CN111204732B - Transition metal doped porous carbon material and preparation method and application thereof - Google Patents

Transition metal doped porous carbon material and preparation method and application thereof Download PDF

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CN111204732B
CN111204732B CN202010030911.4A CN202010030911A CN111204732B CN 111204732 B CN111204732 B CN 111204732B CN 202010030911 A CN202010030911 A CN 202010030911A CN 111204732 B CN111204732 B CN 111204732B
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porous carbon
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CN111204732A (en
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郭玉鹏
吴琴
姜雪
李雅洁
杨枝晨
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Jilin University
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Abstract

The invention provides a transition metal doped porous carbon material and a preparation method and application thereof, and relates to the technical field of preparation of porous carbon materials. The preparation method provided by the invention does not use an activating agent, and comprises the following steps: mixing cane molasses and ethanol solution of soluble transition metal salt, and drying to obtain mixed solid powder; carrying out carbonization reaction on the mixed solid powder under inert atmosphere to obtain a carbonization reaction product; and sequentially carrying out acid etching, washing and drying on the carbonization reaction product to obtain the transition metal doped porous carbon material. According to the invention, cane molasses is used as a carbon source, transition metal is doped to prepare the porous carbon material, and the transition metal doped porous carbon material with developed pore structure, large pore volume, high specific surface area, high specific capacitance and stable electrochemical performance is obtained after etching by using an etching solution. The preparation method provided by the invention does not need to use an active agent to form pores at a high temperature, is simple and convenient to operate, consumes less energy, and is green and economical.

Description

Transition metal doped porous carbon material and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of porous carbon materials, and particularly relates to a transition metal doped porous carbon material and a preparation method and application thereof.
Background
In recent years, industrial development becomes an important engine for regional economic development, but waste generated in the industrial production process also becomes a main cause for aggravating ecological environment deterioration, and the method is contrary to the green development concept of the current times. Therefore, it is important to solve the problem of recycling of waste resources. Cane molasses is a waste of sugar industry, and is a dark brown liquid with sweet taste, thick and semi-liquidity, commonly called syrup, left after sugar is made by a plurality of complicated procedures of heating, neutralizing, precipitating, filtering, concentrating, crystallizing and the like after cane is squeezed into cane juice by the sugar industry. At present, cane molasses is mainly used in the field of fermentation, but still faces some problems, such as complex process, high cost, possibility of secondary pollution in the production process and the like.
In the prior art, for example, "Hanxue, Zhouba, Guxue, et al]The advanced chemical bulletin (6): 1135-. A method of making a high performance carbon material from molasses is disclosed. However, the above methods all use activators such as alkali substances (e.g. KOH) or salt substances (e.g. K) in the preparation process2CO3) The pore-forming is carried out under the high-temperature condition, which not only consumes energy but also corrodes equipment, and the working procedures are relatively complicated.
Disclosure of Invention
In view of this, the invention aims to provide a transition metal doped porous carbon material, and a preparation method and application thereof. The preparation method provided by the invention does not need to use an activating agent to form holes at high temperature, is simple and convenient to operate, consumes less energy, and is green and economical.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a transition metal doped porous carbon material, which does not use an activating agent and comprises the following steps:
mixing and heating cane molasses and an ethanol solution of soluble transition metal salt, and drying to obtain mixed solid powder;
carrying out carbonization reaction on the mixed solid powder under inert atmosphere to obtain a carbonization reaction product;
sequentially carrying out acid etching, washing and drying on the carbonization reaction product to obtain a transition metal doped porous carbon material;
the temperature of the carbonization reaction is 700-900 ℃, and the time of the carbonization reaction is 1-2 h.
Preferably, the heating rate of heating to the temperature of the carbonization reaction is 10-20 ℃/min.
Preferably, the mass ratio of the cane molasses to the soluble transition metal salt is 200 (1-20).
Preferably, the transition metal element in the soluble transition metal salt comprises cobalt, iron, nickel or manganese.
Preferably, the etching liquid for acid etching is hydrochloric acid, sulfuric acid or nitric acid.
