CN106571474B - Preparation method of platinum-nickel alloy nanocluster and fuel cell using the same - Google Patents
Preparation method of platinum-nickel alloy nanocluster and fuel cell using the same Download PDFInfo
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- CN106571474B CN106571474B CN201610967097.2A CN201610967097A CN106571474B CN 106571474 B CN106571474 B CN 106571474B CN 201610967097 A CN201610967097 A CN 201610967097A CN 106571474 B CN106571474 B CN 106571474B
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- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 53
- 239000000446 fuel Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 88
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 39
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 25
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000009792 diffusion process Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 20
- 229910045601 alloy Inorganic materials 0.000 description 15
- 239000000956 alloy Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910002845 Pt–Ni Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 150000004687 hexahydrates Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 PtNi Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910002837 PtCo Inorganic materials 0.000 description 1
- 229910019026 PtCr Inorganic materials 0.000 description 1
- 229910002836 PtFe Inorganic materials 0.000 description 1
- 229910002844 PtNi Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 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
- H01M4/921—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
- H01M4/9008—Organic or organo-metallic compounds
-
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
本发明公开一种铂镍合金纳米团簇的制备方法及采用其的燃料电池，该方法包括：按照铂与镍元素的摩尔比为0.2～5:1准备六水氯化镍和氯铂酸；按照聚乙烯吡咯烷酮与铂和镍元素总摩尔比1:20～30准备聚乙烯吡咯烷酮；将准备好的聚乙烯吡咯烷酮和六水氯化镍加入加热装置中，并加入溶剂，溶剂与聚乙烯吡咯烷酮的质量比设定为100～200:1，加热至75～90摄氏度，搅拌加热20～40分钟；将加热装置的温度冷却至0～5摄氏度，将准备好的氯铂酸加入加热装置中，并向加热装置中加入氢氧化钠溶液以将PH值调节为9～11，加热至185～205摄氏度，搅拌加热1～5小时，冷凝回流获得铂镍合金纳米团簇。
The invention discloses a method for preparing platinum-nickel alloy nano-clusters and a fuel cell using the same. The method comprises: preparing nickel chloride hexahydrate and chloroplatinic acid according to the molar ratio of platinum and nickel elements of 0.2-5:1; Prepare polyvinylpyrrolidone according to the total molar ratio of polyvinylpyrrolidone to platinum and nickel elements of 1:20-30; add the prepared polyvinylpyrrolidone and nickel chloride hexahydrate into the heating device, and add the solvent, the mixture of the solvent and polyvinylpyrrolidone. The mass ratio is set to 100 to 200:1, heated to 75 to 90 degrees Celsius, and heated with stirring for 20 to 40 minutes; the temperature of the heating device is cooled to 0 to 5 degrees Celsius, and the prepared chloroplatinic acid is added to the heating device, and Adding sodium hydroxide solution to the heating device to adjust the pH value to 9-11, heating to 185-205 degrees Celsius, stirring and heating for 1-5 hours, condensing and refluxing to obtain platinum-nickel alloy nanoclusters.
Description
Technical Field
The invention relates to a fuel cell cathode catalyst, in particular to a preparation method of an alloy nano material catalyst and an application of the alloy nano material catalyst in a fuel cell cathode material.
Background
Currently, as fossil fuels are increasingly exhausted, energy crisis is getting worse and environmental deterioration is getting worse, green and renewable energy sources become targets pursued by various countries. To fully utilize renewable energy sources, inexpensive and stable electrical energy storage systems will be critical. The fuel cell has the advantages of high energy conversion efficiency, cleanness, no pollution, low working temperature, quick start, high specific power, simple structure, convenient operation and the like, is known as the preferred energy of electric vehicles, fixed power stations and the like, can be applied to large power plants, small functional equipment, vehicles and the like, and is a main energy of the 21 st century.
