CN108557797B - Cobalt-doped porous carbon material and preparation method thereof - Google Patents
Cobalt-doped porous carbon material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cobalt-doped porous carbon material and a preparation method thereof. The preparation method comprises the following steps: (1) firstly, uniformly stirring cobalt acetate tetrahydrate, dicyandiamide and absolute ethyl alcohol; after being stirred uniformly, the mixture is heated to 70 to 75 ℃ to volatilize the solvent, and a complex sample is obtained; (2) dissolving the complex sample obtained in the step (1), ammonium acetate and gelatin in deionized water at 85-95 ℃, and then pouring the solution into a watch glass for vacuum drying; (3) and (3) carbonizing the sample subjected to vacuum drying in the step (2) at high temperature in an inert atmosphere, and soaking and etching the sample by hydrochloric acid after the sample is carbonized at high temperature to obtain the cobalt-doped porous carbon material. The method is environment-friendly, simple in preparation method and convenient for large-scale production. The cobalt-doped porous carbon material prepared by the method has high nitrogen content, high specific surface area and relatively uniform pore size distribution, and has good application prospect in the fields of toxic gas adsorption and electrochemistry.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a cobalt-doped porous carbon material and a preparation method thereof.
Background
Carbon materials are widely used as electrodes of supercapacitors because of their ready availability, easy processing, large surface area and porosity, low resistivity, good surface chemistry, environmental and physicochemical properties, and low cost. Energy storage is mainly due to the fact that charges are carried out on the surfaces of the carbon material electrode and the electrolyte. Due to the unique properties of the porous carbon material, the synthetic raw materials are rich and easy to obtain, so that the porous carbon material has common application in modern science. The porous carbon material has a series of characteristics of high chemical stability, acid and alkali resistance, high temperature resistance, electric conduction, heat conduction and the like, generally has developed pores, high specific surface area, high chemical stability, excellent heat resistance, acid and alkali resistance and unique electronic conduction property, and is one of indispensable important materials in modern industry.
In recent years, in order to further improve the application of the porous carbon material to the supercapacitor, it is common to dope a heteroatom (e.g., N, B, S or the like) or a heteroatom-containing group (amino group, nitro group, sulfonic group, or the like) into the surface or structure of the porous carbon material, so that various aspects of the performance of the porous carbon material are improved and enhanced. The development of supercapacitors has been facilitated by materials with pseudocapacitive properties, which improve the energy storage capability of the capacitor. However, most pseudocapacitances are redox reactions from the surface of the electrode material, and only a thin layer of the surface participates in the faradaic reaction. Furthermore, simple transition metal oxides, e.g. MnO, during Faraday charging2The electrical conductivity is poor and the conductive polymers are prone to mechanical degradation, preventing their use in electrode materials. Therefore, the construction of the carbon-based composite electrode material can not only improve the utilization rate of the active material, but also improve the conductivity and mechanical strength of the composite material.
The most commonly used nitrogen-containing precursors for preparing the nitrogen-containing supercapacitor electrode material comprise amino saccharides, melamine, benzylamine and the like. Although porous carbon with high nitrogen content can be obtained by in-situ nitrogen doping, there are many problems, such as: a plurality of organic chemical reagents are needed in the preparation process, and the price is relatively high; the introduction of metal and carbon materials in combination to prepare supercapacitors with better performance is worthy of further exploration.
Disclosure of Invention
The invention aims to provide a cobalt-doped porous carbon material with high nitrogen content and a preparation method thereof, which are environment-friendly, simple in preparation method and convenient for large-scale production.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a cobalt-doped porous carbon material comprises the following specific steps:
(1) firstly, uniformly stirring cobalt acetate tetrahydrate, dicyandiamide and absolute ethyl alcohol; after being stirred uniformly, the solution is heated to 70 ℃ to volatilize the solvent, and a complex sample is obtained;
(2) dissolving the complex sample obtained in the step (1), ammonium acetate and gelatin in deionized water at 85-95 ℃, and then pouring the solution into a watch glass for vacuum drying;
(3) and (3) carbonizing the sample subjected to vacuum drying in the step (2) at high temperature in an inert atmosphere, and soaking and etching the sample by hydrochloric acid after the sample is carbonized at high temperature to obtain the cobalt-doped porous carbon material.
In the invention, the mass ratio of cobalt acetate tetrahydrate, ammonium acetate, dicyandiamide and gelatin is (0.25-0.75): (1-2): (1-1.5): (1-2).
In the invention, in the step (2), the vacuum drying temperature is 55-65 ℃.
