CN111864222A - Preparation method of zinc-based bimetallic-nitrogen carbon-doped material and application of zinc-based bimetallic-nitrogen carbon-doped material to electrode catalyst - Google Patents

Preparation method of zinc-based bimetallic-nitrogen carbon-doped material and application of zinc-based bimetallic-nitrogen carbon-doped material to electrode catalyst Download PDF

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CN111864222A
CN111864222A CN202010583353.4A CN202010583353A CN111864222A CN 111864222 A CN111864222 A CN 111864222A CN 202010583353 A CN202010583353 A CN 202010583353A CN 111864222 A CN111864222 A CN 111864222A
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nitrogen
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carbon
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杨石榴
刘鑫河
代晨晨
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Jiangsu University
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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
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    • H—ELECTRICITY
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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
    • H01M4/90—Selection of catalytic material
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    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite

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Abstract

The invention belongs to the technical field of hybrid material preparation, and relates to a preparation method of a zinc-based bimetallic-nitrogen carbon-doped material, which comprises the following steps: dissolving metal chloride, zinc chloride and carbon source molecules in water to form a mixed solution, wherein the metal chloride: zinc chloride: the mass ratio of carbon source molecules is 5-15: 1; taking melamine foam as a framework and a nitrogen source, fully soaking the melamine foam, taking out and drying to obtain a precursor; heating the precursor to 800-1000 ℃ at a heating rate of 5-10 ℃/min in an inert gas atmosphere, annealing for 1-2 h, and cooling to room temperature to obtain a carbonized product; pulverizing, washing with acid, water and alcohol, and drying. The method takes the melamine foam as the framework and the nitrogen source, so that the uniform doping of heteroatoms and the improvement of the specific surface area are facilitated, the zinc chloride-assisted annealing can be used for pore-forming and zinc doping of the carbon-based material, and the synergistic improvement of the specific surface area of the carbon-based material and the density of zinc-nitrogen active sites is facilitated. Compared with the commercialized Pt/C, the prepared material has higher ORR electrocatalytic activity and stability.

Description

Preparation method of zinc-based bimetallic-nitrogen carbon-doped material and application of zinc-based bimetallic-nitrogen carbon-doped material to electrode catalyst
Technical Field
The invention belongs to the technical field of hybrid material preparation, relates to heteroatom doping, and particularly relates to a preparation method of a zinc-based bimetallic-nitrogen carbon-doped material and application of the zinc-based bimetallic-nitrogen carbon-doped material to an electrode catalyst.
Background
Metal-air batteries and hydrogen/alcohol fuel batteries are hot spots for research in the field of energy storage and conversion due to the advantages of high energy density, environmental protection, good safety and the like. During the discharge process of the battery, 4-electron Oxygen Reduction Reaction (ORR) occurs on the air electrode side, and due to the limitation of slow reaction kinetics, high overpotential is generated, so that the energy conversion efficiency and the cycle life of the battery are reduced, and the commercial application process of the battery is hindered. Therefore, there is a need to develop an efficient, stable ORR electrocatalyst to improve the operating efficiency and lifetime of the cell. The Pt-based noble metal catalyst has excellent ORR (organic rare earth) electrocatalytic activity under acidic and alkaline conditions, but has the defects of rare reserves, high price and poor stability, and is not beneficial to large-scale application.
Therefore, the development of non-noble metal electrocatalysts with high efficiency, stability and low price is the development trend of the ORR electrocatalysts at present. The metal-nitrogen doped carbon material has the advantages of many Pt-like active sites (such as pyridine-nitrogen, graphite-nitrogen, metal-nitrogen and the like), large specific surface area, rich pore structure, good stability and the like, and is the most promising ORR electrocatalyst for replacing Pt-based noble metals under acidic or alkaline conditions (Science 2016, 351, 361-.
