CN111682223A - Preparation of in-situ synthesized nitrogen-doped carbon sheet supported (Co, Ni, Fe) nanoparticle electrocatalyst - Google Patents
Preparation of in-situ synthesized nitrogen-doped carbon sheet supported (Co, Ni, Fe) nanoparticle electrocatalyst Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 12
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
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- 238000006722 reduction reaction Methods 0.000 claims abstract description 24
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- 239000002243 precursor Substances 0.000 claims abstract description 12
- -1 (Ni Chemical class 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- CBOJBBMQJBVCMW-BTVCFUMJSA-N (2r,3r,4s,5r)-2-amino-3,4,5,6-tetrahydroxyhexanal;hydrochloride Chemical compound Cl.O=C[C@H](N)[C@@H](O)[C@H](O)[C@H](O)CO CBOJBBMQJBVCMW-BTVCFUMJSA-N 0.000 claims abstract description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 229960001911 glucosamine hydrochloride Drugs 0.000 claims abstract description 6
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- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 125000002791 glucosyl group Chemical class C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 5
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
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- 230000002194 synthesizing effect Effects 0.000 claims 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- MTDHILKWIRSIHB-UHFFFAOYSA-N (5-azaniumyl-3,4,6-trihydroxyoxan-2-yl)methyl sulfate Chemical compound NC1C(O)OC(COS(O)(=O)=O)C(O)C1O MTDHILKWIRSIHB-UHFFFAOYSA-N 0.000 claims 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 229960002849 glucosamine sulfate Drugs 0.000 claims 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 4
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- 238000004519 manufacturing process Methods 0.000 abstract 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
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- 238000012512 characterization method Methods 0.000 description 2
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- 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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Abstract
The invention discloses an in-situ synthesized nitrogen-doped two-dimensional carbon sheet supported ultra-small highly dispersed (Ni, Co, Fe) nanoparticle electrocatalyst for an oxygen reduction reaction of a fuel cell cathode. The catalyst has the advantages that: the preparation method of the material is simple, dicyandiamide and glucosamine hydrochloride are mixed in a molar ratio of 40: 1-10: 1, 1-20% of metal salts such as (Ni, Co, Fe) and the like are dissolved at high temperature to form a uniform intermediate, a precursor is prepared by combining a low-temperature freeze drying technology, a high-activity catalyst can be obtained by further pyrolysis, the size of the supported (Ni, Co, Fe) nanoparticles is about 5nm, the specific surface area of the supported (Ni, Co, Fe) nanoparticles is increased by the ultra-small size nanoparticles, more catalytic active sites are provided for an oxygen reduction reaction, and meanwhile, the number of low-coordination atoms on the surface of the nanocluster is large, so that oxygen molecules can be facilitated to promote the oxygen reduction reaction. The nano particles and the carrier have good bonding property, the catalytic stability is improved, and meanwhile, the use of metals such as Ni, Co, Fe and the like can reduce the production cost, thereby being beneficial to the commercial application of fuel cells. The invention provides a new cathode oxygen reduction catalyst material for a fuel cell, and has good application prospect.
Description
Technical Field
The invention discloses application of noble metal nanoclusters in efficient catalytic oxygen reduction reaction, and belongs to the technical field of catalysts and novel energy materials. In particular to the preparation of a catalyst for reducing cathode oxygen of a fuel cell by in-situ synthesis of nitrogen-doped two-dimensional carbon sheet-supported ultra-small highly dispersed (Co, Ni, Fe) nanoparticles, which is suitable for catalysis of metal air cells, hydrogen-oxygen fuel cells and electrolyzed water.
