CN113839053B - Non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for alkaline direct methanol fuel cell and preparation method thereof - Google Patents
Non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for alkaline direct methanol fuel cell and preparation method thereof Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 46
- 239000000446 fuel Substances 0.000 title claims abstract description 42
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 37
- QTJJWJKXLSDSAQ-UHFFFAOYSA-N [Ni].[Sn].[Ta] Chemical compound [Ni].[Sn].[Ta] QTJJWJKXLSDSAQ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 90
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052718 tin Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 63
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 21
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 14
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 14
- 239000001119 stannous chloride Substances 0.000 claims description 14
- 235000011150 stannous chloride Nutrition 0.000 claims description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229910001414 potassium ion Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 6
- 231100000572 poisoning Toxicity 0.000 abstract description 6
- 230000000607 poisoning effect Effects 0.000 abstract description 6
- -1 tantalum nickel tin nitride Chemical class 0.000 abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910005887 NiSn Inorganic materials 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 4
- VMJRMGHWUWFWOB-UHFFFAOYSA-N nickel tantalum Chemical compound [Ni].[Ta] VMJRMGHWUWFWOB-UHFFFAOYSA-N 0.000 description 4
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003624 transition metals Chemical class 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
- H01M4/9041—Metals or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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Abstract
The invention discloses a non-noble metal carbon-supported nickel-tin tantalum nitride nano electro-catalyst for an alkaline direct methanol fuel cell and a preparation method thereof, wherein the nickel, tin, tantalum nitride and conductive carbon black components of the catalyst account for 7.1-9.1%, 9.2-28.8%, 42.71-54.48% and 21.35-27.24% of the mass percentage of the catalyst, and the preparation method thereof is the non-noble metal NiSn/TaN-C nano electro-catalyst prepared by a microwave-assisted ethylene glycol reduction method. The invention is a non-noble metal nano catalyst for preparing the synthesized conductive carbon black loaded tantalum nickel tin nitride for the first time, has mild preparation conditions, is simple and controllable to operate, and is energy-saving and environment-friendly. Compared with noble metal catalysts such as palladium-based or platinum-based catalysts, the electrocatalyst provided by the invention has the advantages of high electrocatalytic activity, strong CO poisoning resistance, good stability and the like for the oxidation reaction of methanol under alkaline conditions, and is used as an anode material of an alkaline direct methanol fuel cell for the first time.
Description
Technical Field
The invention belongs to the technical field of fuel cell electrocatalysts, and particularly relates to a non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for an alkaline direct methanol fuel cell and a preparation method thereof.
Background
With the reduction of available fossil energy and the increase of environmental pollution, the development of renewable energy technologies is one of the biggest challenges we face. Fuel cells, particularly direct methanol fuel cells, have attracted considerable attention as a new renewable energy technology due to their advantages of higher energy density, low pollution, and simple operation. One of the key elements that has prevented fuel cells from being widely commercialized so far is an electrode catalyst. Many reports indicate that the noble metals palladium and platinum are considered to be the best catalysts for Methanol Oxidation (MOR) in alkaline medium. However, noble metal catalysts are easily adsorbed by intermediates such as CO formed during methanol oxidation, resulting in catalyst poisoning and deactivation. Therefore, there is a need to further try to find new non-noble metals, firstly to achieve the purpose of low cost, and secondly to improve the catalytic activity and stability of the catalyst so as to achieve efficient electrocatalytic oxidation of methanol, thereby meeting the requirements of future commercialization. Among them, transition metal is paid attention as a substitute metal which can maintain high catalytic activity and has better toxicity resistance, and the nickel-based and tantalum nitride composite catalyst is not reported in the oxidation reaction of methanol under alkaline condition at present.
The key factor of the current restriction of the alkaline direct methanol fuel cell is how to design and develop a catalyst with high electrocatalytic activity, strong CO poisoning resistance and low cost, so as to promote the large-scale application of the alkaline direct methanol fuel cell.
