CN110534750B - Positive electrode material, preparation method thereof and carbon dioxide battery - Google Patents

Positive electrode material, preparation method thereof and carbon dioxide battery Download PDF

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CN110534750B
CN110534750B CN201910799875.5A CN201910799875A CN110534750B CN 110534750 B CN110534750 B CN 110534750B CN 201910799875 A CN201910799875 A CN 201910799875A CN 110534750 B CN110534750 B CN 110534750B
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positive electrode
porous carbon
electrode material
nitrogen
sulfur
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CN110534750A (en
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湛菁
徐昌藩
陈军
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Central South 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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • 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
    • 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
    • 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
    • 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
    • H01M4/96—Carbon-based electrodes
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a positive electrode material, a preparation method thereof and a carbon dioxide battery, wherein the positive electrode material comprises 85% -95% of porous carbon, 2% -10% of nitrogen and 1% -5% of sulfur attached to the porous carbon, and the BET specific surface area of the positive electrode material is 400-1200 m2(iv)/g, the average pore size is 2 to 5 nm. The invention has the following beneficial effects: (1) the anode material has higher specific surface area, so that the larger contact area is increased for reaction, and the catalytic efficiency is improved; (2) the method for preparing the nitrogen-sulfur co-doped porous carbon material by using the betel nuts is simple, low in cost, wide and easily available in raw materials, good in structure and honeycomb-shaped, and is beneficial to efficient transmission of ions and electrons; (3) the method for preparing the nitrogen-sulfur co-doped porous carbon material by using the betel nuts provides a new method for developing and utilizing high value-added products of the biomass waste.

Description

Positive electrode material, preparation method thereof and carbon dioxide battery
Technical Field
The invention relates to the field of new energy materials, in particular to a positive electrode material and a preparation method thereof, a carbon dioxide battery positive electrode and a carbon dioxide battery.
Background
In recent years, the increase of population base largely determines the consumption and demand of energy, the use amount of fossil fuels is greatly increased in the world, and the balance between the release amount of carbon dioxide and the environment limits the sustainable development of human society. Global warming has threatened the normal life of human beings and captured CO2And its conversion to fuels and chemicals is CO reduction2An effective way to discharge the amount. In the development and utilization of carbon dioxide, a metal carbon dioxide battery, particularly a sodium carbon dioxide battery, has become a brand new method for carbon dioxide resource utilization due to high energy density, rich sodium resource and low cost, can realize resource recycling of carbon dioxide by combining with an energy storage system, is also beneficial to reducing fossil fuel consumption, is a powerful technology for developing and utilizing renewable clean energy, and has important practical significance for relieving the problems of energy shortage and global warming.
Although the research on metal carbon dioxide batteries has made major breakthroughs in recent years, the development thereof is still relatively slow. DioxygenThe carbon dioxide reduction reaction (CO) is carried out on the positive electrode of the carbon dioxide battery2RR)), the reaction is a multi-electron transfer process, the electrochemical reaction is slow, and in addition, carbonate discharge products are also extremely difficult to decompose, so that the carbon dioxide battery still has the problems of poor cycle performance, high polarization, poor rate performance and the like. The high-performance cathode can effectively reduce the over-potential of battery charge/discharge, and obviously improve the capacity and energy efficiency, rate capability and cycling stability. Therefore, a high-performance cathode material is sought, and the material has important significance for improving the battery performance of the carbon dioxide battery.
Disclosure of Invention
Based on the above, the present invention aims to provide a high-performance carbon dioxide cathode material.
The anode material comprises, by atomic percentage, 85% -90% of porous carbon, 5% -10% of nitrogen and 1% -5% of sulfur attached to the porous carbon, and the BET specific surface area of the anode material is 300-1200 m2(iv)/g, the average pore size is 2 to 5 nm.
In some embodiments, the positive electrode material has a BET surface area of 616m2/g。
In some embodiments, the pore size in the positive electrode material is 2.65 nm.
The second purpose of the invention is to provide a preparation method of the cathode material, which comprises the following steps:
1) soaking the crushed betel nuts in alkali liquor, washing and drying to obtain activated betel nuts;
2) adding an activating agent and the activated betel nuts into water for soaking, drying, carrying out heat preservation calcination, washing and drying to obtain a porous carbon material;
3) and (3) placing the porous carbon material in a mixed solution of ammonium sulfide and an alcohol solution, stirring to dry, and carrying out heat preservation and calcination in a protective atmosphere to obtain a nitrogen-sulfur doped porous carbon material, namely the anode material.