In the present invention, in step (3), the heating procedure for high-temperature carbonization is as follows: heating the mixture from room temperature to 600-950 ℃ at the heating rate of 5 ℃/min, and then preserving the heat for 1-5 h.
In the invention, in the step (3), the concentration of the hydrochloric acid is 0.1-2 mol/L.
In the invention, in the step (3), the soaking and etching time is 2-3 h.
The invention further provides a cobalt-doped porous carbon material prepared by the preparation method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, the gelatin is used as the carbon template of the material, the cobalt and the dicyandiamide have a complexing effect, and the cobalt and the dicyandiamide are doped into the gelatin in a complexing form, so that the raw materials can be mixed more uniformly, the nitrogen content of the material can be increased, and the performance of the material is improved.
2. The invention uses gelatin as carbon source to prepare porous carbon material, with wide source of raw material and low cost.
3. The supercapacitor material prepared by the method has a fluffy porous structure due to ammonia released by thermal decomposition of ammonium acetate, and the structure has uniform pore size distribution, high specific surface area and wide application prospect in the fields of adsorption, supercapacitors, even catalysis, fuel cells and the like.
Drawings
FIG. 1 is a graph showing the adsorption and desorption curves of the cobalt-doped porous carbon material obtained in example 1.
FIG. 2 is an SEM photograph of the cobalt-doped porous carbon material obtained in example 2.
FIG. 3 is a pore size distribution diagram of a cobalt-doped porous carbon material obtained in example 2.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any manner.
Example 1
The content and the composition of the cobalt-doped porous carbon material are as follows:
a preparation method of a cobalt-doped porous carbon material comprises the following steps:
firstly, uniformly stirring cobalt acetate tetrahydrate, dicyandiamide and absolute ethyl alcohol, and heating to 70 ℃ to volatilize a solvent; and then dissolving the complexed sample, ammonium acetate and gelatin in deionized water at 90 ℃, pouring the liquid into a watch glass after the solvent is uniform, and drying in vacuum at 60 ℃. Then the xerogel is put into a quartz boat, the quartz boat is put into a tube furnace to be heated in nitrogen atmosphere, the nitrogen flow rate is 50ml/min, the heating rate is 5 ℃/min, the temperature is slowly heated from room temperature to 600 ℃, and the carbonization time is 2 h; and then preparing hydrochloric acid into a 0.1M solution, etching for 3 hours, cleaning the carbonized material, performing suction filtration, and performing vacuum drying at 60 ℃ to obtain the cobalt-doped porous carbon material. The resulting material had a pore diameter of 4nm, a cumulative pore volume of 0.6ml/g and a specific surface area of 273m2The main element compositions are Co, N, C and O, and figure 1 is a suction and desorption curve chart of the cobalt-doped porous carbon material obtained in example 1.
Application example 1
Grinding the material of example 1, weighing 8mg, then weighing 1mg of carbon black and 0.1ml of 10mg/ml polytetrafluoroethylene, uniformly mixing, drying, wetting 3mg of mixture, coating on foamed nickel, and then drying; 200ml of 6M potassium hydroxide is prepared, 10ml of the foam nickel coated with the sample is soaked for 2h, and the specific capacitance of the material is 308F/g measured in 6M potassium hydroxide solution at a current density of 1A/g.
Example 2
The content and the composition of the cobalt-doped porous carbon material are as follows:
a preparation method of a cobalt-doped porous carbon material comprises the following steps:
firstly, uniformly stirring cobalt acetate tetrahydrate, dicyandiamide and absolute ethyl alcohol, and heating to 80 ℃ to volatilize a solvent; and then dissolving the complexed sample, ammonium acetate and gelatin in deionized water at 80 ℃, pouring the liquid into a watch glass after the solvent is uniform, and drying in vacuum at 60 ℃. Then the xerogel is put into a quartz boat, the quartz boat is put into a tube furnace to be heated in nitrogen atmosphere, the nitrogen flow rate is 50ml/min, the heating rate is 5 ℃/min, the temperature is slowly heated from room temperature to 750 ℃, and the carbonization time is 2 h; and then preparing hydrochloric acid into a 0.3M solution, etching for 2.5h, cleaning the carbonized material, performing suction filtration, and performing vacuum drying at 60 ℃ to obtain the cobalt-doped porous carbon material. The obtained material has a pore diameter of 4.0nm, a cumulative pore volume of 0.65ml/g and a specific surface area of 239m2And/g, the main element compositions are Co, N, C and O, and FIG. 2 is an SEM image of the cobalt-doped porous carbon material obtained in example 2. FIG. 3 is a pore size distribution diagram of a cobalt-doped porous carbon material obtained in example 2.
