江工业大学 | Expanded graphite supported platinum-cobalt catalyst and application thereof |
| CN103121023A (en) * | 2013-01-28 | 2013-05-29 | 江苏国正新材料科技有限公司 | Washing method for electrical carbon material |
| CN103894169B (en) * | 2014-03-25 | 2016-08-17 | 北京宝塔三聚能源科技有限公司 | A kind of catalyst carrier, the preparation method of carrier and the Heavy oil hydrogenation catalyst prepared by this carrier |
| CN105514453B (en) * | 2016-01-11 | 2017-11-21 | 中国科学院过程工程研究所 | A kind of method that electrode is prepared using native graphite |
| CN114177858B (en) * | 2021-12-13 | 2023-06-16 | 清氢(北京)科技有限公司 | Electrocatalyst macro preparation method and macro preparation device |
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