CN116387544A - Cathode catalyst and preparation method and application thereof - Google Patents
Cathode catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000001816 cooling Methods 0.000 claims abstract description 47
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 35
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 150000003057 platinum Chemical class 0.000 claims abstract description 9
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 6
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- 238000005406 washing Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 11
- 239000000446 fuel Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
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- 238000000926 separation method Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
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- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 7
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 2
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- 230000000052 comparative effect Effects 0.000 description 9
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- 238000001914 filtration Methods 0.000 description 4
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- 238000009776 industrial production Methods 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000006731 degradation reaction Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- -1 platinum ions Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
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- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention provides a cathode catalyst, a preparation method and application thereof. The cathode catalyst comprises a carbon carrier and a platinum-based intermetallic compound Pt-M supported on the carbon carrier; m in the platinum-based intermetallic compound Pt-M comprises a lanthanide metal. The preparation method comprises the following steps: (1) Mixing lanthanide metal salt solution, complex solution and platinum salt solution, and performing complex precipitation to obtain Pt-M compound; (2) And (3) mixing the Pt-M compound in the step (1) with a carbon material, and sequentially annealing and cooling in an unnatural manner in a reducing atmosphere to obtain the cathode catalyst. The cathode catalyst provided by the invention has the advantages that Pt and lanthanide metal alloy are loaded on a carbon carrier in a matching way, so that the cathode catalyst can show higher ORR quality and specific activity, has uniform particle size distribution and smaller particle size, is an ordered intermetallic compound structure, and has more excellent ORR performance.
Description
Technical Field
The invention belongs to the technical field of fuel cells, relates to a cathode catalyst and a preparation method and application thereof, and in particular relates to a cathode catalyst in a proton exchange membrane fuel cell and a preparation method and application thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) as a high-efficiency hydrogen energy conversion technology have great application potential in the aspects of reducing carbon emission, environmental energy crisis and the like. However, platinum and platinum-based electrocatalysts as electrode materials for Oxygen Reduction Reactions (ORR) in proton exchange membrane fuel cells have limited commercial applications in PEMFCs due to their high cost, low abundance, high overpotential, low availability of pure Pt, and the like. In addition, when Pt is used as an electrocatalyst, ORR requires an overpotential of about 200 to 250 mV.
Carbon-supported platinum (Pt) -based nanoparticles can be used as oxygen reduction catalysts. These conventional carbon-supported Pt-based nanoparticle catalysts (Pt/C) can provide high surface area and moderate activity; such as CN111146448A and to a platinum carbon catalyst, a process for its preparation and its use. Comprising the following steps: (1) Mixing a carbon material with a nitric acid solution, refluxing, separating and drying to obtain carbon powder; (2) Mixing carbon powder with hydrogen peroxide solution, separating, and oven drying to obtain carbon carrier; (3) Mixing a carbon carrier, a platinum-containing solution and a reducing agent, refluxing under the protection of inert atmosphere, adding an antipole inhibitor for emulsification, carrying out microwave treatment, separating and drying to obtain the platinum-carbon catalyst. Also, as in CN102687320a, there is provided a platinum catalyst for a fuel cell, which has platinum particles of fine particle size and is supported on a carbon support in a highly dispersed manner. However, durability of the ORR catalyst of Pt/C presents a significant problem.
Pt/C catalysts are susceptible to performance degradation during fuel cell operation, at least due to agglomeration and growth of Pt nanoparticles and/or stress of the carbon substrate, which occurs through a combination of mechanisms of Pt crystallite migration, electrochemical Ostwald (Ostwald) ripening, and carbon support corrosion. Degradation of the Pt/C catalyst then reduces the power output of the fuel cell and necessitates the use of larger amounts of noble metals such as platinum, gold, rhodium, palladium and ruthenium, further increasing costs.
Therefore, how to improve the ORR performance of the cathode catalyst is an urgent technical problem to be solved.
