CN112079352B - Preparation method and application of biomass-based porous nitrogen-doped carbon material - Google Patents
Preparation method and application of biomass-based porous nitrogen-doped carbon material Download PDFInfo
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- 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
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Abstract
The invention discloses a preparation method of a biomass-based porous nitrogen-doped carbon material, which is characterized in that a biomass raw material, a nitrogen source chemical substance and an activating agent are prepared into the biomass nitrogen-doped porous carbon material through hydrothermal reaction and high-temperature activation according to a certain mass ratio. The biomass raw material is the seeds of illicium verum, the pretreatment process is simple, the cost is effectively reduced, the yield is improved, and the method is green and sustainable. The biomass-based porous nitrogen-doped carbon material is applied to preparation of electrodes in the super capacitor, and the specific capacitance and the cycle life of the electrode material of the super capacitor are effectively improved.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a preparation method and application of a biomass-based porous nitrogen-doped carbon material.
Background
The porous carbon material has the characteristics of high specific surface area, controllable porosity and pore size, good conductivity, surface modification and the like. Compared with the traditional carbon material, the porous carbon material prepared by using the biomass as the raw material has the advantages of rich resources, lower cost, surface modification and the like.
At present, a plurality of researchers select different biomass raw materials (such as cellulose, lignin, fruit shells, animal hair and the like), different nitrogen source materials for doping and adopt different process technologies to prepare the porous nitrogen-doped carbon material. The yield and application properties of the product are affected by the different biomass materials and nitrogen source materials, and the adoption of different process technologies. For example, Ben-Xue Z and the like are used for carrying out hydrothermal assembly on real silk fibers through low molecular weight phenolic resin, and then carbonization and activation are carried out, so as to obtain the N and O-doped porous carbon material. In the preparation method, the introduction of a graphitized structure of a low molecular weight phenolic resin derived carbon thin layer provides a richer structure, low resistance and graded porosity, so that the BET surface area is as high as 1927 m2 g 1. The specific capacitance of the obtained carbon composite material is as high as 330 F.g 1 (1000 mF.cm < 2 >) under 0.5 A.g 1, the rate capability is good, the circulation stability in 6m KOH electrolyte is good (the capacitance retention rate is 91 percent after 10000 cycles), the N-doped porous carbon nanosheet material is prepared by a method of taking soybean milk as a raw material and adopting the combination of hard template activation and KOH activation, wherein the method comprises the following steps of (Journal of Nanomaterials, 2018, 2018: 1-12), Chen MF and the like. The hard template of the calcium carbonate nanosphere, the KOH activation template and the potassium melting template form macropores, micropores and nanosheet shapes respectively. The precursor contains rich nitrogen and oxygen elements, so that the product has high heteroatom ratio, does not generate capacitance, and can promote electron transfer and conductivity. The obtained carbon has good charge storage capacity, the specific capacitance is 240.7F/g, the initial specific capacitance keeps good (92.2% -20A/g), (Journal of energy storage,2018, 105-. And Li and the like select polyacrylonitrile and nickel acetylacetonate as precursors of CNF and Ni source respectively. Dicyandiamide not only increases the specific surface area and pore volume of PCNF, but also increases the n-doping level of PCNF. The prepared NiO/PCNF electrode shows high specific capacitance of 850F g1, current density of 1 g 16 m KOH aqueous solution, good capability and excellent long-term cycling stability due to the synergistic effect among the nickel oxide nano particles. (document Small, 2018,1704203)
However, most of the existing biomass raw materials with better electrochemical performance are expensive, the nitrogen source materials such as ethylenediamine and the like have higher toxicity, the adopted process technologies such as a template method, a spray drying method and the like have higher technical cost, and the preparation process is more complicated. Therefore, the method for preparing the biomass-based porous carbon material still has limitations and cannot be widely put into production. The search for biomass-based porous carbon materials with low cost, environmental protection and sustainability, which are prepared by simple process technology with high yield and good electrochemical application performance is urgent.
As one of the current electrochemical energy storage technologies, supercapacitors are widely used in heavy vehicles, light rails, hybrid electric vehicles, etc. due to their advantages of high power density, long cycle life, and rapid charging and discharging. Electrode materials which are commercially used for supercapacitors are mainly derived from traditional fossil raw materials. However, the energy is gradually exhausted at present, and the biomass carbon material with low cost, environmental protection and high value is actively developed by fully utilizing wide biomass resources, so that the trend of the application of the supercapacitor in the future is great.