In some embodiments, the lye is selected from at least one of sodium hydroxide and potassium hydroxide.
In some embodiments, the base solution is sodium hydroxide.
In some embodiments, the concentration of the sodium hydroxide is 1-5 mol/L.
In some embodiments, the activator is selected from at least one of potassium bicarbonate, sodium bicarbonate, calcium carbonate, and nitrate.
In some embodiments, in step 2), the washing is with acid and/or water.
In some embodiments, in step 2), the washed solution is selected from at least one of hydrochloric acid and nitric acid.
In some embodiments, the concentration of the hydrochloric acid is 1-5 mol/L.
In some embodiments, in the step 2), the temperature of the heat preservation calcination is 300-500 ℃, the heat preservation time is 1-6 h, and the temperature rise rate is 2-10 ℃/min.
In some embodiments, in step 3), the alcohol solution is selected from at least one of methanol, ethanol, isopropanol, n-butanol, and ethylene glycol.
In some embodiments, the liquid-solid ratio of the ammonium sulfide, the alcohol solution and the porous carbon material is (1-10 ml) to (5-50 ml): (0.1-0.5 g).
In some embodiments, in step 3), the stirring rate is 800 to 2000r/min and the temperature is 40 to 80 ℃.
In some embodiments, in step 3), the temperature of the heat preservation calcination is 700-900 ℃, the heat preservation time is 1-6 h, and the temperature rise rate is 2-10 ℃/min.
In some embodiments, in step 3), the protective atmosphere is selected from at least one of an inert gas and hydrogen.
In some embodiments, the inert gas is at least one of argon, helium.
In some embodiments, in steps 1), 2) and 3), the drying condition is drying for 2-48 h in an oven at 60-150 ℃.
The third purpose of the invention is to provide a carbon dioxide battery anode, which comprises the anode material or the anode material prepared by the preparation method.
A fourth object of the present invention is to provide a carbon dioxide battery comprising the carbon dioxide battery positive electrode.
The invention has the beneficial effects that:
(1) the anode material has higher specific surface area, so that the larger contact area is increased for reaction, and the catalytic efficiency is improved;
(2) the method for preparing the nitrogen-sulfur co-doped porous carbon material by using the betel nuts is simple, low in cost, wide and easily available in raw materials, good in structure and honeycomb-shaped, and is beneficial to efficient transmission of ions and electrons;
(3) the method for preparing the nitrogen-sulfur co-doped porous carbon material by using the betel nuts provides a new method for developing and utilizing high value-added products of the biomass waste;
(4) the anode material applied to the carbon dioxide battery has the advantages of good rate capability, higher specific capacity, smaller charge/discharge voltage difference (0.62V) and the like;
(5) the invention applies the anode material to the carbon dioxide battery to effectively improve CO2The utilization rate of the energy storage device and the release of electric energy have important application values in the fields of energy storage and environmental protection.
