CN111916769B - Preparation method of Cu-doped hollow hexagonal ZIF-8 material for zinc-air battery - Google Patents

Preparation method of Cu-doped hollow hexagonal ZIF-8 material for zinc-air battery Download PDF

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CN111916769B
CN111916769B CN202010841907.6A CN202010841907A CN111916769B CN 111916769 B CN111916769 B CN 111916769B CN 202010841907 A CN202010841907 A CN 202010841907A CN 111916769 B CN111916769 B CN 111916769B
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zinc
copper
air battery
putting
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CN111916769A (en
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高云芳
吴佳豪
武海华
徐新
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Zhejiang University of Technology ZJUT
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H01M4/8885—Sintering or firing
    • 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

Abstract

The invention discloses a preparation method of a Cu-doped hollow hexagonal ZIF-8 material for a zinc-air battery, which comprises the following steps: synthesizing a ZIF-8 material by using dimethyl imidazole and zinc nitrate hexahydrate as raw materials; converting ZIF-8 to a hollow ZIF-8 material with tannic acid; then putting the hollow ZIF-8 into a copper nitrate solution to prepare a CuHZ-8 precursor, and calcining the precursor with dicyandiamide in a muffle furnace at 550 ℃ to obtain g-C3N4Mixing CuHZ-8 with g-C3N4And (3) uniformly mixing, putting into a tube furnace for calcining, and finally washing with sulfuric acid to obtain the Cu-loaded hollow hexagonal ZIF-8 material. The invention has the advantages of sufficient raw material sources, large reserves, easy acquisition, small pollution, easy realization of mass production, high N content of the prepared material, controllable pore size and quantity in a larger range and good electrochemical performance, and shows more excellent ORR performance and stability than Pt/C in RDE, and the assembled zinc-air battery has excellent discharge performance and higher power density.

Description

Preparation method of Cu-doped hollow hexagonal ZIF-8 material for zinc-air battery
Technical Field
The invention relates to the technical field of zinc-air battery materials, in particular to a preparation method of a copper-doped hollow hexagonal ZIF-8 material for a zinc-air battery.
Background
The zinc-air battery has attracted increasing attention because of its advantages of abundant zinc storage, large theoretical energy density (1086 Wh/Kg), high safety, low price, etc. The zinc-air battery mainly comprises: a negative electrode, a positive electrode and an electrolyte. Among them, the slow kinetic reaction rate of the positive electrode is a major factor hindering the performance of the zinc-air battery. Therefore, the development of a positive electrode catalyst having excellent ORR activity is of great significance to the development of zinc-air batteries. Pt/C as a conventional ORR catalyst has the disadvantages of high price, easy poisoning and low storage capacity. Therefore, many researchers have recently studied non-noble metal materials to replace Pt/C. However, non-noble metal materials generally have lower ORR activity. Therefore, the development of non-noble metal materials with high ORR performance is of great value.
The organic metal frameworks (MOFs) are organic-inorganic hybrid materials with pores, which are connected by organic ligands and metal ions through coordination bonds, and have the advantages that: high specific surface area, good conductivity, good morphology and a large number of nitrogen ligands are increasingly gaining attention with the development of science and technology.
ZIF-8 as a typical MOFs material has potential application value in the fields of medicine, food safety, electrode materials, magnetic materials and the like, and has been researched and applied to electrode materials of zinc-air batteries. Whereas heteroatoms can increase the electrochemical activity of the material, e.g., N can not only increase the half-wave potential of the material but also inhibit agglomeration of the metal, S can increase the limiting current. Thus, the addition of a heteroatom may increase the ORR activity of the material to some extent.