Disclosure of Invention
The invention provides a preparation method of a biomass-based porous nitrogen-doped carbon material, which solves the problems of high preparation cost, complex process and low yield; the application of the biomass-based porous nitrogen-doped carbon material in the super capacitor is further provided, and the problems of high cost, environmental pollution and low energy density of the super capacitor are solved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of a biomass-based porous nitrogen-doped carbon material is characterized by comprising the following steps:
s1, pretreatment of the biomass raw material: cleaning fresh illicium verum seeds, soaking the seeds in a mixed solution of ethanol and water, taking out the illicium verum seeds after soaking for a period of time, soaking the seeds in a hydrochloric acid solution again until the seeds fade, cleaning the seeds with deionized water until the seeds are soaked in the deionized water for 1-2 hours, and then drying the seeds to obtain a pretreated biomass raw material;
s2, preparing a mixed solution: mixing the biomass raw material pretreated in the step S1 with a nitrogen source material to obtain a mixed solution; the mass ratio range of the biomass raw material to the nitrogen source material in the mixed solution is 1: 1-1: 5;
s3, preparing a nitrogen-doped carbon material: adding the mixed solution obtained in the step S2 into a high-pressure reaction kettle, reacting for 12 hours at 300 ℃, and then drying to obtain a nitrogen-doped carbon material;
s4, preparing the porous nitrogen-doped carbon material: and (4) mixing the nitrogen-doped carbon material obtained in the step (S3) with an activating agent according to the mass ratio of 1:4, putting the mixture into a tubular furnace for high-temperature activation to obtain a black porous solid, washing the black porous solid, continuously washing the black porous solid with deionized water until the supernatant is neutral, and then carrying out vacuum drying to obtain the porous nitrogen-doped carbon material.
Further, in the step S1, the mass ratio of the ethanol to the water is 1: 2; the soaking time is 1-2 h.
Further, in step S2, the nitrogen source material includes melamine and urea; the mass ratio of the biomass raw material to the melamine is 1: 4-1: 5, and the mass ratio of the biomass raw material to the urea is 1: 1-1: 4. Has low toxicity.
Further, in the step S3, the drying time is 10-13 h.
Further, in step S4, the activating agent includes zinc chloride and potassium hydroxide.
Further, in the step S4, the high temperature activation includes introducing nitrogen into a tube furnace, activating at a temperature of 500 ℃ to 700 ℃ and maintaining for a period of time.
Further, the heat preservation time is 1 h.
Further, in step S4, the cleaning is ultrasonic cleaning.
Further, in the step S4, the temperature rise rate in the tube furnace is 5 ℃/min when the temperature is 0-400 ℃, and the temperature rise rate is 2 ℃/min when the temperature is more than 400 ℃. The heating rate of 5 ℃/min below 400 ℃ is more beneficial to the full decomposition of other organic matters or hemicellulose and the like in the seeds, and can effectively prevent the doped nitrogen from falling off on the surface of the material so that the nitrogen doping is ineffective.
The application of the biomass-based porous nitrogen-doped carbon material is characterized in that the biomass-based porous nitrogen-doped carbon material prepared by the method of any one of claims 1 to 8 is applied to the preparation of electrodes in a supercapacitor.
The invention achieves the following beneficial effects:
(1) the illicium verum seeds are used as biomass raw materials, have wide sources and low cost, are not required to be peeled and de-capsulated, can be directly picked for use, have simple pretreatment process, effectively reduce the cost, improve the yield and are green and sustainable.
(2) The biomass nitrogen-doped porous carbon material is prepared from the illicium verum seeds, a nitrogen source chemical substance and an activating agent according to a certain mass ratio through hydrothermal reaction and high-temperature activation, the preparation process is simple, the operability is strong, and the porous nitrogen-doped carbon material with high energy density, high rate capability and long cycle life can be obtained.
(3) Compared with pure activated carbon materials, the porous nitrogen-doped carbon material has the advantages of higher energy density, long cycle stability, and good wettability. By introducing N groups rich in electrons into the porous carbon material structure, protons are attracted to the surface of the electrode material so as to improve the wettability of the electrode material, ions in the electrolyte are more diffused inside the electrode material to form a pseudo-capacitance phenomenon, and therefore higher specific capacitance and current density are achieved. The method is applied to the super capacitor, and the specific capacitance and the cycle life of the electrode material of the super capacitor are effectively improved.