Drawings
FIG. 1 is an XRD pattern of a nitrogen and sulfur co-doped porous carbon material prepared from Areca catechu in example 1;
FIG. 2 is an SEM photograph of a nitrogen-and sulfur-codoped porous carbon material prepared from Areca catechu in example 1;
FIG. 3 is an EDS diagram of a nitrogen and sulfur co-doped porous carbon material prepared by using Areca catechu in example 1;
FIG. 4 is a nitrogen adsorption and desorption curve of a nitrogen and sulfur co-doped porous carbon material prepared from Areca catechu in example 1;
FIG. 5 shows that in example 1, the nitrogen and sulfur co-doped porous carbon material prepared from betel nut is used as the positive electrode material of the sodium-carbon dioxide battery at 0.1mA/cm2A charge-discharge curve at current density;
FIG. 6 shows nitrogen-and sulfur-codoped porous carbon material prepared from Areca catechu in example 1The anode material of the sodium-carbon dioxide battery is 0.1mA/cm2A cycle curve at current density;
FIG. 7 shows that in example 2, the nitrogen and sulfur co-doped porous carbon material prepared from betel nut is used as the positive electrode material of the sodium-carbon dioxide battery at 0.2mA/cm2A charge-discharge curve at current density;
FIG. 8 shows that in example 2, the nitrogen and sulfur co-doped porous carbon material prepared from betel nut is used as the positive electrode material of the sodium-carbon dioxide battery at 0.5mA/cm2Discharge capacity curve at current density.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
1. A preparation method of a positive electrode material comprises the following steps:
(1) cleaning, drying and mechanically crushing areca nuts, soaking the areca nuts in 2mol/L sodium hydroxide solution for 12 hours, and washing and drying the areca nuts;
(2) weighing 0.8g of potassium bicarbonate and 0.4g of betel nut pretreated in the step (1), adding water to dissolve the potassium bicarbonate and the betel nut, uniformly mixing, soaking for 24 hours, and placing in a 120 ℃ oven until the betel nut is completely dried; carrying out heat preservation calcination in air, wherein the heating rate is 5 ℃/min, the heat preservation temperature is 400 ℃, the heat preservation time is 2 hours, a porous carbon material is generated, and 2mol/L hydrochloric acid and deionized water are respectively washed and dried to obtain a dried porous carbon material;
(3) weighing 0.2g of the porous carbon material obtained in the step (2), soaking in 5ml of ammonium sulfide solution and 50ml of ethanol mixed solution, stirring at the rotating speed of 800r/min and the temperature of 60 ℃ until drying, then carrying out heat preservation calcination under the protective argon atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation temperature is 900 ℃, and the heat preservation time is 2 hours, thus obtaining the nitrogen and sulfur doped porous carbon material.
2. Characterization of the results
Fig. 1 is an XRD pattern of nitrogen and sulfur co-doped porous carbon material prepared by using betel nut in example 1. As can be seen from fig. 1, the prepared nitrogen and sulfur co-doped porous carbon material prepared from betel nut is an amorphous carbon material.
Fig. 2 is an SEM image of nitrogen and sulfur co-doped porous carbon material prepared by using betel nut in example 1. As can be seen from fig. 2, the prepared nitrogen and sulfur co-doped porous carbon material prepared from betel nuts is cellular.
Fig. 3 is an EDS diagram of a nitrogen and sulfur co-doped porous carbon material prepared by using betel nut in example 1. As can be seen from fig. 3, nitrogen and sulfur, which account for 87.33%, 9.48% and 3.19% by atomic percentage, respectively, have been successfully doped into the porous carbon material prepared from betel nut.
Fig. 4 is a nitrogen adsorption and desorption curve of the nitrogen and sulfur co-doped porous carbon material prepared by using betel nuts in example 1. As can be seen from FIG. 2, the curve has an apparent hysteresis loop type IV isotherm indicating the formation of a mesoporous structure. Specific surface area of 616m2In terms of a/g, the mean pore diameter is 2.65 nm.
3. Electrochemical performance test
Dissolving the prepared nitrogen and sulfur CO-doped porous carbon material into 2mL of absolute ethyl alcohol according to 80 wt.% of active material, 10 wt.% of active carbon and 10 wt.% of polytetrafluoroethylene to prepare uniform slurry, uniformly coating the uniform slurry on carbon paper, performing vacuum drying at 80 ℃ for 12h, and assembling into a battery with pure CO at 30 DEG C2And (5) carrying out charge and discharge performance test in atmosphere.
FIG. 5 shows that the nitrogen and sulfur co-doped porous carbon material prepared from betel nut is used as the anode material of the sodium-carbon dioxide battery at 0.1mA/cm2Charge and discharge curves at current density. As can be seen from fig. 5, when the material was used as the positive electrode of the sodium-carbon dioxide battery, the battery exhibited a low charge/discharge voltage difference of only 0.62V.
FIG. 6 shows the nitrogen and sulfur codoping made from Areca catechu LThe porous carbon material is used as the anode material of the sodium-carbon dioxide battery at 0.1mA/cm2Cycling profile at current density. As can be seen from fig. 6, the material used as the positive electrode of the sodium-carbon dioxide battery can stably circulate for more than 30 hours.