In recent years, researches on regulation and control of ORR active sites of carbon-based materials are more and more, wherein the introduction of bimetallic-nitrogen sites can not only form 6-nitrogen coordination bimetallic sites with high ORR activity, but also further improve the electrocatalytic stability of the materials (appl. Catal. B-environ. 2019, 256, 117893; Nano Energy 2019, 63, 103851.). In addition to the widely reported iron and cobalt bi-metal-nitrogen doped carbon materials, studies have shown that zinc-nitrogen sites also have activity close to that of iron-nitrogen and have better electrocatalytic stability than iron-nitrogen species (Angew. chem. int. Ed. 2019, 58, 7035-. At present, a few reports exist on zinc-containing bimetallic-nitrogen-doped carbon materials, such as Liang et al, which seal iron phthalocyanine in dimethyl sulfoxide solution by wet ball milling to ZIF-8, and obtain Fe-Zn-S-N-C material after annealing at 1000 ℃ of 0.5M H2SO4Medium half wave potential and Pt/C only differ by 32 mV, passing through SCN-The poisoning experiments of (A) to obtain Fe-N and Zn-N speciesIs the ORR active site (chem. comm. 2017, 53, 11453); niu et al mix prepared Zn-Co-based Zeolite Imidazolate Frameworks (ZIF) with Polyacrylonitrile (PAN), obtain Zn, Co-ZIF/PAN nanofibers by electrostatic spinning, anneal at 800 ℃ to obtain elastic porous Co-Zn-N doped carbon nanofibers, half-wave potential in 0.1M KOH solution can reach 0.89 Vvs RHE, and limiting current density can reach 5.26 mA/cm 2Relative current decayed to 94.5% and Pt/C to 81.2% by I-t test at 35000s (Nano-Micro lett. 2019, 11, 8.); meng et al pyrolyze Zn/Co-ZIF/P123 at high temperature to obtain Co-Zn-N-C, albeit at 0.1M HClO4The half-wave potential in (1) is still worse than the un-commercialized Pt/C, but the limiting current density and stability are better than the Pt/C, the current density decays only 12.6% after undergoing the I-t test of 30000 s, while the Pt/C decays 36.1% after undergoing the I-t test of 20000 s (appl. Catal. B-environ. 2019, 244, 120.); lu et al use chitosan, cobalt acetate hexahydrate and zinc chloride as raw materials, and anneal at 900 deg.C to obtain Zn/Co-N-C, whose half-wave potential in 0.1M KOH can reach 0.861V vs. RHE, and limiting current density is 6.4 mA/cm2The activity is better than that of Co-N-C, Zn-N-C and Pt/C (Angew. chem. int. Ed. 2019, 58, 2622.). Therefore, the zinc-based bimetallic-nitrogen doped carbon electrocatalyst has very good application prospect.
At present, zinc-containing bimetal-nitrogen doped carbon is prepared by annealing a zinc-nitrogen-based ZIF precursor or annealing a zinc-containing bimetal salt-carbon-based precursor in ammonia gas, wherein the ZIF precursor synthesis has the defects of low yield, large organic solvent consumption and the like, and the ammonia gas nitridation method has the defects of high price, high risk and the like. Therefore, it remains a challenge how to convert inexpensive raw materials into highly efficient and stable zinc-containing bimetallic-nitrogen doped carbon ORR electrocatalysts by direct annealing in an inert atmosphere by a simple method.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a zinc-based bimetallic-nitrogen carbon-doped material.
The method takes commercial melamine foam as a framework and a nitrogen source, adsorbs an aqueous solution containing carbon source molecules and double metal salts, and obtains the high-performance oxygen reduction zinc-based double metal-nitrogen carbon-doped material through the processes of drying, annealing, grinding, acid washing and drying; the material is mixed with a commercial oxygen evolution electrocatalyst and then loaded on the surface of hydrophobic carbon paper to form an air electrode, and the air electrode, a zinc sheet and electrolyte form a rechargeable zinc-air battery.