Background
Today, rapid development of green and sustainable energy technologies can effectively alleviate energy crisis and severe environmental pollution caused by excessive consumption of fossil fuels. Fuel cell and metal-air battery are as energy conversion equipment, mainly convert chemical energy into electric energy through the electrochemistry process and realize the energy conversion, compare the burning of traditional fossil energy, and environmental protection is clean more. The oxygen reduction reaction is a key rate determining step in fuel cells and metal air cells, and determines the energy conversion efficiency, power density and other properties of the cells. In order to ensure normal energy conversion of the fuel cell and to reduce the cost, it is necessary to develop a high-performance and high-stability cathode anode reduction catalyst.
Platinum-based materials have high catalytic activity and low overpotential and are widely used. But the large-scale commercial application of the platinum-based catalyst is hindered due to the high price and the small reserves of platinum. The transition metal nanoparticles are favored by extensive researchers, and the surface structure of the metal nanoparticles has a significant influence on the electrocatalytic activity of oxygen reduction, so that the transition metal nanoparticles are expected to be a novel cathode oxygen reduction electrocatalyst for a fuel cell, which replaces platinum.
The invention discloses an electrocatalyst for an oxygen reduction reaction of a fuel cell cathode, which is prepared by in-situ synthesis of nitrogen-doped two-dimensional carbon sheet-supported ultra-small highly-dispersed (Co, Ni, Fe) nanoparticles. The preparation method of the material is simple, a precursor is prepared by using specific amine salt and specific glucose salt in a molar ratio of 40: 1-10: 1, and the precursor is reduced without a reducing agent; the super-small size of the supported Ni, Co and Fe nano particles increases the specific surface area of the supported Ni, Co and Fe nano particles, and can provide more catalytic active sites; due to the doping of nitrogen, the electronic structure near the metal particles is improved, and the catalytic activity is improved; meanwhile, the surface of the nanocluster has more low coordination atoms, which is beneficial to oxygen molecules to promote oxygen reduction reaction. The invention provides a new catalyst for the application of the catalysis of metal air batteries, hydrogen-oxygen fuel cells and electrolytic water.
The invention relates to an electrocatalyst for a fuel cell cathode oxygen reduction reaction by in-situ synthesis of nitrogen-doped two-dimensional carbon sheet-supported ultra-small highly-dispersed (Co, Ni, Fe) nanoparticles, and a patent report of a preparation scheme for obtaining the two-dimensional porous carbon nanosheet-supported ultra-small highly-dispersed (Co, Ni, Fe) nanoparticles through simple preparation is not found at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation example for in-situ synthesis of N-doped two-dimensional carbon sheet supported ultra-small highly dispersed metal nanoparticles.
The invention is characterized in that: (1) the preparation method of the material is simple, the precursor is reduced without a reducing agent, the supported nanocluster is about 5nm, the specific surface area of the nanoparticle is increased due to the ultra-small size of the nanoparticle, and more catalytic active sites can be provided; (2) meanwhile, the surface of the nano particles is low in coordination atom number and is more, so that the activated oxygen molecules are facilitated to promote the oxygen reduction reaction; (3) the nano particles synthesized in situ have good binding property with the carrier, and the catalytic stability of the nano particles is greatly improved. The specific process route is realized by the following technical scheme, and specifically comprises the following steps.
(1) Preparing a precursor according to a specific amine salt and a specific glucose salt in a molar ratio of 40: 1-10: 1; mixing the two solutions, and grinding into powder in a mortar.
(2) Various amounts of a particular metal salt are dissolved in a quantity of dilute hydrochloric acid. The precursor is prepared by dissolving and adding 1-20% of metal salts (Ni, Co, Fe) and the like at high temperature to form a uniform intermediate and combining a low-temperature freeze drying technology.
(3) After the sample is dried, calcining the sample, and keeping the temperature at 700-1000 DEG CoIn the range of C, the inert atmosphere required by pyrolysis, the specific temperature rise speed and the heat preservation are carried out for a period of time to ensure that the carbon is fully carbonizedAnd (4) converting to obtain the nano-particle catalyst.
(4) The prepared series of metal nano-catalysts are applied to the catalysis of oxygen reduction reaction according to a certain coating process.