The main components of the fuel cell are: anode, cathode, electrolyte separator, current collector, etc. The anode generates oxidation of hydrogen fuel, the cathode generates reduction of oxygen, both electrodes contain catalyst for accelerating electrochemical reaction of the electrode, and the cathode reaction is a rate determining step because of low cathode reaction rate. At present, the major bottleneck restricting the large-scale commercial development of the fuel cell is that the catalytic activity of the platinum-carbon material adopted by the cathode reaction is not ideal enough, the stability is not high, in addition, the platinum is a noble metal, the earth crust content is limited, the cost is very high, and the commercial popularization of the fuel cell is severely restricted.
One effective way to reduce the amount of noble metal platinum used is to incorporate a transition metal into the platinum to make an alloy catalyst. Alloys of platinum with transition metals such as PtNi, PtCo, PtCu, PtFe, PtCr have excellent oxygen reduction catalytic activity. In addition, the PtM (M is transition metal) alloy catalyst has higher specific activity and is more stable than commercial Pt/C. Basic research investigation shows that the synergistic effect of the two metals changes and trims the electronic structure of the metal surface and improves the catalytic activity of platinum in the alloy. The platinum-nickel alloy nano catalyst has simple structure and extremely small size. The nano structure with extremely small size enables the material to have a large specific surface area, active sites of oxygen reduction reaction are fully exposed, a novel cathode material is provided for a fuel cell, and the material has a good application prospect.
The method for preparing the platinum-nickel core-shell structure fuel cell catalyst by microwave reduction disclosed in the Chinese patent application No. 201410289122.7 comprises the following steps: sequentially adding carbon powder and a surfactant into an organic solvent, and uniformly mixing to obtain a mixture A; adding a nickel compound into the mixture A, and uniformly mixing to obtain a mixture B; performing microwave irradiation on the mixture B, wherein the reaction temperature is 80-800 ℃, the reaction time is 0.01-120 min, and then standing and cooling to obtain a mixture C; adding a platinum compound into the mixture C, and uniformly mixing to obtain a mixture D; and (3) performing microwave irradiation on the mixture D at the reaction temperature of 80-800 ℃ for 0.01-120 min, standing and cooling to obtain a mixture E, and washing and drying to obtain the catalyst. However, the microwave process of the patent application has uncertain influence on the preparation result, and the quality of the catalyst is difficult to ensure.
Also, as disclosed in chinese patent application No. 201510218290.1, a magnetic graphene-based platinum-nickel bimetallic catalyst and a preparation method thereof, the catalyst is obtained by loading platinum-nickel alloy bimetallic nanoparticles having a particle size of 10 to 20nm on a graphene carrier, and the saturation magnetization of the catalyst at 15 to 35 ℃ is 8 to 13emu/g, wherein the total mass percentage of the catalyst is 75 to 85 wt% of graphene, 1.5 to 3.6 wt% of platinum, 12.8 to 22.5 wt% of nickel, and the sum of the mass percentages of the components is 100%. The method comprises the following steps: preparing a graphene oxide tannin composite aqueous solution; adding a nickel metal ion solution, and adjusting the pH value to 9-10; adding a reducing agent, and stirring for reaction; and washing the supernatant until the pH value of the supernatant is 6.5-7, and taking the lower layer precipitate to prepare the magnetic graphene-based platinum-nickel bimetallic catalyst. However, the preparation process of the catalyst is complex, graphene is added into the preparation raw materials, the production process is multiple, the production cost is high, and the aim of wide popularization is difficult to achieve.
Further, as disclosed in chinese patent application No. 200980110417.0, a method for producing a catalyst for a fuel cell, which does not corrode in an acid electrolyte and/or at a high potential, is excellent in durability, and has a high oxygen reduction capacity. The method for producing a catalyst for a fuel cell of the patent application includes: a step (I) in which a transition metal carbonitride is heated in an oxygen-containing inert gas; and a step (II) of heating the product obtained in the step (I) in an inert gas substantially free of oxygen. The catalytic activity of the catalyst for the fuel cell is not ideal enough, the stability is not high, and the catalyst is not beneficial to large-scale popularization of the fuel cell in the future.
