CN115133051A - Ultralow platinum fuel cell catalyst and preparation method thereof - Google Patents
Ultralow platinum fuel cell catalyst and preparation method thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 84
- 239000000446 fuel Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011240 wet gel Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 230000006641 stabilisation Effects 0.000 claims abstract description 3
- 238000011105 stabilization Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 150000001868 cobalt Chemical class 0.000 claims description 15
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical group [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 claims description 13
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 10
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 9
- 239000000499 gel Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 11
- 238000004873 anchoring Methods 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 230000010802 Oxidation-Reduction Activity Effects 0.000 description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of an ultralow platinum fuel cell catalyst, belongs to the technical field of fuel cells, and solves the problems of overhigh cost, low platinum utilization rate and easy corrosion of carbon carriers of the existing fuel cell catalysts. The method comprises the following steps: s1, preparing a nitrogen-doped carbon carrier, namely dissolving melamine in a formaldehyde solution, adding sodium hydroxide to adjust the pH to 7-10, after a reaction is set for a set time, adding hydrochloric acid to adjust the pH to 2-3, drying after stabilization, replacing a solvent in dried wet gel with acetone, drying, grinding, mixing with carbon black, and performing heat treatment in a nitrogen environment to obtain the nitrogen-doped carbon carrier; s2, preparing the ultra-low platinum fuel cell catalyst, namely mixing chloroplatinic acid, the prepared nitrogen-doped carbon carrier and deionized water, drying and grinding to obtain powder, and calcining the powder at 100-400 ℃ in a hydrogen environment to obtain the ultra-low platinum fuel cell catalyst. The use of a nitrogen-containing carbon material facilitates the anchoring of platinum and can improve the dispersion of platinum in the catalyst.
Description
Technical Field
The invention relates to the technical field of fuel cell catalysts, in particular to an ultra-low platinum fuel cell catalyst and a preparation method thereof.
Background
At present, a fuel cell engine mainly adopts noble metal platinum (Pt) as an electrode catalytic material, such as a platinum-carbon catalyst, a platinum-based alloy catalyst, and the like, for reducing activation energy of an electrode reaction and accelerating the reaction.
However, due to the shortage of platinum resources and high price, and the inefficient use of platinum atoms in the existing fuel cell catalyst particles, a large amount of noble metal platinum is used, and the cost of the fuel cell engine is too high. In addition, the carbon carrier is easy to corrode, the binding force with catalyst particles is weak, platinum particles are easy to fall off and run off, and the activity of the platinum particles is greatly reduced.
Disclosure of Invention
In view of the foregoing analysis, an embodiment of the present invention aims to provide an ultra-low platinum fuel cell catalyst and a preparation method thereof, so as to solve the problems of the existing fuel cell catalyst, such as high cost, low platinum utilization rate, and easy corrosion of a carbon carrier.
In one aspect, an embodiment of the present invention provides a preparation method of an ultralow platinum fuel cell catalyst, including the following steps:
s1, preparing a nitrogen-doped carbon carrier, which comprises the steps of dissolving melamine in a formaldehyde solution under a heating condition, adding sodium hydroxide to adjust the pH to 7-10, reacting for a set time, adding hydrochloric acid to adjust the pH to 2-3, drying after stabilization, finally replacing a solvent in dried wet gel with acetone, drying, grinding, mixing with carbon black according to a set proportion, and performing heat treatment in a nitrogen environment to obtain the nitrogen-doped carbon carrier;
s2, preparing the ultra-low platinum fuel cell catalyst, which comprises the steps of mixing chloroplatinic acid, the prepared nitrogen-doped carbon carrier and deionized water, drying, grinding to obtain powder, and calcining the powder at 100-400 ℃ in a hydrogen environment to obtain the ultra-low platinum fuel cell catalyst.
The beneficial effects of the above technical scheme are as follows: the preparation method of the fuel cell catalyst is simple, low in cost, large in specific surface area, high in nitrogen content, high in catalytic activity and good in stability, and the cost of the fuel cell catalyst is effectively reduced. The method solves the technical problem which is urgently needed to be solved in the prior art. In order to reduce the cost of the fuel cell catalyst, the ultralow platinum fuel cell catalyst is prepared by adopting a non-noble metal material load and a small amount of platinum. The catalyst can improve the oxidation-reduction activity, and the stability and the corrosion resistance can be effectively improved because the catalyst is not easy to agglomerate, dissolve and the like.