The preparation method according to claim 5, wherein the molar concentration of the etching solution is 1-2 mol/L.
Preferably, the acid etching time is 0.5-1 h.
Preferably, the heating temperature is 80-90 ℃, and the heating time is 2-3 h.
The invention also provides the transition metal doped porous carbon material prepared by the preparation method in the technical scheme, wherein the porosity of the transition metal doped porous carbon material is 27.52-43.88%, and the doping amount of the transition metal is 0.73-5.84%.
The invention also provides application of the transition metal doped porous carbon material in the technical scheme in an adsorbent, a super capacitor and an electrocatalyst.
The preparation method provided by the invention does not use an activating agent, and comprises the following steps: mixing cane molasses and ethanol solution of soluble transition metal salt, and drying to obtain mixed solid powder; carrying out carbonization reaction on the mixed solid powder under inert atmosphere to obtain a carbonization reaction product; sequentially carrying out acid etching, washing and drying on the carbonization reaction product to obtain a transition metal doped porous carbon material; the temperature of the carbonization reaction is 700-900 ℃, and the time of the carbonization reaction is 1-2 h. In the invention, the sugar cane molasses contains higher sugar content, wherein the sugar is 36 percent, other sugar is 24 percent, and the sugar cane molasses is used as carbonThe porous carbon material is prepared by doping transition metal, and the transition metal-doped porous carbon material with developed pore structure, large pore volume, high specific surface area, high specific capacitance and stable electrochemical performance is obtained after etching by the etching solution, and the carbon content of the prepared transition metal-doped porous carbon material can reach 77.43%. The preparation method provided by the invention carries out acid etching on the prepared carbonization reaction product, carries out pore-forming at room temperature, does not need to use an active agent to carry out pore-forming at high temperature, and has the advantages of simple and convenient operation, low energy consumption, greenness and economy. The preparation method provided by the invention not only can solve the problem of recycling of the sugar industry waste and improve the resource utilization rate, but also can provide a new method for preparing the high-performance porous carbon material. The example results show that the porosity of the transition metal doped porous carbon material prepared by the invention is 27.52-43.88%, the doping amount of the transition metal is 0.73-5.84%, and the pore volume is 0.3901-0.5046 cm3A specific surface area of 641.54-831.30 m/g2The specific capacitance is 102.95-204.2F/g, and the carbon content is 64.86-77.43%.
Drawings
FIG. 1 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 1 at 1A/g;
FIG. 2 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 2 at 1A/g;
FIG. 3 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 3 at 1A/g;
FIG. 4 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 4 at 1A/g;
FIG. 5 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 5 at 1A/g;
FIG. 6 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 6 at 1A/g;
FIG. 7 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 7 at 1A/g;
FIG. 8 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 8 at 1A/g;
FIG. 9 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 9 at 1A/g;
FIG. 10 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 10 at 1A/g;
FIG. 11 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 11 at 1A/g;
FIG. 12 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 12 at 1A/g;
FIG. 13 is a constant current charge/discharge curve under the condition of 1A/g for the cobalt-doped porous carbon material prepared in example 13;
FIG. 14 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in example 14 at 1A/g;
FIG. 15 is a constant current charge/discharge curve of the cobalt-doped porous carbon material prepared in comparative example 1 at 1A/g.
Detailed Description
The invention provides a preparation method of a transition metal doped porous carbon material, which does not use an activating agent and comprises the following steps:
mixing cane molasses and ethanol solution of soluble transition metal salt, and drying to obtain mixed solid powder;
carrying out carbonization reaction on the mixed solid powder under inert atmosphere to obtain a carbonization reaction product;
sequentially carrying out acid etching, washing and drying on the carbonization reaction product to obtain a transition metal doped porous carbon material;
the temperature of the carbonization reaction is 700-900 ℃, and the time of the carbonization reaction is 1-2 h.
In the present invention, the raw materials used are all those conventionally available in the art or those prepared by the conventional preparation methods in the art, unless otherwise specified.