Therefore, the problem to be solved by the industry is to provide a fuel cell cathode catalyst which has the advantages of low production cost and strong catalytic activity and is suitable for large-scale commercial application, and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a preparation method of a platinum-nickel alloy nanocluster and a fuel cell adopting the platinum-nickel alloy nanocluster. The platinum-nickel alloy nanocluster as a fuel cell cathode catalyst improves the catalytic activity of platinum in the alloy, reduces industrial cost and is more stable.
According to an aspect of the present invention, there is provided a method of preparing a platinum-nickel alloy nanocluster, including: (1) preparing nickel chloride hexahydrate and chloroplatinic acid according to the molar ratio of platinum to nickel element of 0.2-5: 1; (2) preparing polyvinylpyrrolidone according to the total molar ratio of the polyvinylpyrrolidone to the platinum and nickel elements of 1: 20-30; (3) adding the prepared polyvinylpyrrolidone and nickel chloride hexahydrate into a heating device, adding a solvent, setting the mass ratio of the solvent to the polyvinylpyrrolidone to be 100-200: 1, heating to 75-90 ℃, stirring and heating for 20-40 minutes; (4) adding the prepared chloroplatinic acid into a heating device, adding a sodium hydroxide solution into the heating device to adjust the pH value to 9-11, heating to 185-205 ℃, stirring and heating for 1-5 hours, and performing condensation reflux to obtain the platinum-nickel alloy nanocluster.
Alternatively, the solvent is ethylene glycol.
Alternatively, the solvent may be other solvents such as absolute ethanol.
Alternatively, in the step (2), the polyvinylpyrrolidone to be prepared is polyvinylpyrrolidone-K30.
Preferably, the polyvinylpyrrolidone prepared is PVP (K-30).
Alternatively, in step (2), the prepared polyvinylpyrrolidone may be PVP (K-12), PVP (K-15), PVP (K-17), PVP (K-25), PVP (K-45), PVP (K-60) or the like.
Optionally, in the step (4), the temperature of the reaction solution is cooled to 0-5 ℃, and then chloroplatinic acid is added into the heating device.
Alternatively, the heating device includes, but is not limited to, a beaker, a flask, a three-neck flask, etc., and other types of heating devices, such as a heating tank/container with a heater, etc., may be used.
Preferably, preparing nickel chloride hexahydrate and chloroplatinic acid according to the molar ratio of platinum to nickel element of 1-3: 1; preparing polyvinylpyrrolidone according to the total molar ratio of the polyvinylpyrrolidone to the platinum and nickel elements of 1: 22-28; the mass ratio of the solvent to the polyvinylpyrrolidone is set to 150-180: 1.
Wherein, the polyvinylpyrrolidone is a ligand material for preparing the platinum-nickel alloy nanocluster.
Optionally, the solubility of the sodium hydroxide solution in the step (4) is set to 0.8 to 1.5 mol/l.
Optionally, the time of the condensation reflux in the step (4) is set to be 2.5 to 4 hours.
According to another aspect of the present invention, there is provided a fuel cell employing the platinum-nickel alloy nanoclusters of the present invention, including: the fuel cell comprises an electrolyte membrane, an anode and a cathode, wherein the anode is jointed to one side surface of the electrolyte membrane, the cathode is jointed to the other side surface of the electrolyte membrane, the anode comprises an anode catalyst and an anode gas diffusion layer, the cathode comprises a cathode catalyst and a cathode gas diffusion layer, and the cathode catalyst of the fuel cell is the platinum-nickel alloy nanocluster.
Alternatively, the platinum-nickel alloy nanoclusters are loaded in a range of 70 to 90 mg/cm, preferably 78 to 85 mg/cm, and more preferably about 80 mg/cm.
Preferably, the particle size of the platinum-nickel alloy nanoparticles in the platinum-nickel alloy nanocluster is set to be 0.5-2 nanometers.
Alternatively, the anode gas diffusion layer of a fuel cell employing platinum-nickel alloy nanoclusters is used to pass an oxidant gas and the cathode gas diffusion layer is used to pass a fuel gas.