Disclosure of Invention
In order to solve the bottleneck in the prior art, the invention aims to provide the non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for the alkaline direct methanol fuel cell and the preparation method thereof. The non-noble metal electrocatalyst is also used as an anode material of an alkaline direct methanol fuel cell for the first time, has the advantages of high electrocatalytic activity, strong CO poisoning resistance and the like through the synergistic effect of nickel, tin and tantalum nitride when methanol is not used with any noble metal under alkaline conditions, reduces the cost of the catalyst, improves the efficiency of the fuel cell and accelerates the commercial application process of the fuel cell.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a non-noble metal carbon-supported nickel-tin tantalum nitride nano electro-catalyst for an alkaline direct methanol fuel cell has a molecular formula of NiSn/TaN-C; the mass percentages of nickel, tin, tantalum nitride and conductive carbon black components of the catalyst in the catalyst are 7.1-9.1%, 9.2-28.8%, 42.71-54.48% and 21.35-27.24%, respectively.
The preparation method of the non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for the alkaline direct methanol fuel cell comprises the following steps:
1) Adding tantalum nitride, conductive carbon black and ethylene glycol into a container, placing the container on a magnetic stirrer for stirring uniformly, then performing ultrasonic treatment to uniformly disperse the tantalum nitride and the conductive carbon black in the ethylene glycol, and adding the niobium nitride and the conductive carbon black to make the mass percentages of the niobium nitride and the conductive carbon black in the catalyst be 42.71-54.48% and 21.35-27.24%, respectively, so as to obtain a mixture A;
2) Adding nickel chloride and stannous chloride into the mixture A obtained in the step 1), and uniformly stirring the mixture A on a magnetic stirrer to obtain a uniform mixture B, wherein nickel chloride with corresponding mass is added according to the mass fraction of nickel load of 7.1-9.1%, and stannous chloride with corresponding mass is added according to the mass fraction of tin load of 9.2-28.8%;
3) To the homogeneous mixture B obtained in step 2) was added a potassium hydroxide solution while stirring. Stirring uniformly, and then placing in a microwave oven for reaction. Wherein nickel chloride and stannous chloride are respectively reduced into metallic nickel and tin to obtain a solid-liquid mixture, and then the solid-liquid mixture is cooled to room temperature;
4) And washing the solid-liquid mixture cooled to room temperature by deionized water and absolute ethyl alcohol until no glycol, potassium ions and chloride ions remain, putting the mixture into a baking oven at 60-80 ℃ for drying for 6-12 hours, and grinding to obtain the non-noble metal carbon-supported nickel-tin tantalum nitride nano electro-catalyst for the alkaline direct methanol fuel cell.
Preferably, the mass ratio of the tantalum nitride to the conductive carbon black in the step (1) is 2:1, and the relation between the amounts of the tantalum nitride and the ethylene glycol is 0.78-1.25 mL of ethylene glycol for each 1mg of tantalum nitride.
Preferably, the mass of the potassium hydroxide solution in the step (2) is 5-35 times of the mass of the nickel chloride, wherein the concentration of the potassium hydroxide solution is 1-2mol/L.
Preferably, the microwave reaction time in the step (3) is 3-5 min;
according to the preparation method of the non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for the alkaline direct methanol fuel cell, the dosage of nickel chloride, stannous chloride, tantalum nitride and ethylene glycol can be increased or decreased in an equal ratio. By carrying out structural characterization analysis on the final product, nickel tin tantalum nitride is uniformly dispersed on the surface of the carrier conductive carbon black, and nickel element exists mainly in the form of oxide. The final product is obtained by electrochemical analysis and test, and the product has excellent electrocatalytic oxidation performance of methanol, and the mass activity and the specific activity can reach 11306.83mA/mg and 224.03mA/cm respectively 2 。
Compared with the prior art, the invention has the following advantages:
1. the preparation method is used for preparing the non-noble metal tantalum-nickel carbonitride based electrocatalyst for the first time, has mild conditions, is simple and controllable to operate, is energy-saving and environment-friendly, and is beneficial to realizing industrial production. The tantalum nitride is doped with a nickel-based catalyst for the first time to obtain a tantalum nitride nickel-based non-noble metal nano catalyst which is uniformly dispersed on conductive carbon black and shows excellent methanol electrocatalytic oxidation performance under alkaline conditions.
