CN115116763A - Cyano-rich porous carbon, preparation method thereof and application of cyano-rich porous carbon as electrode material of supercapacitor - Google Patents
Cyano-rich porous carbon, preparation method thereof and application of cyano-rich porous carbon as electrode material of supercapacitor Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides cyano-rich porous carbon, a preparation method thereof and application of the cyano-rich porous carbon as a supercapacitor electrode material, wherein the cyano-rich porous carbon has a micropore and mesopore hierarchical pore structure, and the specific surface area is 1000-1500 m 2 The volume percentage of the micropores accounts for 60-70%, the volume percentage of the mesopores accounts for 30-40%, and the mass percentage of the cyano groups accounts for 4-11%. The cyano-rich porous carbon provided by the invention has a hierarchical porous structure, is large in specific surface area, has excellent cycling stability and electrochemical performance when being used as an electrode material, and is simple in preparation method step, mild in reaction condition, good in repeatability and beneficial to large-scale production and preparation.
Description
Technical Field
The invention belongs to the technical field of capacitors characterized by material composition or structural characteristics in electrodes, and particularly relates to cyano-rich porous carbon, a preparation method thereof and application of the cyano-rich porous carbon as a supercapacitor electrode material.
Background
Supercapacitors, also known as electrochemical capacitors, are a promising class of high performance electrochemical energy storage devices. The super capacitor has excellent rate performance, high power density and long cycle life, and is generally composed of four parts, namely an electrode material, a diaphragm, a current collector and electrolyte. The electrode material determines the performance of the super capacitor to a great extent, and the large specific surface area and the appropriate porous structure are favorable for storage, diffusion and transfer of ions and can show good electrochemical performance.
The electrode material includes carbon material, transition metal compound, conductive polymer, etc., wherein the carbon material (including carbon dots, graphene, carbon nanotubes, porous carbon, etc.) has been a research hotspot due to its excellent conductivity, large specific surface area and stable electrochemical properties. The hydrothermal method is widely applied to the synthesis of porous carbon due to the advantages of low cost, high efficiency, easy regulation, capability of greatly reserving functional groups contained in the material and the like. Carbon sources used for the hydrothermal synthesis of carbon materials so far can be classified into the following categories: pure carbohydrates (glucose, sucrose, cyclodextrin, cellulose, starch, etc.); large molecular weight biomass (lignin, chitosan, etc.); biomass raw materials (pericarp, leaves, shrimp shell, pine needle, etc.). However, the carbon source has a large molecular weight and a relatively complex structure, so that the formation mechanism of the carbon material is also relatively complex, and in addition, the reaction process is difficult to control accurately, so that the structure of the prepared carbon material is uncontrollable, and in addition, the system has a large variety of functional groups and poor stability, which is not favorable for the design and synthesis of high-performance electrode materials.
In order to improve the electrochemical performance of the electrode material of the supercapacitor, reduce the production cost and simplify the preparation process, a micromolecular carbon source is introduced into the synthesis of the carbon material, and then the cyano-rich porous carbon is developed through further activation and carbonization, wherein the electronic structure of carbon atoms can be changed by doping nitrogen atoms contained in cyano groups, and the conductivity and the chemical stability of the carbon material are improved. In addition, the polarization effect of the cyano can increase the wettability of the electrode material (the electrode material can be better soaked by electrolyte and is beneficial to the generation of electrochemical reaction), and further the electrochemical performance of the material is improved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides cyano-rich porous carbon, a preparation method thereof and application of the cyano-rich porous carbon as a supercapacitor electrode material.
In order to achieve the purpose, the technical scheme is as follows:
the cyano-rich porous carbon has a micropore and mesopore hierarchical pore structure, and the specific surface area is 1000-1500 m 2 The volume percentage of the micropores accounts for 60-70%, the volume percentage of the mesopores accounts for 30-40%, and the mass percentage of the cyano groups accounts for 4-11%.