The oxidant gas includes methanol or hydrogen or other gas capable of releasing proton, and the fuel gas includes oxygen or air or other oxygen-containing gas.
Alternatively, the anode gas diffusion layer and the cathode gas diffusion layer are made of hydrophobic carbon cloth or carbon paper.
Alternatively, the electrolyte membrane is a polymer membrane.
Preferably, the platinum-nickel alloy nanoclusters of the present invention are applied to a Proton Exchange Membrane Fuel Cell (PEMFC).
The invention has the beneficial effects that: (1) the preparation method is simple, does not need to load any supporting material, adopts a solution method to prepare the compound, has simple preparation process, more fully compounds materials, avoids the generated pollution and energy consumption, reduces the influence of uncertain factors, is environment-friendly and energy-saving, and simplifies the synthesis process; (2) the particle size of the platinum-nickel alloy nano particles synthesized by the method is less than 2nm, the specific surface area of the particles with extremely small size is large, and a large number of exposed active sites are provided, so that the catalytic activity of the oxygen reduction reaction is greatly improved; (3) the transition metal nickel with wide source and extremely low cost is introduced into the synthesized platinum-nickel alloy nano material, so that the preparation cost is greatly reduced, and due to the synergistic effect of the two metals in the alloy, the electronic structure of the Pt metal surface is improved, and the cycling stability and the durability of the oxygen reduction reaction are improved.
Drawings
Fig. 1 is an ultraviolet-visible spectrum of platinum-nickel alloy nanoclusters prepared in examples 1 to 6 of the present invention at different ratios.
FIG. 2 is a Transmission Electron Microscope (TEM) analysis chart and a particle size histogram analysis chart of platinum-nickel alloy nanoclusters prepared in examples 1 to 5 at different ratios.
FIG. 3 is a cyclic voltammogram of platinum-nickel alloy nanoclusters prepared in examples 1 to 6 at different ratios.
FIG. 4 is a polarization curve diagram of rotating disk ring electrodes of platinum-nickel alloy nanoclusters prepared in examples 1 to 6 at different ratios.
FIG. 5 is a graph showing the electron transfer number (n) and the hydrogen peroxide yield of the platinum-nickel alloy nanoclusters prepared in examples 1 to 6.
FIG. 6 shows Pt-Ni alloy nanoclusters (Pt) prepared in example 1 and having a molar ratio of Pt to Ni of 2:167Ni33NCs) were compared to the cyclic voltammograms of commercial Pt/C catalysts.
FIG. 7 shows Pt-Ni alloy nanoclusters (Pt) prepared in example 1 and having a molar ratio of Pt to Ni of 2:167Ni33NCs) were compared to the rotating disk ring electrode polarization plot of a commercial Pt/C catalyst.
FIG. 8 shows Pt-Ni alloy nanoclusters (Pt) prepared in example 1 and having a molar ratio of Pt to Ni of 2:167Ni33NCs) and commercial Pt/C catalysts, electron transfer number (n) and hydrogen peroxide yield test plots.
FIG. 9 shows Pt-Ni alloy nanoclusters (Pt) prepared in example 1 and having a molar ratio of Pt to Ni of 2:167Ni33NCs) polarization curve of the rotating disk ring electrode at different rotation speeds (100 rpm-2500 rpm).
FIG. 10 shows Pt-Ni alloy nanoclusters (Pt) prepared in example 1 and having a molar ratio of Pt to Ni of 2:167Ni33NCs) dynamic current density plot from polarization curves.
FIG. 11 shows Pt-Ni alloy nanoclusters (Pt) prepared in example 1 and having a molar ratio of Pt to Ni of 2:167Ni33NCs) versus Tafel curve for a commercial Pt/C catalyst.
FIG. 12 shows the Pt element and Ni element prepared in example 1Platinum-nickel alloy nanocluster (Pt) with molar ratio of 2:167Ni33NCs) versus commercial Pt/C catalyst.