A preparation method of a zinc-based bimetal-nitrogen doped carbon material comprises the following steps:
(a) dissolving metal chloride, zinc chloride and carbon source molecules in water to form a mixed solution, wherein the concentration of the carbon source molecules dissolved in the water is 1-5 wt.%, and the metal chloride: zinc chloride: the mass ratio of carbon source molecules is 5-15: 1, preferably 10:10: 1;
(b) taking melamine foam as a framework and a nitrogen source, fully soaking the melamine foam in the mixed solution, taking out and drying to obtain a melamine foam precursor coated by double metal ions and carbon source molecules;
(c) Heating the precursor to 800-1000 ℃ at a heating rate of 5-10 ℃/min in an inert gas atmosphere, annealing for 1-2 h, preferably annealing for 1h at 900 ℃, and cooling to room temperature to obtain a carbonized product;
(d) and (3) crushing the carbonized product, washing with acid, water and alcohol, and drying to obtain the zinc-based bimetallic-nitrogen doped carbon material.
In the preferred embodiment of the present invention, the carbon source molecule in step (a) is a water-soluble saccharide, an organic carboxylic acid, a polyalcohol or a surfactant; the metal chloride is ferric salt, cobalt salt, nickel salt or manganese salt, preferably ferric chloride hexahydrate or anhydrous ferric chloride.
Further, the saccharide is glucose, sucrose, fructose, maltose, preferably glucose; the organic carboxylic acids are citric acid, tartaric acid and malic acid, and citric acid is preferred; the polyalcohol is polyvinyl alcohol, polyethylene glycol and polyglycerol, preferably polyvinyl alcohol 1788; the surfactant is polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, polyethylene glycol laurate, preferably polyvinylpyrrolidone.
In the preferred embodiment of the present invention, the drying in step (b) comprises forced air drying, freeze drying, evaporation drying or natural drying, preferably forced air drying.
In the preferred embodiment of the present invention, the inert gas in step (c) is high purity nitrogen or argon, preferably nitrogen.
In the preferred embodiment of the invention, the pulverization in the step (d) is manual grinding or mechanical ball milling; the acid during acid washing is any one or mixture of hydrochloric acid, sulfuric acid and nitric acid; the washing process is completed by ultrasound or stirring, centrifugation or suction filtration assistance; the drying treatment comprises air-blast drying, evaporation drying or natural drying.
The other purpose of the invention is to apply the prepared zinc-based bimetallic-nitrogen doped carbon material as an electrode catalyst to the technical fields of metal-air batteries, hydrogen/alcohol fuel batteries, carbon dioxide reduction and the like.
Taking a zinc-air battery in a metal-air battery as an example:
mixing the prepared bimetallic-nitrogen-doped carbon material with a ruthenium dioxide catalyst with equal mass, adding a naphthol solution, ultrasonically dispersing in a water-ethanol mixed solvent with the volume ratio of 1:1 to obtain catalyst slurry, loading the catalyst slurry on commercial hydrophobic carbon paper, and drying to obtain an air electrode; the zinc-air battery is assembled by taking the air electrode as the anode, the zinc sheet as the cathode and 0.2M zinc acetate and 6M potassium hydroxide solution as electrolytes.
In the better disclosed example of the invention, the naphthol solution accounts for 0.5-1 wt% of the total mass of the catalyst slurry, and the loading mode is dripping or spraying.
The reagents and melamine foam used in the present invention are commercially available.
Advantageous effects
The method comprises the steps of soaking melamine foam into a solution containing bimetallic ions and carbon source molecules, and drying, annealing at high temperature, pickling and drying to obtain the zinc-based bimetallic-nitrogen doped carbon material. The zinc-nitrogen sites not only have activity close to that of the iron-nitrogen sites, but also have better electrocatalytic stability than the iron-nitrogen sites. And the introduction of the bimetal-nitrogen site can form a hexanitrogen coordination bimetal site with high oxygen reduction activity, so that the electrocatalytic stability of the material can be further improved. The melamine foam is used as a framework and a nitrogen source, so that the uniform doping of heteroatoms and the improvement of the specific surface area of the material are facilitated; the zinc chloride auxiliary annealing method not only can be used for carrying out pore forming on the carbon-based material, but also can be used for carrying out zinc doping on the carbon-based material, so that the synergistic improvement of the specific surface area of the carbon-based material and the density of zinc-nitrogen active sites is facilitated; compared with commercial Pt/C, the prepared zinc-based bimetallic-nitrogen doped chain-like porous carbon ball has higher ORR electrocatalytic activity and stability; the method is simple and efficient, mild in condition, environment-friendly, high in product yield and good in application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of the Fe-Zn-N doped chain-like porous carbon spheres synthesized in example 1.