Application example 2
Grinding the material of the embodiment 2, weighing 8mg, then weighing 1mg of carbon black and 0.1ml of 10mg/ml polytetrafluoroethylene, uniformly mixing, drying, wetting 5mg of mixture, coating on foamed nickel, and then drying; 200ml of 6M potassium hydroxide were added, 10ml of the foam coated with the sample were allowed to soak for 2h, and the specific capacitance of the material was 462F/g, measured at a current density of 1A/g in 6M potassium hydroxide solution.
Example 3
The content and the composition of the cobalt-doped porous carbon material are as follows:
a preparation method of a cobalt-doped porous carbon material comprises the following steps:
firstly, uniformly stirring cobalt acetate tetrahydrate, dicyandiamide and absolute ethyl alcohol, and heating to 80 ℃ to volatilize a solvent; and then dissolving the complexed sample, ammonium acetate and gelatin in deionized water at 80 ℃, pouring the liquid into a watch glass after the solvent is uniform, and drying in vacuum at 60 ℃. Then the xerogel is put into a quartz boat, the quartz boat is put into a tube furnace to be heated in nitrogen atmosphere, the nitrogen flow rate is 50ml/min, the heating rate is 5 ℃/min, the temperature is slowly heated from room temperature to 850 ℃, and the carbonization time is 2 h; and then preparing hydrochloric acid into 1M solution, etching for 2 hours, cleaning the carbonized material, performing suction filtration, and performing vacuum drying at 60 ℃ to obtain the cobalt-doped porous carbon material. The resulting material had a pore size of 5.0nm, a cumulative pore volume of 0.49ml/g and a specific surface area of 239m2The main element composition is Co, N, C and O.
Application example 3
Grinding the material of the embodiment 3, weighing 8mg, then weighing 1mg of carbon black and 0.1ml of 10mg/ml polytetrafluoroethylene, uniformly mixing, drying, wetting 4mg of mixture, smearing on foamed nickel, and then drying; 200ml of 6M potassium hydroxide were added, 10ml of the foam coated with the sample were allowed to soak for 2h, and the specific capacitance of the material was 294F/g, measured in 6M potassium hydroxide solution at a current density of 1A/g.
Claims (6)
1. A preparation method of a cobalt-doped porous carbon material is characterized by comprising the following specific steps:
(1) firstly, uniformly stirring cobalt acetate tetrahydrate, dicyandiamide and absolute ethyl alcohol; after being stirred uniformly, the mixture is heated to 70 to 80 ℃ to volatilize the solvent, and a complex sample is obtained;
(2) dissolving the complex sample obtained in the step (1), ammonium acetate and gelatin in deionized water at the temperature of 80-95 ℃, and then pouring the solution into a watch glass for vacuum drying;
(3) and (3) carbonizing the sample subjected to vacuum drying in the step (2) at high temperature in an inert atmosphere, and soaking and etching the sample by hydrochloric acid after the sample is carbonized at high temperature to obtain the cobalt-doped porous carbon material.
2. The method according to claim 1, wherein the mass ratio of cobalt acetate tetrahydrate, ammonium acetate, dicyandiamide and gelatin is (0.25-0.75): (1-2): (1-1.5): (1-2).
3. The method according to claim 1, wherein in the step (2), the vacuum drying temperature is 55 to 65 ℃.
4. The production method according to claim 1, wherein in the step (3), the heating procedure for the high-temperature carbonization is as follows: heating the mixture from room temperature to 600-950 ℃ at the heating rate of 5 ℃/min, and then preserving the heat for 1-5 h.
5. The production method according to claim 1, wherein in the step (3), the hydrochloric acid concentration is 0.1 to 2 mol/L.
6. The method according to claim 1, wherein in the step (3), the immersion etching time is 2 to 3 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014201463A (en) * | 2013-04-02 | 2014-10-27 | 旭化成ケミカルズ株式会社 | Nitrogen-containing carbon material and method for producing the same, and electrode for fuel cell |
| CN105845915A (en) * | 2016-05-31 | 2016-08-10 | 陕西科技大学 | Method for preparing anode material of three-dimensional porous carbon skeleton/CoO composite structured lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014201463A (en) * | 2013-04-02 | 2014-10-27 | 旭化成ケミカルズ株式会社 | Nitrogen-containing carbon material and method for producing the same, and electrode for fuel cell |
| CN105845915A (en) * | 2016-05-31 | 2016-08-10 | 陕西科技大学 | Method for preparing anode material of three-dimensional porous carbon skeleton/CoO composite structured lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 钴、氮掺杂多孔碳作为氧还原催化剂的研究;葛余俊;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20160215(第2期);第B014-711页 * |
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