Detailed Description
According to a non-limiting embodiment of the present invention, there is provided a method of preparing a platinum-nickel alloy nanocluster, including: (1) preparing nickel chloride hexahydrate and chloroplatinic acid according to the molar ratio of platinum to nickel element of about 2: 1; (2) preparing polyvinylpyrrolidone-K30 according to the molar ratio of the polyvinylpyrrolidone to the total of the platinum and nickel elements being about 1: 24; (3) adding prepared polyvinylpyrrolidone-K30 and nickel chloride hexahydrate into a heating device, adding ethylene glycol, setting the mass ratio of the ethylene glycol to the polyvinylpyrrolidone-K30 to be about 160:1, heating to 80 ℃, stirring and heating for 30 minutes; (4) cooling the temperature of the reaction solution to about 5 ℃, adding the prepared chloroplatinic acid into a heating device, adding a sodium hydroxide solution with the concentration of 1mol/L into the heating device to adjust the pH value to about 9, heating to about 198 ℃, stirring and heating for about 3 hours, and carrying out condensation reflux for about 3 hours to obtain the platinum-nickel alloy nanocluster.
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
0.4006g of PVP (K-30) and 19.80mg of nickel chloride hexahydrate are weighed into a 100mL three-necked flask according to the molar ratio of platinum to nickel element of 2:1, 60mL of ethylene glycol is added, the mixture is heated to 80 ℃, and the mixture is stirred for 30 min.
Cooling to about 5 ℃, adding 8.33mL of chloroplatinic acid hexahydrate solution, adjusting the pH to 9 with NaOH (1mol/l), heating to 198 ℃, continuously stirring, condensing and refluxing for 3h to obtain the platinum-nickel alloy nanocluster (Pt)67Ni33NCs) catalyst.
And (3) testing the catalytic performance:
electrochemical test characterization was performed in a test cell with a three-electrode system on the CHI 750E electrochemical workstation manufactured by chenhua corporation, shanghai. Wherein, the platinum wire is a counter electrode, the Ag/AgCl electrode is a reference electrode, and the glassy carbon electrode loaded with the catalyst is a working electrode. Weighing2mg of catalyst is added into 1.0mL of ethanol solution, 10 mu L of Nafion (perfluorosulfonic acid) is added dropwise to prepare a standard solution, and the mixed solution is subjected to ultrasonic treatment for 30 minutes to obtain a catalyst suspension with the concentration of 2 mg/mL. 10 mu L of catalyst suspension is evenly smeared on a glassy carbon electrode and is naturally dried in the air, and the loading capacity of the catalyst is 80.8 mu g/cm2. The working electrode was placed in an oxygen-saturated KOH (0.1mol/l) solution for voltammetric cyclic characterization. The test results are shown in fig. 3, 4, 5, 9, 10.
FIG. 3 is a voltammetric curve of an oxygen reduction reaction, loaded with Pt of the Pt-Ni alloy nanocluster prepared in this example67Ni33The electrode reduction peak position of the NCs catalyst was 0.79V.
FIG. 4 is a polarization curve of oxygen reduction reaction loaded with Pt of the Pt-Ni alloy nanocluster prepared in this example67Ni33The initial electrode potential of the NCs catalyst is +0.93V relative to the standard hydrogen electrode, and the limiting current density is 0-5.2 mA-2。
FIG. 5 is a graph showing electron transfer numbers of 3.6 to 3.7 and yields of 17 to 22% of hydrogen peroxide.
Fig. 9 is a polarization curve of the electrode supporting the platinum-nickel alloy nanocluster at different rotation speeds, and the limiting current density of the electrode becomes higher as the rotation speed increases.
FIG. 10 is a Koutecky-Levich curve illustrating that the current density of the platinum-nickel alloy nanoclusters is linear with the inverse of the square root of the rotation speed at different voltages, explaining the reaction kinetics.