Based on the further improvement of the method, in step S1, after the reaction is set for a set time, firstly adding cobalt salt and stirring, and then adding hydrochloric acid to adjust the pH value to 2-3, so that the prepared nitrogen-doped carbon carrier is a cobalt-nitrogen co-doped carbon carrier.
Further, in step S1, the cobalt salt includes at least one of cobalt chloride, cobalt nitrate, and cobalt sulfate.
Further, in step S1, the mass ratio of the nitrogen-doped carbon carrier to the deionized water is 5 to 10.
Further, in step S2, the mass ratio of platinum in the chloroplatinic acid to the nitrogen-doped carbon support is 9 to 19.
Further, the cobalt salt is cobalt chloride hexahydrate, and the mass of the cobalt salt is 0-1 g.
Further, in step S1, the mass of melamine is 3.2g, the volume of the formaldehyde solution is 7ml, the volume of the sodium hydroxide is 1mol/L aqueous solution, the volume of the hydrochloric acid is 1mol/L aqueous solution, and the mass of the cobalt chloride hexahydrate is 0.5 g; and the number of the first and second electrodes,
in step S2, the mass of the nitrogen-doped carbon support was 95mg, and the chloroplatinic acid was an aqueous solution having a volume of 1.34mL and a density of 20 g/L.
Further, the step S1 further includes:
s11, dissolving melamine in a formaldehyde solution under a heating condition;
s12, adding sodium hydroxide into the dissolved solution, and adjusting the pH value of the solution to 7-10;
s13, standing the solution, and reacting at the high temperature of 80 ℃ for 0.5h to generate a melamine formaldehyde gel prepolymer in the solution;
s14, magnetically stirring the solution, adding cobalt salt, and continuously stirring for 2 hours until the mixture is uniformly mixed;
s15, adding hydrochloric acid into the uniformly mixed solution to adjust the pH to 2-3, and reacting in an oven at 40-70 ℃ for 24 hours after the solution is stabilized for 0.5 hour to obtain wet gel;
s16, replacing the solvent in the wet gel with acetone, and drying and grinding;
s17, uniformly mixing the dried and ground powder and the carbon black according to the proportion of 3-7 under a ball milling condition;
and S18, carrying out high-temperature heat treatment on the mixed powder for 4 hours at 600-1000 ℃ by using a tubular furnace in a nitrogen environment to obtain the nitrogen-doped carbon carrier.
Further, the step S2 further includes:
s21, weighing a proper amount of chloroplatinic acid and nitrogen-doped carbon carrier;
s22, mixing the weighed chloroplatinic acid and nitrogen-doped carbon carrier with deionized water, drying in an oven, and grinding to obtain powder;
s23, calcining the powder in a hydrogen environment at the temperature of 100-400 ℃ to obtain the ultralow platinum fuel cell catalyst.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
1. the prepared ultra-low platinum fuel cell catalyst effectively reduces the consumption of platinum by combining the nitrogen-doped carbon material with the platinum-cobalt alloy and the interaction of the non-noble metal active sites and the platinum active sites.
2. The cobalt-nitrogen co-doped carbon material is used as a carrier, so that the number of active sites is increased, and the activity of the catalyst is improved.
3. And the cobalt-nitrogen co-doped carbon material is used as a carrier, so that the stability of the catalyst is improved.
4. The use of a nitrogen-containing carbon material facilitates the anchoring of platinum and may improve the dispersion of platinum in the catalyst.
On the other hand, the embodiment of the invention provides an ultralow platinum fuel cell catalyst which is prepared by the method and comprises 90-95% by mass of nitrogen-doped carbon carrier and 5-10% by mass of platinum.
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify key features or essential features of the disclosure, nor is it intended to be used to limit the scope of the disclosure.
Drawings
The foregoing and other objects, features and advantages of the disclosure will be apparent from the following more particular descriptions of exemplary embodiments of the disclosure as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the disclosure.
FIG. 1 is a schematic diagram showing the composition of a process for preparing an ultra-low platinum fuel cell catalyst of example 1;
FIG. 2 shows an XRD (X-ray diffraction) pattern of an ultra-low platinum fuel cell catalyst of example 2;
FIG. 3 shows a LSV (Linear sweep voltammetry) plot of the ultra-low platinum fuel cell catalyst of example 2;
FIG. 4 shows a graph of mass activity after different number of cycles stability tests for the ultra-low platinum fuel cell catalyst and the JM Pt/C catalyst of example 2;
fig. 5 shows a Transmission Electron Microscope (TEM) image of the ultra-low platinum fuel cell catalyst of example 2.