At present, although various preparation methods of ZIF-8 exist, a hollow hexagonal ZIF-8 material loaded with copper is rarely prepared, the ORR activity of the ZIF-8 is not high, and the ZIF-8 material is difficult to be applied to a zinc-air battery, the hollow ZIF-8 can generate more active sites and increase the mass transfer capacity, so that the ORR catalytic activity is enhanced, and the activity of the ORR can be more strongly promoted by using Cu as the active site. In addition, the ZIF-8 material prepared by the prior art has a simpler shape, and a hollow ZIF-8 material with a hexagonal shape is not reported.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-doped ZIF-8 material, which has the advantages of large and easily-obtained natural reserves of raw materials, relatively simple production process, small pollution, easiness in mass production, capability of obtaining a material with mesopores as a main part, controllability of the pore size and the number in a large range and good electrochemical performance, and high power density and excellent discharge performance of an assembled zinc-air battery.
The technical scheme adopted by the invention for solving the technical problem is to provide a preparation method of a copper-doped hollow hexagonal ZIF-8 for a zinc-air battery, which is characterized by comprising the following steps:
the method comprises the following steps: putting dimethyl imidazole and zinc nitrate hexahydrate into a methanol solution according to a certain proportion, stirring for 24 hours to obtain ZIF-8, centrifuging and drying;
step two: putting ZIF-8 into water, putting a tannic acid solution into the solution, stirring to obtain hollow ZIF-8, centrifuging and drying;
step three: placing dicyandiamide in a muffle furnace to be calcined to obtain g-C3N4；
Step four: putting the hollow ZIF-8 into a methanol solution, putting the methanol solution in which copper nitrate is dissolved into the solution, stirring to obtain a precursor CuHZ-8, centrifuging and drying;
step five: mixing and grinding CuHZ-8 and g-C3N4 uniformly in a mortar, and then putting the mixture into a tube furnace for calcining to obtain C-CuHZ-8;
step six: the C-CuHZ-8 was washed with sulfuric acid, filtered and dried.
Preferably, in the first step: the ratio of dimethylimidazole to zinc nitrate hexahydrate may be 4: 1,3: 1 and 2: 1.
preferably, in the second step: the tannic acid solution was added and stirred for 20 minutes.
Preferably, in the second step: the mass ratio of ZIF-8 to tannic acid is 5: 7.
preferably, in the third step: the muffle furnace temperature was 550 ℃ and the calcination time was 4 hours.
Preferably, in the fourth step: the mass ratio of the hollow ZIF-8 to the copper nitrate hexahydrate is 1: 1.5.
preferably, in the step five: the calcining temperature of the tube furnace is 700-900 ℃, and the gas is N2。
Further preferably, in the step five: the calcination temperature in the tube furnace was 800 ℃.
The invention also provides a Cu-doped hollow hexagonal ZIF-8 material for the zinc-air battery, which is prepared by adopting the preparation method.
The prepared hollow hexagonal ZIF-8 material,
the nitrogen content is 6.97-12.36%.
The specific surface area is 321-571 m2/g。
The preparation method of the Cu-doped hollow hexagonal ZIF-8 of the zinc-air battery provided by the invention has the following beneficial effects:
1. the dimethylimidazole and zinc nitrate hexahydrate can be well coordinated to form ZIF-8, and the method has the characteristics of simple operation, more formed products and stable structure.
2. The tannin is widely applied to the printing industry as a fixing agent, uniform dyeing is achieved due to the slow permeation rate of the tannin, and the tannin also has the characteristics of large natural reserve of raw materials and easiness in obtaining; and the tannin is used for changing ZIF-8 into a hollow, so that the purposes of hollowing and maintaining the ZIF-8 crystal form are achieved. In addition, the whole preparation method only has six steps, and no step has higher requirements on production equipment, and the production process is simple.
3. Dicyandiamide is a white crystalline powder, and has the characteristics of low toxicity, rich reserves, wide application and the like. Preparation of g-C with dicyandiamide3N4Has the advantages of simple operation, low requirement on production equipment and the like.
4. The hollow ZIF-8 is used as a precursor, so that the generation of active sites and the enhancement of mass transfer capacity are facilitated, and the catalytic activity is increased.
5. The medicine taking the copper nitrate as the doped Cu source has the characteristic that a large amount of Cu can be loaded on the hollow ZIF-8 material to form Cu-N-C, but a Cu simple substance cannot be formed, and Cu single atoms can be formed.