FIG. 2 is a transmission electron microscope image of the Fe-Zn-N doped chain-like porous carbon spheres synthesized in example 1.
Fig. 3 is a dark field image scanning electron microscope image and a distribution diagram of each doping element of the fe-zn-n doped chain porous carbon sphere synthesized in example 1.
Fig. 4 shows nitrogen adsorption-desorption curves and specific surface areas of the iron-zinc-nitrogen doped chain-shaped porous carbon spheres synthesized in example 1.
Fig. 5 is a pore size distribution diagram of the iron-zinc-nitrogen doped chain-like porous carbon spheres synthesized in example 1.
FIG. 6 is a linear scanning diagram of electrocatalytic oxygen reduction of the iron-zinc-nitrogen doped chain-like porous carbon spheres synthesized in example 1 at different rotation speeds.
Fig. 7 is a linear scan of the iron-zinc-nitrogen doped chain-like porous carbon sphere material synthesized in example 1 and commercial Pt/C after 5000 CV cycles.
Fig. 8 is a plot of the relative current density versus time for the iron-zinc-nitrogen doped chain-like porous carbon sphere material synthesized in example 1 and commercial Pt/C.
Fig. 9 shows the charge-discharge cycle of the zinc-air battery driven by the mixed electrode of the iron-zinc-nitrogen doped chain-like porous carbon sphere material synthesized in example 1 and ruthenium dioxide.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
(1) Mixing 10 g of ferric chloride hexahydrate, 10 g of zinc chloride and 20 ml of 5 wt.% polyvinyl alcohol 1788 (-1 g) and diluting to 40 ml of solution; the size of the sample is 3X 0.5 cm3Soaking the melamine foam into the solution, taking out the melamine foam by using a pair of tweezers, and putting the melamine foam into a 60 ℃ oven for blast drying to obtain a precursor;
(2) putting the precursor into a tube furnace, heating to 900 ℃ at a heating rate of 5 ℃/min by taking high-purity nitrogen of 50 ml/min as a protective gas, keeping the temperature for 1 hour, and cooling to obtain a carbonized product;
(3) grinding the carbonized product into powder by using a mortar, adding 5 ml of 1 mol/L hydrochloric acid, carrying out ultrasonic treatment for 0.5 hour, carrying out centrifugal washing for 3 times by using water and ethanol, and putting the centrifuged product into a 60 ℃ oven for blast drying to obtain an iron-zinc-nitrogen doped chain-like porous carbon sphere material which is named as Fe-Zn-N-C;
(4) ultrasonically dispersing 5 mg of Fe-Zn-N-C and 5 mg of ruthenium dioxide in a mixed solvent of 1 ml of water and 1 ml of ethanol containing 75 microliters of 5 wt.% naphthol solution to form catalyst slurry, dropwise adding 0.8 ml of the slurry into 2 x 2 cm of ethanol under the heating condition2Drying the surface of the carbon cloth to obtain an air electrode;
(5) the zinc-air battery is assembled by taking a zinc sheet as a negative electrode, an air electrode as a positive electrode and 0.2 mol/L zinc acetate and 6 mol/L potassium hydroxide solution as electrolytes.
Fig. 1 shows that the morphology of the iron-zinc-nitrogen doped carbon material is like spherical particle agglomerates.
Figure 2 shows that the iron-zinc-nitrogen doped carbon material is composed of chain-like carbon spheres having a size of about 400 nm and no significant carbon-coated metal particles.
FIG. 3 shows that Fe, Zn and N are uniformly doped into the carbon material.
Fig. 4 shows that the specific surface area of the iron-zinc-nitrogen doped carbon material is as high as 1515.3 m2/g。
Figure 5 shows that the fe-zn-n doped carbon material is rich in 2-3 nm mesopores.