Reference numerals:
theta-diffraction angle; e-voltage; j-current density; commercial catalyst from JM Pt/C-Johnson Matthey (JM).
Detailed Description
Embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The term "including" and variations thereof as used herein is intended to be open-ended, i.e., "including but not limited to". Unless specifically stated otherwise, the term "or" means "and/or". The term "based on" means "based at least in part on". The terms "one example embodiment" and "one embodiment" mean "at least one example embodiment". The term "another embodiment" means "at least one additional embodiment". The terms "first," "second," and the like may refer to different or the same object. Other explicit and implicit definitions are also possible below.
Example 1
One embodiment of the present invention discloses a preparation method of an ultra-low platinum fuel cell catalyst, as shown in fig. 1, comprising the following steps:
s1, preparing a nitrogen-doped carbon carrier, which comprises the steps of dissolving melamine in a certain amount of formaldehyde solution under a heating condition, adding sodium hydroxide (aqueous solution or solid) to adjust the pH to 7-10, reacting for a set time, adding hydrochloric acid (aqueous solution) to adjust the pH to 2-3, drying after the pH is stable, adding acetone to replace a solvent (namely a soluble solid) in wet gel obtained after drying, grinding, mixing with carbon black (powder) according to a set proportion, and performing heat treatment in a nitrogen environment to obtain the nitrogen-doped carbon carrier; the use of a nitrogen-containing carbon material facilitates the anchoring of platinum and can improve the dispersion of platinum in the catalyst.
S2, preparing the ultralow platinum fuel cell catalyst, namely mixing a certain amount of chloroplatinic acid, the nitrogen-doped carbon carrier prepared in the step S1 and deionized water, drying, grinding to obtain powder, and calcining the powder at 100-400 ℃ in a hydrogen environment to obtain the ultralow platinum fuel cell catalyst.
Specifically, the nitrogen-doped carbon carrier may also be co-doped with other elements as needed, for example, cobalt may be added to obtain a cobalt-nitrogen co-doped carbon carrier, as will be understood by those skilled in the art.
The ultralow platinum fuel cell catalyst prepared by the method comprises 90-95% by mass of nitrogen-doped carbon carrier and 5-10% by mass of platinum.
Compared with the prior art, the embodiment provides the preparation method of the fuel cell catalyst, which has the advantages of simple method, lower cost, large specific surface area, high nitrogen content, high catalytic activity and good stability, and the cost of the fuel cell catalyst is effectively reduced. The method solves the technical problem which is urgently needed to be solved in the prior art. In order to reduce the cost of the fuel cell catalyst, the ultralow platinum fuel cell catalyst is prepared by adopting a non-noble metal material load and a small amount of platinum. The catalyst can improve the oxidation-reduction activity, and the stability and the corrosion resistance can be effectively improved because the catalyst is not easy to agglomerate, dissolve and the like.
Example 2
The method is improved on the basis of the embodiment 1, in the step S1, after the reaction is carried out for a set time, firstly, adding cobalt salt and stirring, and then, adding hydrochloric acid to adjust the pH value to 2-3, so that the prepared nitrogen-doped carbon carrier is a cobalt-nitrogen co-doped carbon carrier. The cobalt-nitrogen co-doped carbon material is used as a catalyst carrier, so that the number of catalytic active sites and the catalytic stability can be improved.
Preferably, in step S1, the cobalt salt includes at least one of cobalt chloride, cobalt nitrate and cobalt sulfate.
Preferably, in step S1, the mass ratio of the nitrogen-doped carbon support to the deionized water is 5 to 10.
Preferably, in step S2, the mass ratio of platinum in chloroplatinic acid to the nitrogen-doped carbon support is 9 to 19.
Preferably, the cobalt salt is cobalt chloride hexahydrate, and the mass of the cobalt salt is 0-1 g.
Preferably, in step S1, the mass of melamine is 3.2g, the volume of the formaldehyde solution is 7ml, the volume of the sodium hydroxide solution is 1mol/L aqueous solution, the volume of the hydrochloric acid solution is 1mol/L aqueous solution, and the mass of the cobalt chloride hexahydrate is 0.5 g.
Preferably, in step S2, the mass of the nitrogen-doped carbon support is 95mg, and the chloroplatinic acid is an aqueous solution having a volume of 1.34mL and a density of 20 g/L.