6. The temperature of the high-temperature treatment in the step five is 700-900 ℃, and compared with the preparation methods of other MOFs materials, the energy consumption is lower; the high-temperature treatment is carried out in a nitrogen atmosphere, so that the material oxidation is prevented and the cost is low.
7. Step six with 0.5M H2SO4The sample is treated for 12h, the removal of Cu particles can be achieved andthe purpose of the other impurities.
8. The drying temperature in the sixth step is 60 ℃, so that the effect of preventing the metal from being oxidized can be achieved.
Drawings
FIG. 1 is a scanning electron microscope characterization result graph of a copper-doped hollow hexagonal ZIF-8 material prepared in example 1 of the present invention.
FIG. 2 is a transmission electron microscope characterization result graph of the copper-doped hollow hexagonal ZIF-8 material prepared in example 1 of the present invention.
FIG. 3 is a plot of the nitrogen desorption isotherm for a copper-doped hollow hexagonal ZIF-8 material in example 1 of the present invention.
FIG. 4 is a graph of the pore size distribution of the copper doped hollow hexagonal ZIF-8 material in example 1 of the present invention.
FIG. 5 is a graph of the copper doped hollow hexagonal ZIF-8 material in saturated O respectively in example 1 of the present invention2And cyclic voltammetry test results under Ar.
FIG. 6 is a graph of ORR performance test results for copper doped hollow hexagonal ZIF-8 material compared to 40% Pt/C in example 1 of the present invention.
FIG. 7 is a graph of the performance test results of a zinc air cell comparing the copper doped hollow hexagonal ZIF-8 material of example 1 of the present invention with 40% Pt/C.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.
Example 1
The method comprises the following steps: dimethyl imidazole and zinc nitrate hexahydrate were mixed in a 4: 1 proportion is put into methanol solution to be stirred for 24 hours to obtain ZIF-8, and the ZIF-8 is centrifuged and dried;
step two: putting ZIF-8 into water, putting a tannic acid solution into the solution, stirring to obtain hollow ZIF-8, centrifuging and drying;
step three: placing dicyandiamide in a muffle furnace to be calcined to obtain g-C3N4；
Step four: putting the hollow ZIF-8 into a methanol solution, putting the methanol solution in which copper nitrate is dissolved into the solution, stirring to obtain a precursor CuHZ-8, centrifuging and drying;
step five: mixing CuHZ-8 and g-C3N4Uniformly mixing and grinding the mixture in a mortar, and then putting the mixture into a tubular furnace to calcine the mixture at 800 ℃ to obtain C-CuHZ-8;
step six: the C-CuHZ-8 was washed with 0.5M sulfuric acid, filtered and dried.
The copper-doped hollow ZIF-8 material prepared by the method is subjected to shape characterization by a scanning electron microscope, a Hitachi S4700 type scanning electron microscope of Hitachi corporation of Japan is adopted in an experiment to research the micro-shape of the copper-doped hollow ZIF-8 material, and the result is shown in figure 1. As can be clearly seen from FIG. 1, the prepared copper-doped hollow ZIF-8 material is hexagonal in shape and well inherits the morphology of ZIF-8.
The microscopic morphology of the copper-loaded hollow ZIF-8 material was studied using a transmission electron microscope model Tecnai G2F 30S-Twin, Philips-FEI, the Netherlands, and the results are shown in FIG. 2 (a). It can be clearly seen from FIG. 2 (a) that the resulting copper doped hollow ZIF-8 material is hexagonal in shape. From fig. 2 (b), it can be seen that copper exists in the form of a single atom.
The hollow ZIF-8 material loaded with copper and prepared by the method is subjected to apparent density, specific surface area and pore volume analysis by adopting an ASAP2020 full-automatic physical chemical absorption instrument produced by Micromeritics. Specific surface area measurement N was adsorbed at 77K through the pores of the material by gas adsorption2Obtaining an adsorption isotherm, and calculating the adsorption N of the material2The surface area was calculated by fitting the measured values to a Brunauer-Emmet-teller (bet) model. The results show that the specific surface area of the material prepared by the method is 571m2∙g-1The zinc-air battery positive electrode material belongs to a material with a large specific surface area.