FIG. 6 in 0.1M KOH solution saturated with oxygen, the scanning speed was 5 mV/s, and the areal density of the carbon material was 0.6 mg/cm2It is shown that the Fe-Zn-N doped carbon material is 0.6 mg/cm in 0.1M KOH solution saturated with oxygen at 1600 rpm2The limiting current of the material can reach 6 mA/cm2The initial potential is about 0.96V, and the half-wave potential is about 0.87V.
FIG. 7 shows the scanning speed of 5 mV/s and the areal density of the carbon material of 0.6 mg/cm in an oxygen-saturated 0.1M KOH solution at 1600 rpm2The Pt/C areal density is 0.1 mg/cm2It is shown that after 5000 CV cycles, the half-wave potential of the Fe-Zn-N doped carbon material is attenuated by 9 mV, and the half-wave potential of the Pt/C material is attenuated by 22 mV.
FIG. 8 shows that the relative current of Fe-Zn-N doped carbon material decays by 10.1% and the relative current of Pt/C material decays by 28.3% after 5000 s I-t test in 0.1M KOH solution saturated with oxygen at a set voltage of 0.5V and a rotation speed of 900 rpm.
FIG. 9 at 5 mA/cm2And continuously charging for 5 minutes to discharging for 5 minutes, and showing that the charging and discharging overvoltage of the zinc-air battery driven by the synthesized iron-zinc-nitrogen doped chain-shaped porous carbon sphere material and ruthenium dioxide mixed electrode is kept at about 0.9V after the zinc-air battery is circulated for 72 hours.
Example 2
(1) Mixing 5 g of ferric chloride hexahydrate, 5 g of zinc chloride and 20 ml of 5 wt.% polyvinyl alcohol 1788 (-1 g) and diluting to 40 ml of solution; the size of the sample is 3X 0.5 cm3Soaking the melamine foam into the solution, taking out the melamine foam by using a pair of tweezers, and putting the melamine foam into a 60 ℃ oven for blast drying to obtain a precursor;
(2) putting the precursor into a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min by taking high-purity nitrogen of 50 ml/min as a protective gas, keeping the temperature for 2 hours, and cooling to obtain a carbonized product;
(3) grinding the carbonized product into powder by using a mortar, adding 5 ml of 1 mol/L nitric acid, performing ultrasonic treatment for 0.5 hour, performing centrifugal washing for 3 times by using water and ethanol, and putting the centrifuged product into a 60 ℃ oven for blast drying to obtain an iron-zinc-nitrogen doped chain-shaped porous carbon sphere material which is named as Fe-Zn-N-C2;
(4) ultrasonically dispersing 5 mg of Fe-Zn-N-C2 and 5 mg of ruthenium dioxide in a mixed solvent of 1 ml of water and 1 ml of ethanol containing 75 μ l of 5 wt.% naphthol solution to form a catalyst slurry, and spraying 0.8 ml of the catalyst slurry onto 2X 2 cm of the catalyst slurry under heating 2Drying the surface of the carbon cloth to obtain an air electrode;
(5) the zinc-air battery is assembled by taking a zinc sheet as a negative electrode, an air electrode as a positive electrode and 0.2 mol/L zinc acetate and 6 mol/L potassium hydroxide solution as electrolytes.
The electrochemical test results showed that Fe-Zn-N-C2 was present in 0.1M KOH solution saturated with oxygen at 1600 rpm at 0.6 mg/cm2The limiting current of the material is about 5.5 mA/cm2The initial potential is about 0.90V, and the half-wave potential is about 0.81V.