The invention also provides a preparation method of the cyano-rich porous carbon, which comprises the following specific steps:
1) performing ultrasonic dispersion on glyoxal and acrylonitrile in deionized water uniformly, performing hydrothermal reaction, and performing post-treatment to obtain a precursor;
2) mixing the precursor obtained in the step 1) with an aqueous solution of an activating agent for activation reaction, carbonizing the obtained solid product, and washing and drying to obtain the cyano-rich porous carbon material.
According to the scheme, the molar ratio of the glyoxal to the acrylonitrile in the step 1) is 1: 0.5-2, wherein the molar volume ratio of the glyoxal to the deionized water is 0.001-0.005 mol/mL.
Preferably, the molar ratio of glyoxal to acrylonitrile is 1: 0.5 to 1.
According to the scheme, the hydrothermal reaction conditions in the step 1) are as follows: reacting for 12-24 h at 160-200 ℃.
According to the scheme, the activating agent in the step 2) is one of sodium hydroxide, potassium hydroxide, zinc chloride and calcium chloride, and the concentration of the aqueous solution of the activating agent is 0.5-2 mol/L.
According to the scheme, the mass ratio of the precursor in the step 2) to the activating agent in the aqueous solution of the activating agent is 1: 0.5 to 3.
According to the scheme, the activation reaction conditions in the step 2) are as follows: reacting for 1-15 h at 100-180 ℃.
According to the scheme, the carbonization treatment in the step 2) has the following process conditions: and under the nitrogen atmosphere, heating from room temperature to 500-900 ℃ at the heating rate of 3-8 ℃/min, and preserving heat for 2 hours.
The invention also comprises application of the cyano-rich porous carbon as an electrode material of a supercapacitor.
The invention selects micromolecular glyoxal and acrylonitrile as carbon source and nitrogen source, and the micromolecular components are uniformly mixed in liquid phase under the condition of hydrothermal reaction. Firstly, glyoxal is hydrolyzed and polymerized under a hydrothermal condition to generate an intermediate, aldehyde groups on the intermediate and acrylonitrile are subjected to free radical addition reaction to generate a precursor with cyano groups reserved and relatively stable, then the obtained precursor is subjected to activation treatment to promote the formation of a hierarchical porous structure, so that an excellent ion diffusion channel is provided, in addition, in the activation process, the formation of the porous carbon structure is facilitated by high temperature (100-180 ℃) and saturation pressure, and finally, the cyano-rich porous carbon electrode material with large specific surface area, stable cycle performance, good wettability and excellent electrochemical performance is obtained through further carbonization.
The invention has the beneficial effects that: 1. the cyano-rich porous carbon provided by the invention has a hierarchical porous structure, is large in specific surface area, and has excellent cycling stability and electrochemical performance when used as an electrode material; 2. the preparation method disclosed by the invention is simple in steps, mild in reaction conditions, good in repeatability and beneficial to large-scale production and preparation.
Drawings
FIG. 1 is an x-ray photoelectron spectrum of a cyano-rich porous carbon electrode material prepared in example 1 of the present invention;
FIG. 2 is a nitrogen adsorption/desorption isotherm (BET) plot of the cyano-rich porous carbon electrode material prepared in example 1;
FIG. 3 is a pore size distribution diagram of the cyano-rich porous carbon electrode material prepared in example 1;
FIG. 4 is a Cyclic Voltammetry (CV) test chart of the cyano-rich porous carbon electrode material prepared in example 1;
FIG. 5 is a constant current charge-discharge (GCD) test chart of the cyano-rich porous carbon electrode material prepared in example 1;
fig. 6 is a charge-discharge cycle test chart of the cyano-rich porous carbon electrode material prepared in example 1.
Detailed Description
According to the method, micromolecular glyoxal and acrylonitrile are used as raw materials, activation and carbonization are carried out after a precursor is synthesized, the reaction mechanism is clear, the process is easy to control, and the obtained cyano-rich porous carbon is excellent in performance and stable in circulation. The embodiment of the invention provides a super capacitor electrode material with great potential.