The molar weight of the specific amine salt adopted in the step (1) is 80-160 mmol, and the molar weight of the glucose salt is 2-16 mmol.
The high-temperature dissolving process in the step (2) needs to be heated to a temperature range of 80-100 ℃, and the adopted heating container needs to resist a certain pressure of 1.0-3.0 atm so that the salt solution is fully dissolved to be transparent, and the stirring rotating speed is stabilized within 500-1500 rpm.
The temperature during the calcination in the step (3) is 700-100 DEGoCThe temperature rise rate is 1-10oC/min, keeping the temperature for 1-6 h, and cooling to room temperature at normal temperature.
The unified loading amount of the catalyst in the step (4) is 200 mu g/cm2。
In conclusion, compared with the prior research, the invention has the advantages that.
(1) The preparation method of the product is simple, no extra reducing agent is needed to reduce the precursor of the metal, the process is simplified, the metal particles are better combined with the carrier, and the electrocatalytic activity and stability are improved.
(2) The particle size of metal particles in the synthesized nano material is about 5nm, the metal particles are uniformly embedded into the nitrogen-doped porous carbon nano sheet, the particles with extremely small sizes have a large number of exposed active sites, and the catalytic activity of the oxygen reduction reaction can be greatly improved.
(3) The synthesized nano material takes carbon with wide source and extremely low cost as a carrier, so that the preparation cost is greatly reduced, and due to the doping of nitrogen, the electronic structure near the metal nano particles is improved, and the durability and the stability of the catalyst are improved.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) at different magnifications for example 1 to prepare Ni nanoparticles supported on nitrogen-doped two-dimensional carbon sheets.
Fig. 2 is a cyclic voltammogram in an oxygen-saturated 0.1M KOH solution of samples of ultra-small, highly dispersed (Co, Ni, Fe) nanoparticles supported by two-dimensional porous carbon nanoplatelets prepared in examples 1, 2, 3.
Fig. 3 is a linear scan plot in an oxygen saturated 0.1M KOH solution of two-dimensional porous carbon nanosheet supported ultra-small, highly dispersed (Co, Ni, Fe) nanoparticle samples prepared in examples 1, 2, 3.
Fig. 4 is a summary of electrocatalytic performance of the samples of the two-dimensional porous carbon nanosheet supported ultra-small highly dispersed (Co, Ni, Fe) nanoparticles prepared in examples 1, 2, and 3 in the cathode oxygen reduction reaction of the fuel cell.
Detailed Description
The present invention is further illustrated below by way of examples, but the present invention is not limited to the following examples;
example 1.
(1) A certain amount of glucosamine hydrochloride and a certain amount of dicyandiamide are weighed and mechanically mixed for about 30min so as to be fully and uniformly mixed.
(2) Adding the mixture into a glass bottle with the volume of 30 ml, adding the mixed material, diluting the mixed material to a certain concentration, mechanically stirring for 1 hour, sealing and heating for 15min, adding a certain amount of nickel nitrate solution, and continuously stirring, heating and mixing for about 30min until the nickel nitrate solution is completely dissolved.
(3) Cooling the mixed solution 50oAnd C, performing low-temperature freeze drying for about 48 hours to completely remove water, and grinding into powder. Calcining temperature under inert atmosphere is 900 DEGoAnd C, obtaining the nickel catalyst after calcining.
Example 2.
(1) A certain amount of glucosamine hydrochloride and a certain amount of dicyandiamide are weighed and mechanically mixed for about 30min so as to be fully and uniformly mixed.
(2) Adding the mixture into a glass bottle with the volume of 30 ml, adding the mixed material, diluting the mixed material to a certain concentration, mechanically stirring for 1 hour, sealing and heating for 15min, adding a certain amount of ferric chloride solution, and continuously stirring, heating and mixing for about 30min until the mixed material is completely dissolved.