Example 2
1. A preparation method of a positive electrode material comprises the following steps:
(1) cleaning, drying and mechanically crushing areca nuts, soaking the areca nuts in 5mol/L sodium hydroxide solution for 24 hours, and washing and drying the areca nuts;
(2) weighing 1g of potassium bicarbonate and 1g of betel nuts pretreated in the step (1), adding water to dissolve the potassium bicarbonate and the betel nuts so as to uniformly mix the potassium bicarbonate and the betel nuts, soaking the mixture for 24 hours, and placing the soaked mixture in an oven at 120 ℃ until the mixture is completely dried; carrying out heat preservation calcination in air at the heating rate of 10 ℃/min at the heat preservation temperature of 500 ℃ for 1h to generate a porous carbon material, washing 1mol/L hydrochloric acid and deionized water respectively, and drying to obtain a dried porous carbon material;
(3) weighing 0.8g of the porous carbon material obtained in the step (2), soaking in 10ml of ammonium sulfide solution and 50ml of ethanol mixed solution, stirring at the rotating speed of 200r/min and the temperature of 60 ℃ until drying, then carrying out heat preservation calcination under the protective argon atmosphere, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 700 ℃, and the heat preservation time is 6 hours, thus obtaining the nitrogen and sulfur doped porous carbon material.
Through testing, the specific surface area of the prepared nitrogen and sulfur co-doped porous carbon material is 404m2(ii)/g, average pore diameter 3.06 nm; the carbon, nitrogen and sulfur account for 90.43%, 7.56% and 2.01% respectively in atomic percentage.
2. The electrochemical performance test results are as follows:
dissolving the prepared nitrogen and sulfur CO-doped porous carbon material into 2mL of absolute ethyl alcohol according to 80 wt.% of active material, 10 wt.% of active carbon and 10 wt.% of polytetrafluoroethylene to prepare uniform slurry, uniformly coating the uniform slurry on carbon paper, performing vacuum drying at 80 ℃ for 12h, and assembling into a battery with pure CO at 30 DEG C2And (5) carrying out charge and discharge performance test in atmosphere.
FIG. 7 shows that in example 2, the positive electrode material of the sodium-carbon dioxide battery, which is made of a nitrogen-sulfur co-doped porous carbon material prepared from betel nut and is used as the positive electrode material of the sodium-carbon dioxide battery, is 0.2mA/cm2A charge-discharge curve at current density; as can be seen from FIG. 7, the material was used as a positive electrode of a sodium-carbon dioxide battery at 0.2mA/cm2The cell exhibited a low charge/discharge voltage difference at current density of only 0.82V.
FIG. 8 shows that in example 2, the nitrogen and sulfur co-doped porous carbon material prepared from betel nut is used as the positive electrode material of the sodium-carbon dioxide battery at 0.5mA/cm2Discharge capacity curve at current density; as can be seen from FIG. 8, the material used as the positive electrode of the sodium-carbon dioxide battery can stably discharge, and the capacity of the battery reaches 7151 mAh/g.
Example 3
1. A preparation method of a positive electrode material comprises the following steps:
(1) cleaning, drying and mechanically crushing areca nuts, soaking the areca nuts in 1mol/L sodium hydroxide solution for 12 hours, and washing and drying the areca nuts;
(2) weighing 4g of potassium bicarbonate and 1g of betel nuts pretreated in the step (1), adding water to dissolve the potassium bicarbonate and the betel nuts so as to uniformly mix the potassium bicarbonate and the betel nuts, soaking the mixture for 24 hours, and placing the soaked mixture in an oven at 150 ℃ until the mixture is completely dried; carrying out heat preservation calcination in air at the heating rate of 10 ℃/min, the heat preservation temperature of 350 ℃ and the heat preservation time of 1h to generate a porous carbon material, respectively washing with 5mol/L hydrochloric acid and deionized water, and drying to obtain a dry porous carbon material;
(3) weighing 0.8g of the porous carbon material obtained in the step (2), soaking in 10ml of ammonium sulfide solution and 50ml of ethanol mixed solution, stirring at the rotating speed of 2000r/min and the temperature of 40 ℃ until drying, then carrying out heat preservation calcination under the protective argon atmosphere, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 700 ℃, and the heat preservation time is 6 hours, thus obtaining the nitrogen and sulfur doped porous carbon material.