In order to make the aforementioned and other objects, features, and advantages of the present invention more comprehensible, several embodiments of the present invention are described below.
Example 1
A cyano-rich porous carbon is prepared by the following steps:
1) ultrasonically dispersing glyoxal (10mL, 0.22mol) and acrylonitrile (10mL, 0.15mol) with 50mL of deionized water uniformly, placing the mixture into a stainless steel hydrothermal reaction kettle with the volume of 100mL and a Teflon lining, carrying out hydrothermal reaction at 180 ℃ for 24 hours, after the reaction is finished, naturally cooling the hydrothermal reaction kettle to room temperature, filtering out brown solid granular substances, washing the brown solid granular substances with ethanol, acetone and deionized water in sequence until the filtrate is colorless and neutral, and then carrying out vacuum drying on the sample at 50 ℃ overnight to obtain a precursor;
2) mixing 3g of precursor with 60mL of KOH solution (the concentration is 1mol/L), transferring the mixture into a stainless steel hydrothermal reaction kettle with the volume of 100mL and a Teflon lining, carrying out activation reaction for 12 hours at 140 ℃, drying the product for 24 hours at 100 ℃, and fully removing water to obtain an activated precursor;
3) and (3) putting 1g of the activated precursor into a tubular furnace, heating to 700 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 2h, washing for several times by using 1mol/L HCl solution and deionized water in sequence to remove KOH and other byproducts, and drying to obtain the cyano-rich porous carbon.
FIG. 1 is an X-ray photoelectron spectroscopy (XPS) plot of samples of cyano-rich porous carbon prepared in this example, having strong peaks corresponding to C1s, O1 s and N1s at about 285, 532 and 401eV, respectively, wherein the nitrogen in the sample is primarily due to the presence of cyano groups. The mass fraction of cyano groups in the sample was 5.6% by XPS test.
FIG. 2 shows N of the cyano-rich porous carbon material prepared in this example 2 Adsorption/desorption isotherms with samples at lower relative pressures (P/P) 0 Less than 0.05) has stronger N 2 Adsorbing and at P/P 0 When the specific surface area is more than 0.45, an adsorption hysteresis loop appears, which indicates that micropores (less than 2nm) and mesopores (2-50 nm) exist in the sample at the same time, and the specific surface area of the sample is calculated to be 1404.8m 2 /g。
Fig. 3 is a pore size distribution diagram obtained after nitrogen isothermal adsorption and desorption tests on the cyano-rich porous carbon material prepared in the embodiment, wherein the pore size of a sample is mainly distributed between 0.4 nm and 10nm, and the pore volumes of micropores and mesopores are respectively as follows: 0.46cm 3 g -1 And 0.22cm 3 g -1 The result shows that the prepared cyano-rich porous carbon has a hierarchical pore structure with an enhanced specific capacitance effect.
FIGS. 4 and 5 are CV and GCD graphs of electrochemical tests of the cyano-rich porous carbon electrode material obtained in this example in a three-electrode system with a platinum sheet electrode as the counter electrode and a calomel electrode as the reference electrode in a KOH solution of 6mol/L at room temperature, and it can be seen from the CV and GCD graphs that the curves are kept in a rectangular shape even at a high scan rate of 100mV/s, reflecting excellent electrochemical stability, and that the electrochemical performance of the material is better, and the specific capacitances at current densities of 0.5A/g, 1A/g, 2A/g, 3A/g, 5A/g, 10A/g and 20A/g are 261.4F/g, 245.6F/g, 231.7F/g, 224.0F/g, 214.7F/g, 203.1F/g and 189.6F/g, respectively.
Fig. 6 is a charge-discharge cycle chart of the cyano-rich porous carbon electrode material prepared in this example in a three-electrode system with a platinum sheet electrode as a counter electrode and a calomel electrode as a reference electrode in a KOH solution of 6mol/L at room temperature, and the cycle stability of the cyano-rich porous carbon electrode material at a constant current density (5A/g) is tested, and it can be seen that after 5000 charge-discharge cycles, the specific capacitance retention rate is as high as 98.5%, which proves that the cyano-rich porous carbon electrode material has excellent cycle stability.