The invention mixes and heats cane molasses and ethanol solution of soluble transition metal salt, and then dries to obtain mixed solid powder. In the invention, the cane molasses is preferably liquid cane molasses discarded in the sugar industry, and the water content in the liquid cane molasses is preferably 20-25%. In the invention, the mass ratio of the cane molasses to the soluble transition metal salt is preferably 200 (1-20), more preferably 200 (2-10), and even more preferably 200 (2-4). In the present invention, the soluble transition metal salt preferably includes a transition metal nitrate, a transition metal acetate or a transition metal chloride; the transition metal element in the soluble transition metal salt preferably comprises cobalt, iron, nickel or manganese. The dosage of the ethanol is not specially limited, and the soluble transition metal salt can be dissolved.
In the invention, the mixing mode is preferably stirring, the stirring speed is preferably 20r/min, the heating temperature is preferably 80-90 ℃, the heating time is preferably 2-3 h, and the heating rate for raising the temperature to the mixing temperature is preferably 5 ℃/min. According to the invention, cane molasses and an ethanol solution of soluble transition metal salt are mixed under a heating condition, the transition metal salt is decomposed into corresponding transition metal oxides, and in the subsequent carbonization reaction process, the cane molasses undergoes deoxidation, cyclization, polycondensation and crosslinking reactions, so that most of non-carbon elements such as hydrogen and oxygen are removed, a porous carbon material is obtained, and the carbon content is increased; the transition metal oxide and the porous carbon material are subjected to reduction reaction to be reduced into metal simple substances, the metal simple substances can be dissolved in the amorphous carbon, metal particles are gradually separated out, and the transition metal doped porous carbon material is prepared.
In the present invention, the drying is preferably drying, and in the embodiment, the drying may be specifically performed in an oven; the drying temperature is preferably 140-150 ℃, and the drying time is preferably 5-6 h. The present invention preferably dries the weight of the mixture to a constant weight to obtain the mixed solid powder.
After the mixed solid powder is obtained, the mixed solid powder is subjected to carbonization reaction under inert atmosphere to obtain a carbonization reaction product. In the invention, the temperature of the carbonization reaction is 700-900 ℃, more preferably 750-800 ℃, the time of the carbonization reaction is 1-2 h, more preferably 1.5h, and the heating rate of heating to the temperature of the carbonization reaction is preferably 10-20 ℃/min, more preferably 10 ℃/min. In the present invention, the protective atmosphere is preferably a nitrogen atmosphere. The carbonization reaction conditions adopted by the invention can ensure the porous structure of the transition metal doped porous carbon material and the doping effect of the transition metal. In the invention, when the temperature of the carbonization reaction is too high, the graphitization degree of the transition metal doped porous carbon material is too high, the density is high, and partial holes in the porous carbon material collapse; when the temperature of the carbonization reaction is too low, the soluble transition metal salt is difficult to be converted into a metal simple substance, and the subsequent process is difficult to be carried out; when the time of the carbonization reaction is too long, the porous carbon material holes can collapse; when the time period of the carbonization reaction is over, the carbonization reaction may not be completely performed.
After obtaining the carbonization reaction product, the invention sequentially carries out acid etching, washing and drying on the carbonization reaction product to obtain the transition metal doped porous carbon material. In the invention, the etching liquid for acid etching preferably comprises hydrochloric acid, sulfuric acid or nitric acid, and the time for acid etching is preferably 0.5-1 h; the molar concentration of the etching liquid is preferably 1-2 mol/L, and more preferably 1 mol/L. The invention preferably puts the carbonized reaction product in the etching solution for acid etching. The invention carries out acid etching on the carbonized product, can remove the transition metal in the carbonized product, improves the pore structure of the carbonized product and improves the specific capacitance of the transition metal material.
In the invention, the washing is preferably carried out in distilled water, and the specific operation mode of the washing is not particularly limited, and the pH value of the acid etching product can be washed to be neutral.
In the present invention, the drying is preferably oven drying; the embodiment can be specifically carried out in a drying box; the drying temperature is preferably 120-140 ℃, and the drying time is preferably 12-24 h.
After the washing product is dried, the invention preferably crushes the dried product to obtain the transition metal doped porous carbon material. In the present invention, the crushing is preferably performed in a mortar, and the particle size of the crushed product is preferably 50 to 100 nm.