Example 3
(1) Mixing and diluting 15 g of ferric chloride hexahydrate, 15 g of zinc chloride and 20 ml of 5 wt.% polyvinyl alcohol 1788 (-1 g) to 40 ml of solution; the size of the sample is 3X 0.5 cm3Soaking the melamine foam into the solution, taking out the melamine foam by using a pair of tweezers, and putting the melamine foam into a 60 ℃ oven for blast drying to obtain a precursor;
(2) putting the precursor into a tube furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min by taking high-purity argon gas of 50 ml/min as protective gas, keeping the temperature for 1 hour, and cooling to obtain a carbonized product;
(3) grinding the carbonized product into powder by using a mortar, adding 5 ml of 1 mol/L sulfuric acid, performing ultrasonic treatment for 0.5 hour, performing centrifugal washing for 3 times by using water and ethanol, and putting the centrifuged product into a 60 ℃ oven for blast drying to obtain an iron-zinc-nitrogen doped chain-shaped porous carbon sphere material which is named as Fe-Zn-N-C3;
(4) Ultrasonically dispersing 5 mg of Fe-Zn-N-C3 and 5 mg of ruthenium dioxide in a mixed solvent of 1 ml of water and 1 ml of ethanol containing 75 microliters of 5 wt.% naphthol solution to form catalyst slurry, and heating 0.8 ml of the slurryDropwise adding to 2 x 2 cm2Drying the surface of the carbon cloth to obtain an air electrode;
(5) the zinc-air battery is assembled by taking a zinc sheet as a negative electrode, an air electrode as a positive electrode and 0.2 mol/L zinc acetate and 6 mol/L potassium hydroxide solution as electrolytes.
The electrochemical test results showed that Fe-Zn-N-C3 was present in 0.1M KOH solution saturated with oxygen at 1600 rpm at 0.6 mg/cm2The limiting current of the material is about 5.8 mA/cm2The initial potential is about 0.95V, and the half-wave potential is about 0.86V.
Example 4
(1) Dissolving 10 g of anhydrous ferric chloride, 10 g of zinc chloride and 1 g of glucose in 40 ml of water; the size of the sample is 3X 0.5 cm3Soaking the melamine foam into the solution, taking out the melamine foam by using a pair of tweezers, and putting the melamine foam into a 60 ℃ oven for blast drying to obtain a precursor;
(2) the product obtained by the procedure of (5) was named Fe-Zn-N-C4, similarly to example 1.
The electrochemical test results showed that Fe-Zn-N-C4 was present in 0.1M KOH solution saturated with oxygen at 1600 rpm at 0.6 mg/cm 2The limiting current of the material is about 5.7 mA/cm2The initial potential is about 0.94V, and the half-wave potential is about 0.85V.
Example 5
Similar to example 4, except that 1 g polyvinylpyrrolidone was used instead of 1 g glucose, the resulting product was named Fe-Zn-N-C5.
The electrochemical test results showed that Fe-Zn-N-C5 was present in 0.1M KOH solution saturated with oxygen at 1600 rpm at 0.6 mg/cm2The limiting current of the material is about 5.3 mA/cm2The initial potential is about 0.92V, and the half-wave potential is about 0.84V.
Example 6
Similar to example 4, except that 1 g of citric acid was used instead of 1 g of glucose, the resulting product was named Fe-Zn-N-C6.
The electrochemical test results showed that Fe-Zn-N-C6 was present in 0.1M KOH solution saturated with oxygen at 1600 rpm at 0.6 mg/cm2Limiting current of the material is about 5.7mA/cm2The initial potential is about 0.96V, and the half-wave potential is about 0.85V.
Example 7
Similar to example 4, except that 10 grams of cobalt chloride hexahydrate was used in place of 10 grams of ferric chloride hexahydrate, the resulting product was named Co-Zn-N-C.
The electrochemical test result shows that Co-Zn-N-C is 0.6 mg/cm in 0.1M KOH solution saturated by oxygen at 1600 rotating speeds2The limiting current of the material is about 5.4 mA/cm2The initial potential is about 0.90V, and the half-wave potential is about 0.81V.
Example 8
Similar to example 4, except that 10 grams of nickel chloride hexahydrate were used in place of 10 grams of ferric chloride hexahydrate, the resulting product was named Ni-Zn-N-C.
The electrochemical test result shows that Ni-Zn-N-C is in 0.1M KOH solution saturated by oxygen and at 1600 rotating speeds, 0.6 mg/cm2The limiting current of the material is about 4.9 mA/cm2The initial potential is about 0.88V, and the half-wave potential is about 0.78V.