Example 2
A cyano-rich porous carbon is prepared by the following steps:
1) ultrasonically dispersing glyoxal (10mL, 0.22mol) and acrylonitrile (10mL, 0.15mol) with 50mL of deionized water uniformly, placing the mixture into a stainless steel hydrothermal reaction kettle with the volume of 100mL and a Teflon lining, carrying out hydrothermal reaction at 180 ℃ for 24 hours, after the reaction is finished, naturally cooling the hydrothermal reaction kettle to room temperature, filtering out brown solid granular substances, washing the brown solid granular substances with ethanol, acetone and deionized water in sequence until the filtrate is colorless and neutral, and then carrying out vacuum drying on the sample at 50 ℃ overnight to obtain a precursor;
2) mixing 3g of precursor with 60mL of KOH solution (the concentration is 1mol/L), then transferring the mixture into a stainless steel hydrothermal reaction kettle with the volume of 100mL and a Teflon lining, activating and reacting for 12h at 140 ℃, drying the product for 24h at 100 ℃, and fully removing water to obtain an activated precursor;
3) and (3) putting 1g of activated precursor into a tubular furnace, heating to 600 ℃ at a heating rate of 5 ℃/min in the nitrogen atmosphere, preserving heat for 2h, washing for several times by using 1mol/L HCl solution and deionized water in sequence to remove KOH and other byproducts, and drying to obtain the cyano-rich porous carbon.
Electrochemical tests are carried out on the cyano-rich porous carbon material prepared in the embodiment in a three-electrode system with a platinum sheet electrode as a counter electrode and a calomel electrode as a reference electrode in 6mol/L KOH solution at room temperature, and the specific capacitance of the cyano-rich porous carbon material can reach 217.7F/g under the current density of 1A/g.
Example 3
A cyano-rich porous carbon is prepared by the following steps:
1) ultrasonically dispersing glyoxal (10mL, 0.22mol) and acrylonitrile (10mL, 0.15mol) with 50mL deionized water uniformly, placing the mixture into a stainless steel hydrothermal reaction kettle with a volume of 100mL and a Teflon lining, carrying out hydrothermal reaction at 180 ℃ for 24 hours, after the reaction is finished, naturally cooling the hydrothermal reaction kettle to room temperature, filtering out brown solid granular substances, washing the brown solid granular substances with ethanol, acetone and deionized water in sequence until the filtrate is colorless and neutral, and then carrying out vacuum drying on the sample at 50 ℃ overnight to obtain a precursor;
2) mixing 3g of precursor with 60mL of KOH solution (the concentration is 1mol/L), then transferring the mixture into a stainless steel hydrothermal reaction kettle with the volume of 100mL and a Teflon lining, activating and reacting for 12h at 140 ℃, drying the product for 24h at 100 ℃, and fully removing water to obtain an activated precursor;
3) and (3) putting 1g of the activated precursor into a tubular furnace, heating to 800 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 2h, washing for several times by using 1mol/L HCl solution and deionized water in sequence to remove KOH and other byproducts, and drying to obtain the cyano-rich porous carbon.
Electrochemical tests are carried out on the cyano-rich porous carbon material prepared in the embodiment in a three-electrode system with a platinum sheet electrode as a counter electrode and a calomel electrode as a reference electrode in 6mol/L KOH solution at room temperature, and the specific capacitance of the cyano-rich porous carbon material can reach 196.4F/g under the current density of 1A/g.