（3）Cooling the mixed solution 50oAnd C, performing low-temperature freeze drying for about 48 hours to completely remove water, and grinding into powder. Calcining temperature under inert atmosphere is 900 DEGoAnd C, obtaining the iron catalyst after calcining.
Example 3.
(1) A certain amount of glucosamine hydrochloride and a certain amount of dicyandiamide are weighed and mechanically mixed for about 30min so as to be fully and uniformly mixed.
(2) Adding the mixture into a glass bottle with the volume of 30 ml, adding the mixed material, diluting the mixed material to a certain concentration, mechanically stirring for 1 hour, sealing and heating for 15min, adding a certain amount of cobalt nitrate solution, continuously stirring, heating and mixing for about 30min until the cobalt nitrate solution is completely dissolved.
(3) Cooling the mixed solution 50oAnd C, performing low-temperature freeze drying for about 48 hours to completely remove water, and grinding into powder. Calcining temperature under inert atmosphere is 900 DEGoAnd C, obtaining the Co catalyst after calcining.
Example 4.
Electrochemical testing characterization was performed in a test cell with a three-electrode system on a CHI 660C electrochemical workstation manufactured by chenhua corporation, supra. Wherein, the carbon rod is a counter electrode, the Ag/AgCl electrode is a reference electrode, and the glassy carbon electrode (4 mm diameter) loaded with the catalyst is a working electrode. Weighing 2.5 mg of catalyst into 1.0 mL of ethanol solution, dropwise adding 10 mu of LNafion to prepare a standard solution, and carrying out ultrasonic treatment on the mixed solution for 30 minutes to obtain a catalyst suspension with the concentration of 2.5 mg/mL. Uniformly coating 10 mu L of catalyst suspension on a glassy carbon electrode and naturally drying in the air to obtain the catalyst loading of 200 mu g/cm2. And (3) placing the working electrode in 0.1M KOH solution saturated with oxygen to carry out volt-ampere cyclic characteristic test and polarization curve test, testing the stability i-t curve and ADT of the working electrode, and assembling the zinc-air battery to test the battery performance.
Example 5.
Electrochemical test characterization was performed in a test cell with a three-electrode system on CHI 660C electrochemical workstation manufactured by Shanghai Chenghua, Inc. Wherein, the carbon rod is a counter electrode, the Ag/AgCl electrode is a reference electrode, and the glassy carbon electrode (3 mm diameter) loaded with the catalyst is a working electrode. Weighing 2.5 mg of catalyst into 1.0 mL of ethanol solution, dropwise adding 10 mu of LNafion to prepare a standard solution, and carrying out ultrasonic treatment on the mixed solution for 30 minutes to obtain a catalyst suspension with the concentration of 2.5 mg/mL. Uniformly coating 6 mu L of catalyst suspension on a glassy carbon electrode and naturally drying in the air to obtain the catalyst loading of 200 mu g/cm2. The working electrode was placed at 0.5M H saturated with oxygen2SO4And performing volt-ampere cyclic characteristic test and polarization curve test in the solution.