Preferably, the step S1 further includes:
s11, dissolving melamine in a formaldehyde solution under a heating condition;
s12, adding sodium hydroxide into the dissolved solution, and adjusting the pH value of the solution to 7-10;
s13, standing the solution, and reacting at the high temperature of 80 ℃ for 0.5h to generate a melamine formaldehyde gel prepolymer in the solution;
s14, magnetically stirring the solution, adding cobalt salt, and continuing stirring for 2 hours (time) until the mixture is uniformly mixed;
s15, adding hydrochloric acid into the uniformly mixed solution, adjusting the pH of the solution to 2-3, and reacting in an oven at 40-70 ℃ for 24 hours after the solution is stabilized for 0.5 hour (time) to obtain wet gel;
s16, replacing the solvent in the wet gel with acetone to obtain cobalt-doped melamine formaldehyde gel, and drying and grinding the cobalt-doped melamine formaldehyde gel;
s17, uniformly mixing the dried and ground powder and carbon black according to the mass ratio of 3-7 under a ball milling condition to obtain mixed powder;
s18, carrying out high-temperature heat treatment on the mixed powder for 4 hours at 600-1000 ℃ by using a tubular furnace in a nitrogen environment to obtain the nitrogen-doped carbon carrier. In the obtained nitrogen-doped carbon carrier, the mass ratio of the melamine formaldehyde gel is 90-99%, and the mass ratio of the cobalt is 1-10%.
Preferably, the step S2 further includes:
s21, weighing a proper amount of chloroplatinic acid and nitrogen-doped carbon carrier;
s22, mixing the weighed chloroplatinic acid and nitrogen-doped carbon carrier with deionized water, drying in an oven, and grinding to obtain powder;
s23, calcining the powder in a hydrogen environment at 100-400 ℃ for a set time to obtain the ultralow platinum fuel cell catalyst.
To illustrate the technical effect of the example method, 5 sets of tests are listed below.
Test one: adding 3.2g of melamine into 7mL of formaldehyde solution, heating to 70 ℃ to dissolve the melamine into the formaldehyde solution, and uniformly mixing by magnetic stirring; adjusting the pH value of the solution to 8 by using 1mol/L sodium hydroxide aqueous solution, reacting for half an hour at the temperature of 80 ℃ to form melamine formaldehyde gel prepolymer, adding 0.5g of cobalt chloride hexahydrate into the reaction solution under magnetic stirring, and uniformly mixing the solution after 2 hours of magnetic stirring; adjusting the pH value of the solution to 2-3 by using 1mol/L hydrochloric acid aqueous solution, stabilizing for 0.5h, reacting the solution in a 60 ℃ oven for one day to obtain cobalt-doped melamine formaldehyde wet gel, replacing the solvent in the wet gel by using acetone, drying and grinding to obtain cobalt-doped melamine formaldehyde gel, weighing 100 mg of cobalt-doped melamine formaldehyde gelMixing aldehyde gel and 20 mg carbon black under ball milling condition, placing the obtained powder in a porcelain boat, and adding N 2 Under the condition, the cobalt-nitrogen co-doped carbon carrier is obtained by carrying out high-temperature heat treatment on the cobalt-nitrogen co-doped carbon carrier for 4 hours at 900 ℃ by using a tubular furnace. Then weighing 95mg of the cobalt-codoped carbon carrier obtained above, adding 0.67 mL of chloroplatinic acid aqueous solution (20 g/L) and 10 mL of deionized water, uniformly mixing under the ultrasonic condition, placing the obtained powder in a porcelain boat, and adding the porcelain boat into the porcelain boat 2 Under the condition, the catalyst I is subjected to high-temperature heat treatment for 4 hours at 200 ℃ by using a tube furnace to obtain the ultra-low platinum catalyst I.
And (2) test II: compared with the first test, 90 mg of the cobalt-nitrogen co-doped carbon carrier obtained above is weighed, 1.34mL of chloroplatinic acid aqueous solution (20 g/L) is added, and other conditions are not changed, so that the second ultralow platinum fuel cell catalyst is obtained.
And (3) test III: compared with the first test, 1g of cobalt chloride hexahydrate is added into the reaction solution, and the conditions are not changed, so that the ultra-low platinum fuel cell catalyst III is obtained.
Trial four (comparative example one): compared with the first test, no cobalt is added during the preparation of the carbon carrier, and other conditions are not changed, so that the ultra-low platinum fuel cell catalyst IV is obtained.