Disclosure of Invention
The invention aims to provide a cathode catalyst, a preparation method and application thereof. The cathode catalyst provided by the invention has the advantages that Pt and lanthanide metal alloy are loaded on a carbon carrier in a matching way, so that the cathode catalyst can show higher ORR quality and specific activity, has uniform particle size distribution and smaller particle size, is an ordered intermetallic compound structure, and has more excellent ORR performance.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a cathode catalyst comprising a carbon support and a platinum-based intermetallic compound Pt-M supported on the carbon support; m in the platinum-based intermetallic compound Pt-M comprises a lanthanide metal.
According to the cathode catalyst provided by the invention, the Pt-lanthanide metal is used for modifying the electronic structure of Pt by forming an intermetallic compound structure, so that the electronic structure of Pt has better adsorption strength on reactants and active intermediates, and the ORR reaction is promoted in dynamics, so that the Pt-lanthanide intermetallic compound has higher ORR specific activity and mass activity, and has stronger stability compared with single-metal Pt/C. The platinum-based (platinum-lanthanide) substance provided by the invention has an ordered intermetallic compound structure, and the ordered structure has better ORR activity and stability than an unordered structure.
Preferably, the particle size of the platinum-based intermetallic compound Pt-M is less than or equal to 5nm, such as 0.5nm, 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.2nm, 3.5nm, 4nm, 4.5nm or 5nm, etc.
The platinum-based intermetallic compound provided by the invention has smaller particle size which is not more than 5nm, and the platinum-based intermetallic compound with small particle size can be better contacted with reactants, so that the activity is higher, while if the particle size is too large and is more than 5nm, the number of exposed catalytic sites is reduced, and the ORR activity is reduced.
Preferably, the mass ratio of the platinum-based intermetallic compound to the carbon support is 1 (1-4), such as 1:1, 1:2, 1:3, or 1:4.
Preferably, the molar ratio of Pt to M in the platinum-based intermetallic compound Pt-M is (1-5): 1, e.g. 1:1, 2:1, 3:1, 4:1 or 5:1, etc.
In a second aspect, the present invention provides a method for preparing a cathode catalyst according to the first aspect, the method comprising the steps of:
(1) Mixing lanthanide metal salt solution, complex solution and platinum salt solution, and performing complex precipitation to obtain Pt-M compound;
(2) And (3) mixing the Pt-M compound in the step (1) with a carbon material, and sequentially annealing and cooling in an unnatural manner in a reducing atmosphere to obtain the cathode catalyst.
According to the preparation method provided by the invention, the platinum-lanthanide compound with uniform dispersion is obtained through complex precipitation of lanthanide metal ions and platinum ions, annealing and unnatural cooling are further carried out, so that the intermetallic compound with orderly-distributed atoms, uniform particle size distribution and smaller particle size is obtained, and the preparation method has high operability and potential of large-scale industrial production;
in the invention, the step (1) adopts a complexation precipitation method to play a role of uniformly dispersing Pt and lanthanide metals, while other methods cannot obtain uniformly dispersed platinum-lanthanide metal precursors; and after annealing, highly ordered intermetallic compound synthesis cannot be achieved if a period of unnatural cooling process is not performed.
Preferably, the complex of step (1) comprises any one or a combination of at least two of bipyridine, phenanthroline or terpyridine.
Preferably, the ratio of the molar amount of the complex to the lanthanide metal salt of step (1) is not less than 3.
Preferably, the solvent in the complex solution of step (1) comprises ethanol.
Preferably, the solvent in the platinum salt solution of step (1) comprises ethanol.
Preferably, the platinum salt of step (1) comprises chloroplatinic acid and/or tetraamineplatinum nitrate.
Preferably, the complex precipitation in step (1) is followed by solid-liquid separation, washing and drying.
Preferably, the annealing in step (2) is performed at a temperature of 700 to 1000 ℃, for example 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, or the like.
Preferably, the cooling rate in the unnatural cooling process in the step (2) is 1-3 ℃/min, such as 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min or 3 ℃/min, etc.
In the invention, if the cooling rate in the unnatural cooling process is too high, the time for rearranging metal atoms is insufficient, a good intermetallic compound structure cannot be obtained, and the crystallinity of the alloy is reduced.
Preferably, the temperature after the unnatural cooling in the step (2) is 400-700 ℃, such as 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, or the like.