The pore size distribution of the copper-loaded hollow hexagonal ZIF-8 material is obtained by measuring a nitrogen adsorption and desorption isotherm. The copper load prepared by the method is subjected to the full-automatic physical and chemical adsorption instrument ASAP2020 manufactured by MicromeriticsThe hollow ZIF-8 material was subjected to pore size distribution analysis. The test temperature is 77K, and the adsorption medium is N2. The pore size distribution was calculated by the non-local density functional theory (NLDFT) method. Fig. 3 is a nitrogen adsorption and desorption isotherm diagram of the copper-loaded hollow ZIF-8 material, and it can be seen from the diagram that the nitrogen adsorption and desorption isotherm of the copper-loaded hollow ZIF-8 material is of a typical type iv, which indicates that the sample has mesoporous channels, and the mesopores can improve a large number of active sites for the carbon material, thereby improving the activity. FIG. 4 is a pore size distribution plot of a copper-loaded hollow hexagonal ZIF-8 material, where it can be seen that the pore size of the carbon material is dominated by micropores, which provide active sites, and mesopores and macropores, which provide channels. Thereby effectively improving the ORR activity of the catalyst.
The catalyst was uniformly dispersed in a mixed solution of 2mL of ethanol and 50uL of nafion (5% by weight) with 6mg of the catalyst, and then sonicated in a sonicator for 2 hours to completely disperse the catalyst in the mixed solution. And (3) uniformly coating 25uL of catalyst slurry on a glassy carbon electrode by using a liquid transfer gun, naturally airing at room temperature, and using for CV test and LSV test. The electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the Hg/HgO electrode is used as a reference electrode, a 0.1M KOH solution is used as an electrolyte, and a cyclic voltammetry test is carried out by using a three-electrode test, wherein the test result is shown in figure 5. ORR activity test As shown in FIG. 6, we can see that the half-wave potential of the material is even 8mV higher than 40% Pt/C, and the limiting current is 0.9mA/cm higher than 40% Pt/C2This indicates that the material has strong ORR activity.
The n-electron number can be calculated by the following formula:
Figure RE-750036DEST_PATH_IMAGE001
wherein J is the current density, JKIs the dynamic current density, n is the electron transfer number, F is the Faraday constant, CoIs the saturation concentration of O2 in the electrolyte，DoIs the diffusion coefficient of O2 in the electrolyte,
Figure RE-676403DEST_PATH_IMAGE002
is the viscosity of the electrolyte and ω is the rotational speed of the working electrode. The number of n electrons of the copper-supported hollow ZIF-8 material prepared by the method is calculated to be 3.96 and is close to 4, which means 4 electron transfer.
Example 2
The method comprises the following steps: dimethyl imidazole and zinc nitrate hexahydrate were mixed in a 4: 1 proportion is put into methanol solution to be stirred for 24 hours to obtain ZIF-8, and the ZIF-8 is centrifuged and dried;
step two: putting ZIF-8 into water, putting 8mg/mL tannic acid solution into the solution, stirring to obtain hollow ZIF-8, centrifuging and drying;
step three: placing dicyandiamide in a muffle furnace to be calcined for 4 hours at 550 ℃ to obtain g-C3N4；
Step four: putting the hollow ZIF-8 into a methanol solution, putting the methanol solution in which copper nitrate is dissolved into the solution, stirring to obtain a precursor CuHZ-8, centrifuging and drying;
step five: mixing CuHZ-8 and g-C3N4Uniformly mixing and grinding the mixture in a mortar, and then putting the mixture into a tubular furnace to calcine the mixture at 700 ℃ to obtain C-CuHZ-8;
step six: the C-CuHZ-8 was washed with 0.5M sulfuric acid, filtered and dried at 60 ℃.