2. According to the invention, a non-noble metal tantalum nickel carbonitride based electrocatalyst is prepared by using a microwave-assisted ethylene glycol reduction method, wherein the ethylene glycol solution can effectively prevent agglomeration due to higher viscosity, so that nickel metal is more fully mixed with tantalum nitride and uniformly dispersed on conductive carbon black, and finally active sites are increased; according to the invention, glycol is used as a reducing agent, nickel tin and tantalum nitride are deposited on the conductive carbon black under the auxiliary action of microwaves, the reaction conditions are relatively mild and the reaction is uniform, and agglomeration of metals due to the excessively high reaction speed in the reduction process can be avoided.
3. The transition metal tantalum nitride is added to the nickel-based catalyst for the first time. Considering the electronic characteristics of tantalum nitride platinum, the introduction of tantalum nitride leads to certain interaction between nickel tin and tantalum nitride, thus changing the integral electronic characteristics of the catalyst, further improving the adsorption of intermediate products, simultaneously improving the catalytic activity and stability and improving the poisoning resistance of the catalyst.
4. The NiSn/TaN-C non-noble metal nano electrocatalyst prepared by the invention is firstly applied to the aspect of alkaline direct methanol fuel cells. Is characterized in that the methanol still shows high electrocatalytic activity under alkaline condition under the condition of only using nonmetal (the mass activity and the specific activity can reach 11306.83mA/mg and 224.03mA/cm respectively) 2 ) The catalyst has the advantages of strong CO poisoning resistance, strong stability and the like, thereby reducing the cost, improving the efficiency of the fuel cell and providing a new idea for promoting the development of high-efficiency and low-cost fuel cell catalysts.
Drawings
FIG. 1 is an X-ray diffraction pattern of a non-noble metal tantalum nickel tin carbonitride nanoelectrocatalyst prepared in example one.
Fig. 2 (a) and fig. 2 (b) are respectively a nickel and tin element peak-splitting fit of an X-ray photoelectron spectrum of the non-noble metal tantalum nickel tin carbonitride nano-electrocatalyst prepared in example one.
Fig. 3 is a high-definition transmission electron microscope photograph of a non-noble metal tantalum nickel tin carbonitride nano electro-catalyst prepared in example one.
FIGS. 4 (a) and 4 (b) are cyclic voltammograms of the non-noble metal supported tantalum nickel tin carbonitride nanocatalyst prepared in example one in a nitrogen saturated 1M potassium hydroxide and 1M methanol mixture at a scan rate of 50mV/s at room temperature.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
Embodiment one:
in the preparation method of the non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for the alkaline direct methanol fuel cell, 18mg of tantalum nitride, 9mg of conductive carbon black and 15mL of ethylene glycol are added into a beaker, and the mixture is placed on a magnetic stirrer to be stirred for 15min and subjected to ultrasonic treatment for 60min, so that the tantalum nitride and the conductive carbon black are uniformly dispersed in the ethylene glycol, and a mixture A is obtained.
12.2mg of nickel chloride and 9.7mg of stannous chloride are added to the mixture A, the mixture A is placed on a magnetic stirrer to be stirred for 120min, then 2ml of 1mol/L potassium hydroxide solution is added to be stirred for 10min, and the obtained uniform mixture B is placed in a microwave oven to react for 3min. Wherein nickel chloride and stannous chloride are reduced to metallic nickel and tin, respectively, to give a solid-liquid mixture, which is then cooled to room temperature.
Washing the solid-liquid mixture cooled to room temperature by deionized water and absolute ethyl alcohol until no glycol, potassium ions and chloride ions remain, putting the mixture into an oven at 60 ℃ for drying for 12 hours, and grinding to obtain the non-noble metal nickel-tin-carbon tantalum nitride nano electrocatalyst (the mass percentages of nickel, tin, tantalum nitride and conductive carbon black components are 8.32%, 16.83%, 49.9% and 24.95%) for the alkaline direct methanol fuel cell.