Example 9
Similar to example 4, except that 10 g of manganese chloride tetrahydrate were used instead of 10 g of ferric chloride hexahydrate, the resulting product was named Mn-Zn-N-C.
The electrochemical test results show that Mn-Zn-N-C is 0.6 mg/cm in 0.1M KOH solution saturated with oxygen at 1600 rotation speeds2The limiting current of the material is about 4.5 mA/cm2The initial potential is about 0.90V, and the half-wave potential is about 0.81V.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (10)

1. A preparation method of a zinc-based bimetal-nitrogen doped carbon material is characterized by comprising the following steps:
(a) Dissolving metal chloride, zinc chloride and carbon source molecules in water to form a mixed solution, wherein the concentration of the carbon source molecules dissolved in the water is 1-5 wt.%, and the metal chloride: zinc chloride: the mass ratio of carbon source molecules is 5-15: 1;
(b) taking melamine foam as a framework and a nitrogen source, fully soaking the melamine foam in the mixed solution, taking out and drying to obtain a melamine foam precursor coated by double metal ions and carbon source molecules;
(c) heating the precursor to 800-1000 ℃ at a heating rate of 5-10 ℃/min in an inert gas atmosphere, annealing for 1-2 h, and cooling to room temperature to obtain a carbonized product;
(d) and (3) crushing the carbonized product, washing with acid, water and alcohol, and drying to obtain the zinc-based bimetallic-nitrogen doped carbon material.
2. The method of claim 1, wherein the zinc-based bi-metal-nitrogen doped carbon material is prepared by: the metal chloride in step (a): zinc chloride: the mass ratio of carbon source molecules is 10: 10: 1.
3. The method of claim 1, wherein the zinc-based bi-metal-nitrogen doped carbon material is prepared by: the carbon source molecule in step (a) is a water-soluble saccharide, an organic carboxylic acid, a polyalcohol or a surfactant; the metal chloride is ferric salt, cobalt salt, nickel salt or manganese salt, preferably ferric chloride hexahydrate or anhydrous ferric chloride.
4. The method of claim 3, wherein the zinc-based bi-metal-nitrogen doped carbon material is prepared by: the saccharide in the step (a) is glucose, sucrose, fructose and maltose, and is preferably glucose; the organic carboxylic acids are citric acid, tartaric acid and malic acid, and citric acid is preferred; the polyalcohol is polyvinyl alcohol, polyethylene glycol and polyglycerol, preferably polyvinyl alcohol 1788; the surfactant is polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, polyethylene glycol laurate, preferably polyvinylpyrrolidone.
5. The method of claim 1, wherein the zinc-based bi-metal-nitrogen doped carbon material is prepared by: the drying of step (b) comprises forced air drying, freeze drying, evaporative drying or natural drying, preferably forced air drying.
6. The method of claim 1, wherein the zinc-based bi-metal-nitrogen doped carbon material is prepared by: the inert gas in step (c) is high-purity nitrogen or argon, preferably nitrogen.
7. The method of claim 1, wherein the zinc-based bi-metal-nitrogen doped carbon material is prepared by: and (c) heating the precursor to 900 ℃ at a heating rate of 5-10 ℃/min in an inert gas atmosphere, and annealing for 1 h.
8. The method of claim 1, wherein the zinc-based bi-metal-nitrogen doped carbon material is prepared by: the crushing in the step (d) is manual grinding or mechanical ball milling; the acid during acid washing is any one or mixture of hydrochloric acid, sulfuric acid and nitric acid; the washing process is completed by ultrasound or stirring, centrifugation or suction filtration assistance; the drying treatment comprises air-blast drying, evaporation drying or natural drying.
9. A zinc-based bimetallic-nitrogen doped carbon material produced according to the method of any one of claims 1 to 8.
10. Use of a zinc-based bimetallic-nitrogen doped carbon material as defined in claim 9, wherein: it is applied to an electrode catalyst.
CN202010583353.4A 2020-06-22 2020-06-22 Preparation method of zinc-based bimetallic-nitrogen carbon-doped material and application of zinc-based bimetallic-nitrogen carbon-doped material to electrode catalyst Pending CN111864222A (en)

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