In the invention, natural cooling is carried out after the unnatural cooling period reaches the target temperature.
Preferably, in the step (2), the cooled substance is subjected to acid washing, solid-liquid separation, washing and drying.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) Mixing lanthanide metal salt solution, complex solution and platinum salt solution, performing complex precipitation, solid-liquid separation, washing and drying to obtain Pt-M compound;
(2) And (3) mixing the Pt-M compound in the step (1) with a carbon material, annealing at 700-1000 ℃ in sequence in a reducing atmosphere, then cooling to 400-700 ℃ at a cooling rate of 1-3 ℃/min, and finally cooling naturally, carrying out acid washing, solid-liquid separation, washing and drying to obtain the cathode catalyst.
In a third aspect, the present invention also provides a fuel cell comprising a cathode catalyst according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the cathode catalyst structure obtained by the preparation method provided by the invention firstly obtains complexation precipitation in the preparation process, and then carries out annealing and unnatural cooling, wherein the platinum-based intermetallic compound has uniform particle size distribution, smaller particle size and ordered intermetallic compound structure, thereby realizing more excellent ORR performance; and the preparation process has high operability and potential of large-scale industrial production. The cathode catalyst provided by the invention has the ORR half-wave potential of more than 888mV, and the ORR half-wave potential of more than 902mV when the cooling rate in the unnatural cooling process is further regulated and controlled to be 1-3 ℃/min.
Drawings
Fig. 1 is a TEM image of the cathode catalyst provided in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a cathode catalyst, which comprises a carbon black carrier and a Pt-Gd ordered intermetallic compound structure positioned on the carbon black carrier, wherein the molar ratio of Pt to Gd is 5:1, and the mass ratio of the carbon black carrier to the Pt-Gd ordered intermetallic compound structure is 1:1.
The preparation method of the cathode catalyst comprises the following steps:
s1: 2mmol of gadolinium metal salt (gadolinium nitrate) was dissolved in 20mL of deionized water, and 6mmol of bipyridine was dissolved in 20mL of ethanol (99.9%), the two solutions were mixed together and stirred at room temperature for 24h to obtain [ Gd (bpy) 3 ] 2+ A complex solution;
10mmol of chloroplatinic acid was dissolved in 40mL of ethanol (99.9%) and then added [ M (bpy) 3 ] 2+ Precipitating a bright yellow Pt-Gd compound in the complex solution, centrifuging the Pt-Gd compound at a centrifugal speed of 10000rpm for 3 minutes, washing the Pt-Gd compound with ethanol, and drying the powder in an oven at 50 ℃ overnight;
s2: 750mg of Pt-Gd compound and 210mg of carbon black were ground together in a mortarTo obtain a mixture, the mixture is treated with H 2 After thermal annealing for 2 hours at 900 ℃ in Ar atmosphere, cooling to 600 ℃ at a cooling rate of 1 ℃/min, and then naturally cooling;
s3: and (3) treating the Pt-Gd/C material obtained by natural cooling in dilute acid, filtering, washing and drying to obtain the cathode catalyst.
FIG. 1 shows a TEM image of the cathode catalyst provided in example 1, and as can be seen from FIG. 1, pt synthesized by the preparation method provided by the present invention 5 The particle diameters of the Gd intermetallic compounds are smaller than 5nm, and the particle size distribution is uniform.
Example 2
The embodiment provides a cathode catalyst, which comprises a carbon black carrier and a Pt-Sm ordered intermetallic compound structure positioned on the carbon black carrier, wherein the molar ratio of Pt to Sm is 3:1, and the mass ratio of the carbon black carrier to the Pt-Sm ordered intermetallic compound structure is 4:1.