In the drawings, a, b, c, d, e and f are used for identifying Pt100NCs、Pt75Ni25NCs、Pt67Ni33NCs、Pt50Ni50NCs、Pt33Ni67NCs、Ni100NPs corresponding curve. A. B, C, D, E, F, G, H, I are used to identify curves corresponding to rotational speeds 100, 225, 400, 625, 900, 1225, 1600, 2025, 2500, respectively.
Example 2
0.4006g of PVP (K-30) was weighed into a 100mL three-necked flask according to the molar ratio of 1:0 of platinum to nickel, 60mL of ethylene glycol was added, the mixture was heated to 80 ℃ and stirred for 30 min.
Cooling to about 2 deg.C, adding 8.33mL chloroplatinic acid hexahydrate solution, adjusting pH to 10 with NaOH (1mol/l), heating to 180 deg.C, stirring, and condensing and refluxing for 3 hr to obtain (Pt)100NCs) catalyst.
Example 3
0.4006g of PVP (K-30) and 14.86mg of nickel chloride hexahydrate are weighed into a 100mL three-necked flask according to the molar ratio of platinum to nickel element of 3:1, 60mL of ethylene glycol is added, the mixture is heated to 80 ℃, and the mixture is stirred for 30 min.
Cooling to about 3 ℃, adding 9.37mL of chloroplatinic acid hexahydrate solution, adjusting the pH to 11 with NaOH (1mol/l), heating to 200 ℃, continuously stirring, and carrying out condensation reflux for 3h to obtain the platinum-nickel alloy nanocluster (Pt)75Ni25NCs) catalyst.
Example 4
0.4006g of PVP (K-30) and 29.71mg of nickel chloride hexahydrate are weighed into a 100mL three-necked flask according to the molar ratio of platinum to nickel element of 1:1, 60mL of ethylene glycol is added, the mixture is heated to 80 ℃, and the mixture is stirred for 30 min.
Cooling to about 5 ℃, adding 6.25mL of chloroplatinic acid hexahydrate solution, adjusting the pH to 9 with NaOH (1mol/l), heating to 198 ℃, continuously stirring, condensing and refluxing for 3h to obtain the platinum-nickel alloy nanocluster (Pt)50Ni50NCs) catalyst.
Example 5
0.4006g of PVP (K-30) and 39.61mg of nickel chloride hexahydrate are weighed into a 100mL three-neck flask according to the molar ratio of platinum to nickel element of 1:2, 60mL of ethylene glycol is added, the mixture is heated to 80 ℃, and the mixture is stirred for 30 min.
Cooling to about 4 ℃, adding 4.17mL of chloroplatinic acid hexahydrate solution, adjusting the pH to 10 with NaOH (1mol/l), heating to 210 ℃, continuously stirring, condensing and refluxing for 3h to obtain the platinum-nickel alloy nanocluster (Pt)33Ni67NCs) catalyst.
Example 6
0.4006g of PVP (K-30) and 59.42mg of nickel chloride hexahydrate were weighed into a 100mL three-necked flask according to the molar ratio of platinum to nickel element of 0:1, 60mL of ethylene glycol was added, the mixture was heated to 80 ℃ and stirred for 30 min.
Adjusting pH to 9 with NaOH (1mol/l), heating to 198 ℃, continuously stirring, and condensing and refluxing for 3h to obtain Ni100NPs catalyst.
The electrochemical test methods of examples 2 to 6 were the same as in example 1. The test results are shown in FIGS. 3 to 5.
As can be seen from FIGS. 1 to 12, the synthesized platinum-nickel alloy nanoclusters (Pt) prepared in example 1 with a molar ratio of platinum to nickel of 2:167Ni33NCs) catalyst performance is best, initial potential, limiting current density and electron transfer number are close to commercial Pt/C, and stability is much higher than commercial Pt/C.
Although preferred embodiments of the present invention have been described in detail herein, it is to be understood that this invention is not limited to the precise construction and steps herein shown and described, and that other modifications and variations may be effected by one skilled in the art without departing from the spirit and scope of the invention. In addition, the parameters such as temperature, concentration, or time in the present invention may be appropriately selected within the range disclosed in the present invention depending on the specific use conditions.
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