Example 4
A cyano-rich porous carbon is prepared by the following steps:
1) ultrasonically dispersing glyoxal (10mL, 0.22mol) and acrylonitrile (50mL, 0.75mol) with 50mL deionized water uniformly, placing the mixture into a stainless steel hydrothermal reaction kettle with the volume of 200mL and a Teflon lining, carrying out hydrothermal reaction at 180 ℃ for 24 hours, after the reaction is finished, naturally cooling the hydrothermal reaction kettle to room temperature, filtering out brown solid granular substances, washing the brown solid granular substances with ethanol, acetone and deionized water in sequence until the filtrate is colorless and neutral, and then carrying out vacuum drying on the sample at 50 ℃ overnight to obtain a precursor;
2) mixing 3g of precursor with 60mL of KOH solution (the concentration is 1mol/L), then transferring the mixture into a stainless steel hydrothermal reaction kettle with the volume of 100mL and a Teflon lining, activating and reacting for 12h at 140 ℃, drying the product for 24h at 100 ℃, and fully removing water to obtain an activated precursor;
3) and (3) putting 1g of the activated precursor into a tubular furnace, heating to 600 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 2h, washing for several times by using 1mol/L HCl solution and deionized water in sequence to remove KOH and other byproducts, and drying to obtain the cyano-rich porous carbon.
According to the invention, a micromolecular carbon source is introduced into a system for hydrothermally synthesizing the graded porous carbon material, glyoxal and acrylonitrile are used as raw materials, compared with other commonly used synthesis methods, the raw materials are micromolecules, the adopted hydrothermal synthesis method has simple steps and controllable structure, the specific surface area of the prepared precursor is larger, the defects of larger molecular weight and relatively complex structure of a common carbon source are overcome, the forming mechanism of the carbon material is simpler, the specific surface area of the product obtained after the activated precursor is carbonized is larger, the electrochemical performance is excellent, the cycle is stable, and the electrode material is a super capacitor electrode material with great potential.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. The cyano-rich porous carbon is characterized by having a micropore and mesopore hierarchical pore structure, and the specific surface area of the cyano-rich porous carbon is 1000-1500 m 2 The volume percentage of the micropores accounts for 60-70%, the volume percentage of the mesopores accounts for 30-40%, and the mass percentage of the cyano groups accounts for 4-11%.
2. The preparation method of the cyano-rich porous carbon according to claim 1, which comprises the following specific steps:
1) performing ultrasonic dispersion on glyoxal and acrylonitrile in deionized water uniformly, performing hydrothermal reaction, and performing post-treatment to obtain a precursor;
2) mixing the precursor obtained in the step 1) with an aqueous solution of an activating agent for activation reaction, carbonizing the obtained solid product, and washing and drying to obtain the cyano-rich porous carbon material.
3. The method for preparing cyano-rich porous carbon according to claim 2, wherein the molar ratio of glyoxal and acrylonitrile in step 1) is 1: 0.5-2, wherein the molar volume ratio of the glyoxal to the deionized water is 0.001-0.005 mol/mL.
4. The method for preparing cyano-rich porous carbon according to claim 2, wherein the hydrothermal reaction conditions in step 1) are as follows: reacting for 12-24 h at 160-200 ℃.
5. The preparation method of the cyano-rich porous carbon according to claim 2, wherein the activating agent in the step 2) is one of sodium hydroxide, potassium hydroxide, zinc chloride and calcium chloride, and the concentration of the aqueous solution of the activating agent is 0.5-2 mol/L.
6. The method for preparing cyano-rich porous carbon according to claim 2, wherein the mass ratio of the precursor in step 2) to the activator in the aqueous solution of the activator is 1: 0.5 to 3.
7. The method for preparing cyano-rich porous carbon according to claim 2, wherein the activation reaction conditions in step 2) are as follows: reacting for 1-15 h at 100-180 ℃.
8. The preparation method of cyano-rich porous carbon according to claim 2, wherein the process conditions of the carbonization treatment in the step 2) are as follows: and under the nitrogen atmosphere, heating from room temperature to 500-900 ℃ at the heating rate of 3-8 ℃/min, and preserving heat for 2 hours.
9. Use of the cyano-rich porous carbon of claim 1 as an electrode material for supercapacitors.
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