Example 3
The method comprises the following steps: dimethyl imidazole and zinc nitrate hexahydrate were mixed in a ratio of 3: 1 proportion is put into methanol solution to be stirred for 24 hours to obtain ZIF-8, and the ZIF-8 is centrifuged and dried;
step two: putting ZIF-8 into water, putting a tannic acid solution into the solution, stirring to obtain hollow ZIF-8, centrifuging and drying;
step three: placing dicyandiamide in a muffle furnace to be calcined for 4 hours at 550 ℃ to obtain g-C3N4；
Step four: putting the hollow ZIF-8 into a methanol solution, putting the methanol solution in which copper nitrate is dissolved into the solution, stirring to obtain a precursor CuHZ-8, centrifuging and drying;
step five: mixing CuHZ-8 and g-C3N4Uniformly mixing and grinding the mixture in a mortar, and then putting the mixture into a tubular furnace to calcine the mixture at 800 ℃ to obtain C-CuHZ-8;
step six: the C-CuHZ-8 was washed with 0.5M sulfuric acid, filtered and dried at 60 ℃.
Example 4
The method comprises the following steps: dimethyl imidazole and zinc nitrate hexahydrate were mixed in a ratio of 2: 1 proportion is put into methanol solution to be stirred for 24 hours to obtain ZIF-8, and the ZIF-8 is centrifuged and dried;
step two: putting ZIF-8 into water, putting a tannic acid solution into the solution, stirring to obtain hollow ZIF-8, centrifuging and drying;
step three: placing dicyandiamide in a muffle furnace to be calcined for 4 hours at 550 ℃ to obtain g-C3N4；
Step four: putting the hollow ZIF-8 into a methanol solution, putting the methanol solution in which copper nitrate is dissolved into the solution, stirring to obtain a precursor CuHZ-8, centrifuging and drying;
step five: mixing CuHZ-8 and g-C3N4Uniformly mixing and grinding the mixture in a mortar, and then putting the mixture into a tubular furnace to calcine the mixture at 900 ℃ to obtain C-CuHZ-8;
step six: the C-CuHZ-8 was washed with 0.5M sulfuric acid, filtered and dried at 60 ℃.
The specific surface areas of the three materials were compared by changing the temperature of the high temperature treatment in step five using the controlled variable method with the experimental conditions of example 1 as basic experimental conditions (i.e., the experimental conditions except for the variables are the same as in example 1 unless otherwise specified).
Figure RE-287513DEST_PATH_IMAGE003
Wherein the specific surface area analysis is performed by gas adsorption method with ASAP2020 model full-automatic physical chemical adsorption apparatus manufactured by Micromeritics company, and N is adsorbed at 77K temperature through pores of the material2Obtaining adsorption isotherm and calculating the materialMaterial adsorption of N2The surface area was calculated by fitting the measured values to a Brunauer-Emmet-teller (bet) model.
Various copper-doped hollow ZIF-8 materials as shown in table 2 were prepared by changing the temperature of the high-temperature treatment in the fifth step using the controlled variable method with the experimental conditions of example 1 as basic experimental conditions (i.e., the experimental conditions except for the variables are the same as in example 1 if no particular description is made), and four materials were compared with the half-wave potential of commercial 40% Pt/C by performing comparative experiments, with the results as shown in table 2.
Figure RE-906713DEST_PATH_IMAGE004
As can be seen from tables 1 and 2, the specific surface area of the active material is the greatest and the ORR activity is the best at a temperature of 800 ℃, due to: the mesoporous volume rate and the area rate of the prepared material can be increased along with the increase of the temperature, the specific surface area of the active material is increased, the electrochemical performance is correspondingly improved, and when the temperature reaches 900 ℃, the material collapses due to the too high temperature, so that the specific surface area is reduced, and the ORR activity is reduced. The pore size and the nitrogen content of the copper-doped hollow hexagonal ZIF-8 can be controlled by controlling the temperature, so that the copper-doped hollow ZIF-8 material with the required pore size and specific surface area is obtained.
Comparative example 1
The difference from example 1 is that no tannic acid was used in step two.