Run five (comparative example two): at H 2 Under the condition, the catalyst is subjected to high-temperature heat treatment for 4 hours at 400 ℃ by using a tubular furnace to obtain the ultra-low platinum fuel cell catalyst V.
The catalyst performance tests were performed on 5 sets of experiments and the test results are shown in table 1.
TABLE 1 results of catalyst Performance testing
| Sample name | Mass Activity |
| Experiment one | 0.48 A/mgPt |
| Experiment two | 0.42 A/mgPt |
| Experiment three | 0.30 A/mgPt |
| Experiment four | 0.43 A/mgPt |
| Experiment five | 0.35 A/mgPt |
As can be seen from table 1, the ultra-low platinum fuel cell catalyst prepared in test one has the highest mass activity and better performance. Compared with the first test, the second test has the advantages that the ratio of the cobalt-nitrogen co-doped carbon carrier to the chloroplatinic acid is reduced, the quality activity is reduced, and the particle size of Pt is increased due to the increase of the content of Pt, so that the utilization rate of Pt is reduced. Test three compared with test one, when 1g of cobalt chloride hexahydrate is added into the reaction solution, the quality activity is reduced because the cobalt in the carrier is easy to agglomerate due to the high content of Co, and the number of active sites is reduced. Compared with the first test, the fourth test has the advantage that the quality activity is reduced without adding cobalt, which is the lack of electronic regulation and control of cobalt on platinum, so that the activity of the catalyst is reduced. Experiment five compares with experiment one, at H 2 Under the condition, the Pt is subjected to heat treatment for 4 hours at the high temperature of 400 ℃ by using a tube furnace, the quality activity is reduced, and the Pt is agglomerated in the reduction process due to the overhigh reduction temperature, so that the utilization rate of the Pt is reduced.
Figure 2 is an XRD pattern of the ultra-low platinum fuel cell catalyst of run one, with the abscissa representing diffraction angle times 2 and the ordinate representing diffraction intensity, and the diffraction angle corresponding to the diffraction peak can be used to characterize the lattice constant. The platinum peak was seen to shift positively indicating that platinum formed an alloy structure with cobalt.
FIG. 3 is a LSV plot of the ultra-low platinum fuel cell catalyst in run one, as measured in a 0.1 mol/L HClO4 solution, with voltage on the abscissa and current density on the ordinate. The calculated mass activity of the catalyst is 0.48A/mgPt, and the performance of the catalyst is superior to that of a Pt/C (JM Pt/C, 20%) catalyst in Wen Wanfeng of business.
FIG. 4 is a graph of mass activity of ultra-low platinum fuel cell catalysts and JM Pt/C catalysts after different cycles of stability testing, with the abscissa being the number of cycles tested and the ordinate being the mass activity, the activity being the performance of the catalyst. It can be found that the activity of the JM Pt/C catalyst decreased considerably, about 32%, while the activity of the ultra-low platinum catalyst decreased only 15%. It should be noted that the JM Pt/C catalyst is a commercial catalyst produced by Johnson Matthey (JM), has a wide application range and can be used as a standard for comparison.
Fig. 5 is a TEM image of an ultra-low platinum fuel cell catalyst in test one, where it was found that the platinum was uniformly distributed on the support without significant agglomeration.
Compared with example 1, the ultra-low platinum fuel cell catalyst provided by the present example has the following beneficial effects:
1. the prepared ultra-low platinum fuel cell catalyst effectively reduces the consumption of platinum by combining the nitrogen-doped carbon material with the platinum-cobalt alloy and enabling non-noble metal active sites to interact with platinum active sites.
2. The cobalt-nitrogen co-doped carbon material is used as a carrier, so that the number of active sites is increased, and the activity of the catalyst is improved.
3. And the cobalt-nitrogen co-doped carbon material is used as a carrier, so that the stability of the catalyst is improved.
4. The use of a nitrogen-containing carbon material facilitates the anchoring of the platinum and may improve the dispersion of the platinum in the catalyst.
Example 3
The invention also provides an ultralow platinum fuel cell catalyst which is prepared by the method in the embodiment 1 or the embodiment 2 and comprises 90-95% by mass of nitrogen-doped carbon carrier and 5-10% by mass of platinum.