The invention also provides the transition metal doped porous carbon material prepared by the preparation method in the technical scheme, wherein the porosity of the transition metal doped porous carbon material is 27.52-43.88%, and the doping amount of the transition metal is 0.73-5.84%.
The invention also provides application of the transition metal doped porous carbon material in the technical scheme in an adsorbent, a super capacitor and an electrocatalyst.
In the invention, the transition metal doped porous carbon material is preferably used as a carrier of an adsorbent and a catalyst in the application of the adsorbent and the catalyst; in supercapacitor applications, it is preferred to use as a double layer capacitor. The application mode of the transition metal doped porous carbon material in the catalyst and the supercapacitor is not particularly limited, and the application mode is known by the skilled person in the art.
The transition metal doped porous carbon material and the preparation method and application thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dissolving 1g of cobalt nitrate hexahydrate in 10mL of ethanol to obtain a cobalt nitrate ethanol solution; mixing the obtained cobalt nitrate ethanol solution with 100g of cane molasses, and stirring for 2 hours at 80 ℃; and then placing the obtained mixed liquid in an oven at 140 ℃ for drying for 5 hours to obtain mixed solid powder.
And carrying out carbonization reaction on the obtained mixed solid powder at 700 ℃ in a nitrogen atmosphere for 1.5 hours to obtain a carbonization reaction product.
And (3) carrying out acid etching on the obtained carbonization reaction product by using hydrochloric acid with the molar concentration of 1mol/L, washing the carbonization reaction product to be neutral by using distilled water, drying the carbonization reaction product for 12 hours at 120 ℃, and crushing the carbonization reaction product in a mortar, wherein the particle size of the crushed carbonization reaction product is 50-100 nm, so as to prepare the cobalt-doped porous carbon material.
Testing the pore structure and performance of the prepared cobalt-doped porous carbon materialThe test results showed that the porosity was 31.85%, the doping amount of cobalt metal was 1.46%, and the pore volume was 0.4185cm3Per g, specific surface area 785.7m2The specific capacitance is 160.15F/g, and the carbon content is 77.43 percent.
Fig. 1 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 1 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 160.15F/g.
Example 2
The temperature of the carbonization reaction in example 1 was changed to 750 ℃, and the remaining preparation conditions were the same as in example 1, to prepare a cobalt-doped porous carbon material.
The pore structure and performance of the prepared cobalt-doped porous carbon material are tested, and the test result shows that the porosity is 38.96%, the doping amount of cobalt metal is 1.46%, and the pore capacity is 0.4458cm3Per g, specific surface area 796.46m2The specific capacitance is 195.95F/g, and the carbon content is 65.42%.
Fig. 2 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 2 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 195.95F/g.
Example 3
The temperature of the carbonization reaction in example 1 was changed to 800 ℃, and the remaining preparation conditions were the same as in example 1, to prepare a cobalt-doped porous carbon material.
Testing the pore structure and performance of the prepared cobalt-doped porous carbon material, and obtaining a test resultThe porosity was 43.88%, the amount of cobalt metal doped was 1.46%, and the pore volume was 0.5046cm3In a ratio of 831.30m2The specific capacitance is 204.2F/g, and the carbon content is 70.15%.
Fig. 3 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 3 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 204.2F/g.
Example 4
The temperature of the carbonization reaction in example 1 was changed to 850 ℃, and the remaining preparation conditions were the same as in example 1, to prepare a cobalt-doped porous carbon material.
The pore structure and performance of the prepared cobalt-doped porous carbon material are tested, and the test result shows that the porosity is 35.72%, the doping amount of cobalt metal is 1.46%, and the pore volume is 0.4205cm3Per g, specific surface area 754.62m2The specific capacitance was 150.45F/g, and the carbon content was 70.55%.
Fig. 4 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 4 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 150.45F/g.
Example 5
The temperature of the carbonization reaction in example 1 was changed to 900 ℃, and the remaining preparation conditions were the same as in example 1, to prepare a cobalt-doped porous carbon material.