Comparative example 2
The difference from the example 1 is that in the first step, the mass ratio of the dimethyl imidazole to the zinc nitrate hexahydrate is 5: 1.
comparative example 3
The difference from the example 1 is that in the first step, the mass ratio of the dimethyl imidazole to the zinc nitrate hexahydrate is 1: 1.
comparative example 4
The difference from example 1 is that the calcination temperature in step five is 600 ℃.
Comparative example 5
The difference from example 1 is that the calcination temperature in step five is 1000 ℃.
The specific surface area and half-wave potential of the materials obtained in each proportion were measured, and the results are shown in table 3:
Figure RE-236064DEST_PATH_IMAGE005
to verify the feasibility of the actual zinc-air cell, we made a mold and placed the catalyst in the mold for testing. As a result, as shown in FIG. 7, it was found that the power density was 247mW/cm2. The current density at 1V was 167mA/cm2. Shows superior performance to the commercial 40% Pt/C. Provides good prospect for applying non-noble metal to the zinc-air battery.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (9)

1. A preparation method of a copper-doped hollow hexagonal ZIF-8 material for a zinc-air battery is characterized by comprising the following steps:
the method comprises the following steps: putting dimethyl imidazole and zinc nitrate hexahydrate into a methanol solution according to a certain proportion, stirring for 22-25 hours to obtain ZIF-8, centrifuging and drying;
step two: putting ZIF-8 into water, putting a tannic acid solution into the solution, stirring to obtain hollow ZIF-8, centrifuging and drying;
step three: placing dicyandiamide in a muffle furnace to be calcined to obtain g-C3N4；
Step four: putting the hollow ZIF-8 into a methanol solution, putting the methanol solution in which copper nitrate is dissolved into the solution, stirring to obtain a precursor CuHZ-8, centrifuging and drying;
step five: mixing CuHZ-8 and g-C3N4Uniformly mixing and grinding the mixture in a mortar, and then putting the mixture into a tubular furnace for calcination at the calcination temperature of 800 ℃ to obtain C-CuHZ-8;
step six: the C-CuHZ-8 was washed with sulfuric acid, filtered and dried.
2. The method for preparing the copper-doped hollow hexagonal ZIF-8 material for the zinc-air battery according to claim 1, wherein the method comprises the following steps:
in the first step, the mass ratio of the dimethyl imidazole to the zinc nitrate hexahydrate is 4: 1 or 3: 1 or 2: 1.
3. the method for preparing the copper-doped hollow hexagonal ZIF-8 material for the zinc-air battery as claimed in claim 2, wherein:
in the second step, the tannic acid solution is added and stirred for 15-20 minutes.
4. The method for preparing the copper-doped hollow hexagonal ZIF-8 material for the zinc-air battery as claimed in claim 3, wherein:
in the second step, the mass ratio of ZIF-8 to tannic acid is 4:7-5: 7.
5. The method for preparing the copper-doped hollow hexagonal ZIF-8 material for the zinc-air battery according to claim 4, wherein the method comprises the following steps:
in the second step, the concentration of the tannic acid is 8 mg/mL.
6. The method for preparing the copper-doped hollow hexagonal ZIF-8 material for the zinc-air battery as claimed in any one of claims 1 to 5, wherein:
in the third step, the temperature of the muffle furnace is 450-600 ℃, and the calcining time is 3-6 hours.
7. The method for preparing the copper-doped hollow hexagonal ZIF-8 material for the zinc-air battery as claimed in any one of claims 1 to 5, wherein:
in the fourth step, the mass ratio of the hollow ZIF-8 to the copper nitrate hexahydrate is 1:1-1: 3.
8. A copper-doped hollow hexagonal ZIF-8 material for a zinc-air battery, characterized in that it is obtained by the preparation method according to any one of claims 1 to 5.
9. The copper-doped hollow hexagonal ZIF-8 material for the zinc-air battery as claimed in claim 8, wherein the shape is hollow hexagonal, the nitrogen content is 6.97% -12.36%, and the specific surface area is 321-571 m2/g。
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