Through tests, the specific surface area of the prepared nitrogen and sulfur co-doped porous carbon material is 368m2(ii)/g, average pore diameter 3.83 nm; the carbon, nitrogen and sulfur account for 89.03%, 8.26% and 2.71% in atomic percentage respectively.
Example 4
1. A preparation method of a positive electrode material comprises the following steps:
(1) cleaning, drying and mechanically crushing areca nuts, soaking the areca nuts in 3mol/L sodium hydroxide solution for 18 hours, and washing and drying the areca nuts;
(2) weighing 1.8g of potassium bicarbonate and 1g of areca catechu pretreated in the step (1), adding water to dissolve the potassium bicarbonate and the areca catechu, uniformly mixing the potassium bicarbonate and the areca catechu, soaking the mixture for 18 hours, and placing the mixture in an oven at 150 ℃ until the mixture is completely dried; carrying out heat preservation calcination in air at the heating rate of 10 ℃/min, the heat preservation temperature of 450 ℃ and the heat preservation time of 3h to generate a porous carbon material, respectively washing with 3mol/L hydrochloric acid and deionized water, and drying to obtain a dry porous carbon material;
(3) weighing 0.8g of the porous carbon material obtained in the step (2), soaking in 10ml of ammonium sulfide solution and 30ml of ethanol mixed solution, stirring at the rotating speed of 1600r/min and the temperature of 50 ℃ until drying, then carrying out heat preservation calcination under the protective argon atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation temperature is 800 ℃, and the heat preservation time is 2 hours, thus obtaining the nitrogen and sulfur doped porous carbon material.
The specific surface area of the prepared nitrogen and sulfur co-doped porous carbon material is 564m through testing2(ii)/g, average pore diameter of 2.47 nm; the carbon, nitrogen and sulfur account for 87.53%, 8.46% and 3.91% respectively in atomic percentage.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. The positive electrode material is characterized by comprising, by atomic percentage, 85% -95% of porous carbon, 2% -10% of nitrogen and 1% -5% of sulfur attached to the porous carbon, and the positive electrode material is characterized by comprising, by atomic percentage, the porous carbon, the nitrogen and the sulfur which are attached to the porous carbon, wherein the positive electrode material comprisesThe electrode material is cellular, and the BET specific surface area is 300-616 m2(ii)/g, the average pore size is 2-5 nm; the preparation method of the cathode material comprises the following steps:
1) soaking the crushed betel nuts in alkali liquor, washing and drying to obtain pretreated betel nuts;
2) adding an activating agent and the pretreated areca nuts into water for soaking, drying, carrying out heat preservation calcination, washing and drying to obtain a porous carbon material;
3) and (3) placing the porous carbon material in a mixed solution of ammonium sulfide and an alcohol solution, stirring to dry, and carrying out heat preservation and calcination in a protective atmosphere to obtain a nitrogen-sulfur doped porous carbon material, namely the anode material.
2. The positive electrode material according to claim 1, wherein the alkali solution is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide, and the concentration of the alkali solution is 1 to 5 mol/L.
3. The positive electrode material according to claim 1, wherein the activator is at least one selected from the group consisting of potassium bicarbonate, sodium bicarbonate, calcium carbonate, and nitrate.
4. The cathode material according to claim 1, wherein in the step 2), the washing is performed by using hydrochloric acid and/or water, and the concentration of the hydrochloric acid is 1-5 mol/L.
5. The positive electrode material according to claim 1, wherein in the step 2), the temperature of the heat preservation calcination is 300-500 ℃, the heat preservation time is 1-6 h, and the temperature rise rate is 2-10 ℃/min; in the step 3), the temperature of the heat preservation calcination is 700-900 ℃, the heat preservation time is 1-6 h, and the temperature rise rate is 2-10 ℃/min.
6. The positive electrode material as claimed in claim 1, wherein the liquid-solid ratio of the ammonium sulfide to the alcohol solution to the porous carbon material is (1-10 ml) to (5-50 ml): (0.1-0.5 g).
7. The positive electrode material according to claim 1, wherein in the step 3), the stirring rate is 800 to 2000r/min and the temperature is 40 to 80 ℃.
8. A carbon dioxide battery positive electrode comprising the positive electrode material according to any one of claims 1 to 7.
9. A carbon dioxide battery comprising the carbon dioxide battery positive electrode according to claim 8.
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