The prepared cobalt-doped porous carbon material is tested for pore structure and performance, and the test result shows that the porosity is 28.71 percentThe doping amount of cobalt metal is 1.46%, and the pore volume is 0.395cm3Per g, specific surface area 709.31m2The specific capacitance was 109.35F/g, and the carbon content was 72.89%.
Fig. 5 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 5 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 109.35F/g.
Example 6
The cobalt nitrate hexahydrate in example 3 was changed to 0.5g, and the remaining preparation conditions were the same as in example 3, to prepare a cobalt-doped porous carbon material.
The pore structure and performance of the prepared cobalt-doped porous carbon material are tested, and the test results show that the porosity is 32.27%, the doping amount of cobalt metal is 0.73%, and the pore volume is 0.4100cm3Per g, specific surface area 760.35m2The specific capacitance was 157.5F/g, and the carbon content was 72.58%.
Fig. 6 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 6 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 157.5F/g.
Example 7
The cobalt nitrate hexahydrate in example 3 was changed to 2g, and the remaining preparation conditions were the same as in example 3, thereby preparing a cobalt-doped porous carbon material.
The pore structure and the performance of the prepared cobalt-doped porous carbon material are tested, and the test result shows that the porosity is 42.08 percent and the doping amount of cobalt metal2.92% and a pore volume of 0.4387cm3Per g, specific surface area 726.32m2(iv)/g, specific capacitance of 196F/g, carbon content of 73.93%.
Fig. 7 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 7 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 196F/g.
Example 8
The cobalt nitrate hexahydrate in example 3 was changed to 3g, and the remaining preparation conditions were the same as in example 3, to prepare a cobalt-doped porous carbon material.
The pore structure and performance of the prepared cobalt-doped porous carbon material are tested, and the test result shows that the porosity is 39.79%, the doping amount of cobalt metal is 4.38%, and the pore capacity is 0.4239cm3Per g, specific surface area 712.24m2The specific capacitance was 188.25F/g, and the carbon content was 72.11%.
Fig. 8 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 8 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 188.25F/g.
Example 9
The cobalt nitrate hexahydrate in example 3 was changed to 4g, and the remaining preparation conditions were the same as in example 3, thereby preparing a cobalt-doped porous carbon material.
The pore structure and performance of the prepared cobalt-doped porous carbon material were tested, and the test results showed that the porosity was 43.29%, the doping amount of cobalt metal was 5.84%, and the pore volume was 0.4006cm3Per g, specific surface area 641.54m2The specific capacitance is 167.8F/g, and the carbon content is 73.22%.
Fig. 9 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 9 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 167.8F/g.
Example 10
The time of the carbonization reaction in example 3 was changed to 1h, and the remaining preparation conditions were the same as in example 3, thereby preparing a cobalt-doped porous carbon material.
The pore structure and performance of the prepared cobalt-doped porous carbon material are tested, and the test result shows that the porosity is 30.12%, the doping amount of cobalt metal is 1.46%, and the pore volume is 0.4005cm3Per g, specific surface area 710.74m2The specific capacitance was 115.65F/g, and the carbon content was 67.56%.
Fig. 10 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 10 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 115.65F/g.
Example 11
The time of the carbonization reaction in example 3 was changed to 2 hours, and the remaining preparation conditions were the same as in example 3, thereby preparing a cobalt-doped porous carbon material.
The pore structure and performance of the prepared cobalt-doped porous carbon material are tested, and the test results show that the porosity is 32.76%, the doping amount of cobalt metal is 1.46%, and the pore volume is 0.4193cm3Per g, specific surface area 764.32m2The specific capacitance is 157.55F/g, and the carbon content is 64.85 percent.
Fig. 11 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 11 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 157.55F/g.
Example 12
The hydrochloric acid in the example 3 was changed to dilute sulfuric acid, and the remaining preparation conditions were the same as in the example 3, thereby preparing a cobalt-doped porous carbon material.
The pore structure and performance of the prepared cobalt-doped porous carbon material are tested, and the test result shows that the porosity is 31.25%, the doping amount of cobalt metal is 1.46%, and the pore volume is 0.4015cm3Per g, specific surface area 745.55m2The specific capacitance was 138.5F/g, and the carbon content was 66.60%.