The preparation method of the cathode catalyst comprises the following steps:
s1: 2mmol of samarium metal salt (samarium nitrate) was dissolved in 20mL of deionized water, and 6mmol of bipyridine was dissolved in 20mL of ethanol (99.9%), and the two solutions were mixed together and stirred at room temperature for 24h to obtain [ Sm (bpy) 3 ] 2+ A complex solution;
6mmol of chloroplatinic acid was dissolved in 40mL of ethanol (99.9%) and then added [ M (bpy) 3 ] 2+ Precipitating a bright yellow Pt-Sm compound in the complex solution, centrifuging the Pt-Sm compound for 3 minutes at a centrifugal speed of 10000rpm, washing the Pt-Sm compound with ethanol, and drying the powder in an oven at 50 ℃ overnight;
s2: 750mg of Pt-Sm compound and 210mg of carbon black were ground together in a mortar to obtain a mixture, and the mixture was subjected to H 2 After thermal annealing for 2 hours at 1000 ℃ in Ar atmosphere, cooling to 700 ℃ at a cooling rate of 2 ℃/min, and then naturally cooling;
s3: and (3) treating the Pt-Sm/C material obtained by natural cooling in dilute acid, filtering, washing and drying to obtain the cathode catalyst.
Example 3
The embodiment provides a cathode catalyst, which comprises a carbon black carrier and a Pt-La ordered intermetallic compound structure positioned on the carbon black carrier, wherein the molar ratio of Pt to La is 1:1, and the mass ratio of the carbon black carrier to the Pt-La ordered intermetallic compound structure is 1:1.
The preparation method of the cathode catalyst comprises the following steps:
s1: 2mmol of lanthanide metal salt (lanthanum nitrate) was dissolved in 20mL of deionized water, and 8mmol of bipyridine was dissolved in 20mL of ethanol (99.9%), the two solutions were mixed together and stirred at room temperature for 24h to obtain [ La (bpy) 3 ] 2+ A complex solution;
2mmol of chloroplatinic acid was dissolved in 40mL of ethanol (99.9%) and then added [ M (bpy) 3 ] 2+ Precipitating a bright yellow Pt-La compound in the complex solution, centrifuging the Pt-La compound for 3 minutes at a centrifugal speed of 10000rpm, washing the Pt-La compound with ethanol, and drying the powder in an oven at 50 ℃ overnight;
s2: 750mg of Pt-La compound and 210mg of carbon black were ground together in a mortar to obtain a mixture, and the mixture was subjected to H 2 After thermal annealing for 2 hours at 700 ℃ in Ar atmosphere, cooling to 400 ℃ at a cooling rate of 3 ℃/min, and then naturally cooling;
s3: and (3) treating the Pt-La/C material obtained by natural cooling in dilute acid, filtering, washing and drying to obtain the cathode catalyst.
Example 4
The difference between this example and example 1 is that the complex in step (1) of this example is phenanthroline.
The remaining preparation methods and parameters were consistent with example 1.
Example 5
The difference between this example and example 1 is that the cooling rate in step (2) of this example is 5 ℃/min.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 1
The difference between the comparative example and example 1 is that the temperature in step (2) of the comparative example is directly and naturally lowered after annealing, and the non-natural temperature lowering stage is not performed.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 2
The preparation method provided in this comparative example is a conventional impregnation method: 2mmol of lanthanide metal salt (lanthanum nitrate) and 10mmol of chloroplatinic acid were dissolved in 20mL of deionized water, 2.0g of carbon black was added to the above solution, and the cloudy solution was stirred with heating at 60 ℃ until the water content of the solution was completely evaporated. Grinding the dried mixture in a mortar to obtain a mixture, and subjecting the mixture to H 2 And (3) carrying out thermal annealing at 700 ℃ in Ar atmosphere for 2 hours, cooling to 400 ℃ at a cooling rate of 1 ℃/min, and then carrying out natural cooling. And (3) treating the Pt-La/C material obtained by natural cooling in dilute acid, filtering, washing and drying to obtain the cathode catalyst.
The cathode catalysts provided in examples 1-5 and comparative examples 1-2 were subjected to performance testing under the following conditions: o at 0.1M 2 Saturated HClO 4 A linear scan test (0.05-1.10V vs RHE,20mV/s) was performed on the solution and the test results are shown in Table 1. Table 1 also shows the particle size ranges of the cathode catalysts provided in examples 1-5 and comparative examples 1-2.