The catalyst prepared in this example was characterized by its structure, as shown in the X-ray diffraction pattern (fig. 1), the characteristic peaks of tantalum nitride, the X-ray photoelectron spectrum (fig. 2a and 2 b), and the transmission electron micrograph (fig. 3), and the nickel-tin characteristics of the catalyst, wherein a majority of the nickel was present in the oxidized state on the catalyst surface. Wherein the mass activity and the specific activity of the catalyst (shown in FIG. 4a and FIG. 4b, table 1) represent the electrocatalytic oxidation performance, and the mass activity and the specific activity of the non-noble metal carbon-supported nickel-tin-tantalum nitride nano electrocatalyst methanol electrocatalytic can reach 11306.83mA/mg and 224.03mA/cm respectively 2 It is illustrated that the synergistic effect of tantalum nitride and tin on nickel catalyst can make methanol catalysis reach high catalytic performance.
TABLE 1 catalyst Performance for direct methanol Fuel cells
Embodiment two:
in the preparation method of the non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for the alkaline direct methanol fuel cell, 18mg of tantalum nitride, 9mg of conductive carbon black and 15mL of ethylene glycol are added into a beaker, and the mixture is placed on a magnetic stirrer to be stirred for 15min and subjected to ultrasonic treatment for 60min, so that the tantalum nitride and the conductive carbon black are uniformly dispersed in the ethylene glycol, and a mixture A is obtained.
12.2mg of nickel chloride and 9.7mg of stannous chloride are added to the mixture A, the mixture A is placed on a magnetic stirrer to be stirred for 120min, then 2ml of 1mol/L potassium hydroxide solution is added to be stirred for 10min, and the obtained uniform mixture B is placed in a microwave oven to react for 5min. Wherein nickel chloride and stannous chloride are reduced to metallic nickel and tin, respectively, to give a solid-liquid mixture, which is then cooled to room temperature.
Washing the solid-liquid mixture cooled to room temperature by deionized water and absolute ethyl alcohol until no glycol, potassium ions and chloride ions remain, putting the mixture into an oven at 60 ℃ for drying for 12 hours, and grinding to obtain the non-noble metal nickel-tin-carbon tantalum nitride nano electrocatalyst (the mass percentages of nickel, tin, tantalum nitride and conductive carbon black components are 8.32%, 16.83%, 49.9% and 24.95%) for the alkaline direct methanol fuel cell.
The performance of this catalyst was evaluated, wherein the mass activity and specific activity of methanol oxidation were 10511.15mA/mg and 208.27mA/cm, respectively 2 。
Embodiment III:
in the preparation method of the non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for the alkaline direct methanol fuel cell, 18mg of tantalum nitride, 9mg of conductive carbon black and 15mL of ethylene glycol are added into a beaker, and the mixture is placed on a magnetic stirrer to be stirred for 15min and subjected to ultrasonic treatment for 60min, so that the tantalum nitride and the conductive carbon black are uniformly dispersed in the ethylene glycol, and a mixture A is obtained.
12.2mg of nickel chloride and 9.7mg of stannous chloride are added to the mixture A, the mixture A is placed on a magnetic stirrer to be stirred for 120min, then 1ml of 2mol/L potassium hydroxide solution is added to be stirred for 10min, and the obtained uniform mixture B is placed in a microwave oven to react for 3min. Wherein nickel chloride and stannous chloride are reduced to metallic nickel and tin, respectively, to give a solid-liquid mixture, which is then cooled to room temperature.
Washing the solid-liquid mixture cooled to room temperature by deionized water and absolute ethyl alcohol until no glycol, potassium ions and chloride ions remain, putting the mixture into an oven at 60 ℃ for drying for 12 hours, and grinding to obtain the non-noble metal nickel-tin-carbon tantalum nitride nano electrocatalyst (the mass percentages of nickel, tin, tantalum nitride and conductive carbon black components are 8.32%, 16.83%, 49.9% and 24.95%) for the alkaline direct methanol fuel cell.