Fig. 12 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 12 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 138.5F/g.
Example 13
The concentration of hydrochloric acid in example 3 was changed to 2mol/L, and the remaining preparation conditions were the same as in example 3, thereby preparing a cobalt-doped porous carbon material.
The pore structure and performance of the prepared cobalt-doped porous carbon material are tested, and the test result shows that the porosity is 29.75%, the doping amount of cobalt metal is 1.46%, and the pore volume is 0.3901cm3In terms of/g, specific surface area of704.11m2The specific capacitance was 138.9F/g, and the carbon content was 65.73%.
Fig. 13 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 13 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 138.9F/g.
Example 14
The cobalt nitrate hexahydrate in the example 1 was changed to nickel nitrate hexahydrate, the temperature of the carbonization reaction was changed to 800 ℃, and the rest of the preparation conditions were the same as those in the example 1, thereby preparing a cobalt-doped porous carbon material.
The pore structure and performance of the prepared cobalt-doped porous carbon material are tested, and the test results show that the porosity is 33.51%, the doping amount of nickel metal is 1.43%, and the pore capacity is 0.4013cm3Per g, specific surface area 757.42m2The specific capacitance is 150F/g, and the carbon content is 64.86%.
Fig. 14 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in example 14 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 150F/g.
Comparative example 1
The comparative example was prepared under the same conditions as in example 1 except that the carbonized reaction product was not acid-etched with an etching solution.
The pore structure and performance of the prepared cobalt-doped porous carbon material were tested, and the test results showed that the porosity was 27.52%, the doping amount of cobalt metal was 1.46%, and the pore volume was 0.390cm3Per g, specific surface area 704.41m2The specific capacitance is 102.95F/g, and the carbon content is 66.71%.
Fig. 15 is a constant current charge and discharge curve of the cobalt-doped porous carbon material prepared in comparative example 1 under a condition of 1A/g, and it can be seen from the graph that the charge and discharge curve is isosceles triangle-like, which shows that the pore structure inside the porous carbon material provides an excellent transmission channel for electrolyte ions, and the developed pores reduce the resistance of ion transfer, enhance elastic buffering, and facilitate the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge, and it can be seen from the graph that the specific capacitance of the porous carbon material is 102.95F/g.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A preparation method of a transition metal doped porous carbon material is characterized by comprising the following steps without using an activating agent:
mixing and heating cane molasses and an ethanol solution of soluble transition metal salt, and drying to obtain mixed solid powder;
carrying out carbonization reaction on the mixed solid powder under inert atmosphere to obtain a carbonization reaction product;
sequentially carrying out acid etching, washing and drying on the carbonization reaction product to obtain a transition metal doped porous carbon material;
the temperature of the carbonization reaction is 700-900 ℃, and the time of the carbonization reaction is 1-2 h;
the cane molasses is waste liquid cane molasses in sugar industry, and the water content of the liquid cane molasses is 20% -25%;
the mass ratio of the cane molasses to the soluble transition metal salt is 200 (1-20);
the etching liquid for acid etching is hydrochloric acid, sulfuric acid or nitric acid;
the molar concentration of the etching liquid is 1-2 mol/L; the acid etching time is 0.5-1 h.
2. The production method according to claim 1, wherein a temperature rise rate of raising the temperature to the temperature of the carbonization reaction is 10 to 20 ℃/min.
3. The method according to claim 1, wherein the transition metal element in the soluble transition metal salt comprises cobalt, iron, nickel, or manganese.
4. The preparation method according to claim 1, wherein the heating temperature is 80-90 ℃ and the heating time is 2-3 h.
5. The transition metal-doped porous carbon material prepared by the preparation method according to any one of claims 1 to 4, wherein the porosity of the transition metal-doped porous carbon material is 27.52 to 43.88%, and the doping amount of the transition metal is 0.73 to 5.84%.
6. Use of the transition metal doped porous carbon material of claim 5 in adsorbents, supercapacitors and electrocatalysts.
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