TABLE 1
From the data of examples 1 and 5, it is understood that too fast a cooling rate during the unnatural cooling process may result in a decrease in crystallinity of the intermetallic compound and a decrease in catalyst performance.
From the data of example 1 and comparative example 1, it is understood that formation of ordered intermetallic compounds cannot be achieved without performing an unnatural cooling process after annealing, and catalyst performance is lowered.
From the data of examples 1 to 5 and comparative example 2, it is understood that other production methods cannot obtain particles having a small particle diameter and a uniform particle diameter distribution, and thus the ORR performance thereof is not excellent enough.
In summary, the cathode catalyst structure obtained by the preparation method provided by the invention has the advantages that complex precipitation is obtained in the preparation process, and then annealing and unnatural cooling are performed, wherein the platinum-based intermetallic compound has uniform particle size distribution, smaller particle size and ordered intermetallic compound structure, so that more excellent ORR performance can be realized; and the preparation process has high operability and potential of large-scale industrial production. The cathode catalyst provided by the invention has the ORR half-wave potential of more than 888mV, and the ORR half-wave potential of more than 902mV when the cooling rate in the unnatural cooling process is further regulated and controlled to be 1-3 ℃/min.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. A cathode catalyst, characterized in that the cathode catalyst comprises a carbon support and a platinum-based intermetallic compound Pt-M supported on the carbon support; m in the platinum-based intermetallic compound Pt-M comprises a lanthanide metal.
2. The cathode catalyst according to claim 1, wherein the particle size of the platinum-based intermetallic compound Pt-M is 5nm or less.
3. The cathode catalyst according to claim 1 or 2, wherein the mass ratio of the platinum-based intermetallic compound to the carbon support is 1 (1-4);
preferably, the molar ratio of Pt to M in the platinum-based intermetallic compound Pt-M is (1-5): 1.
4. A method for preparing the cathode catalyst according to any one of claims 1 to 3, comprising the steps of:
(1) Mixing lanthanide metal salt solution, complex solution and platinum salt solution, and performing complex precipitation to obtain Pt-M compound;
(2) And (3) mixing the Pt-M compound in the step (1) with a carbon material, and sequentially annealing and cooling in an unnatural manner in a reducing atmosphere to obtain the cathode catalyst.
5. The method of preparing a cathode catalyst according to claim 4, wherein the complex of step (1) comprises any one or a combination of at least two of bipyridine, phenanthroline, and terpyridine;
preferably, the ratio of the molar amount of the complex to the lanthanide metal salt in step (1) is not less than 3;
preferably, the solvent in the complex solution of step (1) comprises ethanol;
preferably, the solvent in the platinum salt solution of step (1) comprises ethanol;
preferably, the platinum salt of step (1) comprises chloroplatinic acid and/or tetraamineplatinum nitrate.
6. The method for preparing a cathode catalyst according to claim 4 or 5, wherein the complex precipitation in step (1) is followed by solid-liquid separation, washing and drying.
7. The method for preparing a cathode catalyst according to any one of claims 4 to 6, wherein the annealing temperature in step (2) is 700 to 1000 ℃;
preferably, the cooling rate in the unnatural cooling process in the step (2) is 1-3 ℃/min;
preferably, the temperature after the unnatural cooling in the step (2) is 400-700 ℃.
8. The method for producing a cathode catalyst according to any one of claims 4 to 7, wherein in the step (2), the cooled substance is subjected to acid washing, solid-liquid separation, washing and drying.
9. The method for producing a cathode catalyst according to any one of claim 4 to 8, wherein,
(1) Mixing lanthanide metal salt solution, complex solution and platinum salt solution, performing complex precipitation, solid-liquid separation, washing and drying to obtain Pt-M compound;
(2) And (3) mixing the Pt-M compound in the step (1) with a carbon material, annealing at 700-1000 ℃ in sequence in a reducing atmosphere, then cooling to 400-700 ℃ at a cooling rate of 1-3 ℃/min, and finally cooling naturally, carrying out acid washing, solid-liquid separation, washing and drying to obtain the cathode catalyst.
10. A fuel cell comprising the cathode catalyst according to any one of claims 1 to 3.
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