The performance of this catalyst was evaluated, wherein the mass activity and specific activity of methanol oxidation were 8469.175mA/mg and 167.81mA/cm, respectively 2 。
Embodiment four:
in the preparation method of the non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for the alkaline direct methanol fuel cell, 18mg of tantalum nitride, 9mg of conductive carbon black and 15mL of ethylene glycol are added into a beaker, and the mixture is placed on a magnetic stirrer to be stirred for 15min and subjected to ultrasonic treatment for 60min, so that the tantalum nitride and the conductive carbon black are uniformly dispersed in the ethylene glycol, and a mixture A is obtained.
12.2mg of nickel chloride and 9.7mg of stannous chloride are added to the mixture A, the mixture A is placed on a magnetic stirrer to be stirred for 120min, then 3ml of 2mol/L potassium hydroxide solution is added to be stirred for 10min, and the obtained uniform mixture B is placed in a microwave oven to react for 3min. Wherein nickel chloride and stannous chloride are reduced to metallic nickel and tin, respectively, to give a solid-liquid mixture, which is then cooled to room temperature.
Washing the solid-liquid mixture cooled to room temperature by deionized water and absolute ethyl alcohol until no glycol, potassium ions and chloride ions remain, putting the mixture into an oven at 60 ℃ for drying for 12 hours, and grinding to obtain the non-noble metal nickel-tin-carbon tantalum nitride nano electrocatalyst (the mass percentages of nickel, tin, tantalum nitride and conductive carbon black components are 8.32%, 16.83%, 49.9% and 24.95%) for the alkaline direct methanol fuel cell.
The performance of this catalyst was evaluated, wherein the mass activity and specific activity of methanol oxidation were 10300mA/mg and 204.08mA/cm, respectively 2 。
Comparative example one:
according to the preparation method of the non-noble metal carbon-supported nickel tantalum nitride nano electrocatalyst for the alkaline direct methanol fuel cell, 18mg of tantalum nitride, 9mg of conductive carbon black and 15mL of ethylene glycol are added into a beaker, the mixture is placed on a magnetic stirrer to be stirred for 15min, and ultrasonic treatment is carried out for 60min, so that the tantalum nitride and the conductive carbon black are uniformly dispersed in the ethylene glycol, and a mixture A is obtained.
12.2mg of nickel chloride was added to the above mixture A, which was placed on a magnetic stirrer and stirred for 120min, then 2ml of 1mol/L potassium hydroxide was added and stirred for 10min, and the resulting homogeneous mixture B was placed in a microwave oven and reacted for 3min. Wherein nickel chloride is reduced to metallic nickel to give a solid-liquid mixture which is then cooled to room temperature.
And washing the solid-liquid mixture cooled to room temperature by deionized water and absolute ethyl alcohol until no glycol, potassium ions and chloride ions remain, putting the mixture into a 60 ℃ oven for drying for 12 hours, and grinding to obtain the non-noble metal nickel-loaded tantalum carbide-nitride nano electrocatalyst (the mass percentages of nickel, tantalum nitride and conductive carbon black components are 10%, 60% and 30%) for the alkaline direct methanol fuel cell.
The performance of the catalyst is evaluated (as shown in Table 1), and the mass activity and the specific activity of the non-noble metal carbon-supported nickel tantalum nitride nano electrocatalyst are 8170.48mA/mg and 161.89mA/cm respectively 2 。
Comparative example two:
according to the preparation method of the non-noble metal carbon-supported nickel nano electro-catalyst for the alkaline direct methanol fuel cell, 27mg of conductive carbon black and 15mL of ethylene glycol are added into a container, the mixture is placed on a magnetic stirrer to be stirred for 15min, and ultrasonic treatment is carried out for 60min, so that the conductive carbon black is uniformly dispersed in the ethylene glycol, and a mixture A is obtained.
12.2mg of nickel chloride was added to the above mixture A, which was placed on a magnetic stirrer and stirred for 120min, then 2ml of 1mol/L potassium hydroxide was added and stirred for 10min, and the resulting homogeneous mixture B was placed in a microwave oven and reacted for 3min. Wherein nickel chloride is reduced to metallic nickel to give a solid-liquid mixture which is then cooled to room temperature.