The above embodiments are preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (6)
1. An electrocatalyst for in-situ synthesis of N-doped two-dimensional carbon sheet-supported ultra-small highly dispersed (Ni, Co, Fe) nanoparticles for fuel cell cathode oxygen reduction reaction, characterized in that: the preparation method of the material is simple, a precursor is reduced without a reducing agent, and the specific surface area of the supported nano particles of Ni, Co and Fe is increased due to the ultra-small size of the nano particles, so that more catalytic active sites can be provided; meanwhile, the surface of the nano particles is low in coordination atom number and is more, so that the activated oxygen molecules are facilitated to promote the oxygen reduction reaction; the nano particles synthesized in situ have good binding property with a carrier, can improve the catalytic stability and is beneficial to the commercial application of fuel cells, and the specific preparation process route of the catalyst comprises the following steps:
(1) preparing a precursor by using amine salt and glucose salt at a molar ratio of 40: 1-10: 1, fully mixing the amine salt and the glucose salt, adding the mixture into a mortar, and grinding for 5-60 min;
(2) adding 1-20% by mass of corresponding salts of (Ni, Co, Fe), dissolving into a dilute hydrochloric acid solution with a certain concentration, dissolving at a high temperature, adding 1-20% by mass of metal salts of (Ni, Co, Fe) and the like to form a uniform intermediate, and preparing a precursor by combining a low-temperature freeze-drying technology;
(3) after the precursor is dried, carrying out high-temperature pyrolysis on the sample, and carrying out 1-20 times of inert atmosphereoCarrying out pyrolysis at the temperature rise rate of C/min to obtain a catalyst;
(4) the prepared series of catalysts are applied to catalyzing oxygen reduction reaction, assembling batteries and testing relevant electrochemical properties of the batteries, and the catalysts are suitable for catalyzing metal air batteries, hydrogen-oxygen fuel batteries and electrolyzed water.
2. The method for preparing the electrocatalyst for the cathode oxygen reduction reaction of the fuel cell by in-situ synthesizing the N-doped two-dimensional carbon sheet-supported ultra-small highly dispersed (Ni, Co, Fe) nanoparticles according to claim 1, is characterized in that: preparing a precursor from dicyandiamide and glucosamine hydrochloride in the step (1) at a molar ratio of 40: 1-10: 1, wherein the adopted amine salt can be one or a mixture of more of amine salts rich in amino groups, such as dicyandiamide, cyanuric acid, diethylenetriamine, triethylenetetramine and the like, and has certain water solubility.
3. The method for preparing the electrocatalyst for the cathode oxygen reduction reaction of the fuel cell by in-situ synthesizing the N-doped two-dimensional carbon sheet-supported ultra-small highly dispersed (Ni, Co, Fe) nanoparticles according to claim 1, is characterized in that: the sugar is one or two of glucosamine hydrochloride or glucosamine sulfate, serves as a carbon source, is easy to complex with amine salt, and forms C-like carbon in the pyrolysis process3N4And a skeleton support for protecting the high dispersibility of the metal nanoclusters.
4. The method for preparing the electrocatalyst for the cathode oxygen reduction reaction of the fuel cell by in-situ synthesizing the N-doped two-dimensional carbon sheet-supported ultra-small highly dispersed (Ni, Co, Fe) nanoparticles according to claim 1, is characterized in that: selecting acetate, chloride or corresponding nitrate of the salt (Ni, Co, Fe) in the step (2), and requiring the salt to be dissolved in the range of pH = 2-4; the high temperature dissolution process needs to be heated to the range of 80-100 ℃, the adopted heating container needs to resist a certain pressure of 1.0-3.0 atm, so that the salt solution is fully dissolved to be transparent, and the stirring speed is stabilized within 500-1500 rpm.
5. The method for preparing the electrocatalyst for the fuel cell cathode oxygen reduction reaction by in-situ synthesizing the N-doped two-dimensional carbon sheet-supported ultra-small highly dispersed (Ni, Co, Fe) nanoclusters according to claim 1, wherein the method comprises the following steps: keeping the temperature in the calcining in the step (3) at 700-100 DEGoIn the range of C, high-purity nitrogen or high-purity argon is selected as the inert atmosphere required by pyrolysis, and the heating rate is 1-10oC/min, and preserving the heat for a period of time to ensure that the carbon nano sheets are fully carbonized and orderly generated.
6. The method for preparing the electrocatalyst for the fuel cell cathode oxygen reduction reaction by in-situ synthesizing the N-doped two-dimensional carbon sheet-supported ultra-small highly dispersed (Ni, Co, Fe) nanoclusters according to claim 1, wherein the method comprises the following steps: the unified loading amount of the catalyst in the step (4) is 200 mu g/cm2Ensuring that the catalyst achieves the strongest catalytic activity.
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