Having described embodiments of the present disclosure, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles of the embodiments, the practical application, or improvements made to the prior art, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. A preparation method of an ultralow platinum fuel cell catalyst is characterized by comprising the following steps:
s1, preparing a nitrogen-doped carbon carrier, which comprises the steps of dissolving melamine in a formaldehyde solution under a heating condition, adding sodium hydroxide to adjust the pH value to 7-10, reacting for a set time, adding hydrochloric acid to adjust the pH value to 2-3, drying after stabilization, finally replacing a solvent in dried wet gel with acetone, drying, grinding, mixing with carbon black according to a set proportion, and performing heat treatment in a nitrogen environment to obtain the nitrogen-doped carbon carrier;
s2, preparing the ultralow platinum fuel cell catalyst, namely mixing chloroplatinic acid, the prepared nitrogen-doped carbon carrier and deionized water, drying, grinding to obtain powder, and calcining the powder at 100-400 ℃ in a hydrogen environment to obtain the ultralow platinum fuel cell catalyst.
2. The preparation method of the ultralow platinum fuel cell catalyst according to claim 1, wherein in the step S1, after the reaction is set for a set time, firstly adding cobalt salt and stirring, and then adding hydrochloric acid to adjust the pH value to 2-3, so that the prepared nitrogen-doped carbon carrier is a cobalt-nitrogen co-doped carbon carrier.
3. The preparation method of the ultra-low platinum fuel cell catalyst according to claim 2, wherein in step S1, the cobalt salt comprises at least one of cobalt chloride, cobalt nitrate and cobalt sulfate.
4. The preparation method of the ultra-low platinum fuel cell catalyst according to any one of claims 1 to 3, wherein in the step S1, the mass ratio of the nitrogen-doped carbon support to the deionized water is 5 to 10.
5. The method of claim 4, wherein in step S2, the mass ratio of the platinum in the chloroplatinic acid to the nitrogen-doped carbon support is 9-19.
6. The preparation method of the ultra-low platinum fuel cell catalyst as claimed in claim 2 or 3, wherein the cobalt salt is cobalt chloride hexahydrate, and the mass of the cobalt salt is 0-1 g.
7. The method for preparing the ultra-low platinum fuel cell catalyst according to claim 6, wherein in the step S1, the mass of melamine is 3.2g, the volume of formaldehyde solution is 7ml, the volume of sodium hydroxide is 1mol/L aqueous solution, the volume of hydrochloric acid is 1mol/L aqueous solution, and the mass of cobalt chloride hexahydrate is 0.5 g; and the number of the first and second electrodes,
in step S2, the mass of the nitrogen-doped carbon support was 95mg, and the chloroplatinic acid was an aqueous solution having a volume of 1.34mL and a density of 20 g/L.
8. The method for preparing an ultra-low platinum fuel cell catalyst according to any one of claims 1, 2, 3, 5, and 7, wherein said step S1 further comprises:
s11, dissolving melamine in a formaldehyde solution under a heating condition;
s12, adding sodium hydroxide into the dissolved solution, and adjusting the pH value of the solution to 7-10;
s13, standing the solution, and reacting at the high temperature of 80 ℃ for 0.5h to generate a melamine formaldehyde gel prepolymer in the solution;
s14, magnetically stirring the solution, adding cobalt salt, and continuously stirring for 2 hours until the solution is uniformly mixed;
s15, adding hydrochloric acid into the uniformly mixed solution to adjust the pH to 2-3, and reacting in an oven at 40-70 ℃ for 24 hours after the solution is stabilized for 0.5 hour to obtain wet gel;
s16, replacing the solvent in the wet gel with acetone, and drying and grinding;
s17, uniformly mixing the dried and ground powder and carbon black according to the proportion of 3-7 under a ball milling condition;
and S18, carrying out high-temperature heat treatment on the mixed powder for 4 hours at 600-1000 ℃ by using a tubular furnace in a nitrogen environment to obtain the nitrogen-doped carbon carrier.
9. The method for preparing an ultra-low platinum fuel cell catalyst according to any one of claims 1 to 2 and 4 to 6, wherein the step S2 further comprises:
s21, weighing a proper amount of chloroplatinic acid and nitrogen-doped carbon carrier;
s22, mixing the weighed chloroplatinic acid and nitrogen-doped carbon carrier with deionized water, drying in an oven, and grinding to obtain powder;
s23, calcining the powder in a hydrogen environment at the temperature of 100-400 ℃ to obtain the ultralow platinum fuel cell catalyst.
10. An ultra-low platinum fuel cell catalyst prepared by the method of any one of claims 1 to 9, comprising 90 to 95% by mass of a nitrogen-doped carbon support and 5 to 10% by mass of platinum.
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