And washing the solid-liquid mixture cooled to room temperature by deionized water and absolute ethyl alcohol until no glycol, potassium ions and chloride ions remain, putting the mixture into a 60 ℃ oven for drying for 12 hours, and grinding to obtain the non-noble metal carbon-supported nickel nano electro-catalyst (the mass percent of nickel and conductive carbon black components is 10% and 90%) for the alkaline direct methanol fuel cell.
The performance of this catalyst was evaluated (as in Table 1), wherein the mass activity and specific activity of methanol oxidation were 5780.9mA/mg and 114.54mA/cm, respectively 2 。
Applicant states that the above embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention. That is, the present invention is described in detail by way of the above examples, but is not limited to the scope of the present invention. It should be clear to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc. are included in the scope of the present invention and the scope of disclosure.
Claims (5)
1. The non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for the alkaline direct methanol fuel cell is characterized in that: the catalyst is a non-noble metal nano catalyst, wherein the mass percentages of nickel, tin, tantalum nitride and conductive carbon black in the catalyst are 7.1-9.1%, 9.2-28.8%, 42.71-54.48% and 21.35-27.24% respectively;
the preparation method of the non-noble metal carbon-supported nickel-tin tantalum nitride nano electrocatalyst for the alkaline direct methanol fuel cell has the advantages of mild reaction conditions and simple operation; the method comprises the following steps:
1) Adding tantalum nitride, conductive carbon black and ethylene glycol into a container, placing the container on a magnetic stirrer for stirring uniformly, then performing ultrasonic treatment to uniformly disperse the tantalum nitride and the conductive carbon black in the ethylene glycol, and adding the niobium nitride and the conductive carbon black to make the mass percentages of the niobium nitride and the conductive carbon black in the catalyst be 42.71-54.48% and 21.35-27.24%, respectively, so as to obtain a mixture A;
2) Adding nickel chloride and stannous chloride into the mixture A obtained in the step 1), and uniformly stirring the mixture A on a magnetic stirrer to obtain a mixture B, wherein nickel chloride with corresponding mass is added into a catalyst according to the nickel load of 7.1-9.1% by mass, and stannous chloride with corresponding mass is added into the catalyst according to the tin load of 9.2-28.8% by mass;
3) Adding potassium hydroxide solution to the mixture B obtained in the step 2) while stirring; stirring uniformly, and then placing the mixture in a microwave oven for reaction; wherein nickel chloride is mainly converted into nickel oxide to obtain a solid-liquid mixture, and then the mixture is cooled to room temperature;
4) And washing the solid-liquid mixture cooled to room temperature by deionized water and absolute ethyl alcohol until no glycol, potassium ions and chloride ions remain, putting the mixture into a baking oven at 60-80 ℃ for drying for 6-12 hours, and grinding to obtain the non-noble metal carbon-supported nickel-tin tantalum nitride nano electro-catalyst for the alkaline direct methanol fuel cell.
2. The non-noble metal nickel tin tantalum nitride nanoelectrocatalyst for alkaline direct methanol fuel cells of claim 1, wherein: the nickel tin tantalum nitride is uniformly dispersed on the surface of the carrier conductive carbon black, and nickel element in the catalyst mainly exists in the form of oxide.
3. The non-noble metal nickel tin tantalum nitride nanoelectrocatalyst for alkaline direct methanol fuel cells of claim 1, wherein:
the relation between the amounts of tantalum nitride and ethylene glycol in the step 1) is that each 1.78-1.25 mL of ethylene glycol corresponds to each 1mg of tantalum nitride.
4. The non-noble metal nickel tin tantalum nitride nanoelectrocatalyst for alkaline direct methanol fuel cells of claim 1, wherein: the mass of the potassium hydroxide solution in the step 3) is 5-35 times of the mass of the nickel chloride, wherein the concentration of the potassium hydroxide solution is 1-2mol/L, and the microwave reaction time in the step (3) is 3-5 min.
5. The use of the carbon-supported nickel-tin tantalum nitride nano electrocatalyst according to claim 1, wherein: the catalyst can be used as an anode electrocatalyst of an alkaline direct methanol fuel cell.
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