Drawings
FIG. 1 is a cyclic voltammogram of urea at 1:3 of the starting material at different scan rates.
FIG. 2 is a graph showing the charge and discharge curves obtained from urea and the starting material 1:3 at different current densities.
Detailed Description
The invention will be further described with reference to figures 1 and 2. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1:
s1, pretreatment of the biomass raw material: cleaning fresh illicium verum seeds, soaking the seeds in a mixed solution of ethanol and water in a mass ratio of 1:2, soaking for 1.5h, taking out the illicium verum seeds, soaking the seeds in a hydrochloric acid solution until the solution is dark and the surface layers of the seeds are faded, cleaning the seeds with deionized water until the seeds are soaked in the deionized water for 2h, testing the water solution to be neutral, and drying the seeds to obtain the pretreated biomass raw material.
S2, preparing a mixed solution: mixing the biomass raw material pretreated in the step S1 with melamine to obtain a mixed solution; the mass ratio of the biomass raw material to the melamine in the mixed solution is 1: 5.
S3, preparing a nitrogen-doped carbon material: and (4) adding the mixed solution obtained in the step S2 into a high-pressure reaction kettle, reacting for 12h at 300 ℃, and then drying for 12h to obtain the nitrogen-doped carbon material.
S4, preparing the porous nitrogen-doped carbon material: and (3) mixing the nitrogen-doped carbon material obtained in the step (S3) with potassium hydroxide according to the mass ratio of 1:4, putting the mixture into a tubular furnace for high-temperature activation, introducing nitrogen into the tubular furnace, activating at the temperature of 650 ℃, preserving heat for 1h to obtain a black porous solid, ultrasonically cleaning the black porous solid, continuously washing with deionized water until the supernatant is neutral, and then carrying out vacuum drying to obtain the porous nitrogen-doped carbon material. In the process, the temperature rise rate of the tube furnace is 5 ℃/min when the temperature is 0-400 ℃, and the temperature rise rate is 2 ℃/min when the temperature is more than 400 ℃.
Example 2:
s1, pretreatment of the biomass raw material: cleaning fresh illicium verum seeds, soaking the seeds in a mixed solution of ethanol and water in a mass ratio of 1:2, taking out the illicium verum seeds after soaking for 1h, then soaking the seeds in a hydrochloric acid solution until the solution is dark and the surface layers of the seeds are faded, cleaning the seeds with deionized water until the seeds are soaked in the deionized water for 1.5h, testing the water solution to be neutral, and drying the seeds to obtain the pretreated biomass raw material.
S2, preparing a mixed solution: mixing the biomass raw material pretreated in the step S1 with melamine to obtain a mixed solution; the mass ratio of the biomass raw material to the melamine in the mixed solution is 1: 4.
S3, preparing a nitrogen-doped carbon material: and (4) adding the mixed solution obtained in the step S2 into a high-pressure reaction kettle, reacting for 12 hours at 300 ℃, and then drying for 11 hours to obtain the nitrogen-doped carbon material.
S4, preparing the porous nitrogen-doped carbon material: and (3) mixing the nitrogen-doped carbon material obtained in the step (S3) with potassium hydroxide according to the mass ratio of 1:4, putting the mixture into a tubular furnace for high-temperature activation, introducing nitrogen into the tubular furnace, activating at the temperature of 500 ℃, preserving heat for 1h to obtain a black porous solid, ultrasonically cleaning the black porous solid, continuously washing with deionized water until the supernatant is neutral, and then carrying out vacuum drying to obtain the porous nitrogen-doped carbon material. In the process, the temperature rise rate of the tube furnace is 5 ℃/min when the temperature is 0-400 ℃, and the temperature rise rate is 2 ℃/min when the temperature is more than 400 ℃.
Example 3:
s1, pretreatment of the biomass raw material: cleaning fresh illicium verum seeds, soaking the seeds in a mixed solution of ethanol and water in a mass ratio of 1:2, taking out the illicium verum seeds after soaking for 2 hours, soaking the seeds in a hydrochloric acid solution again until the solution is dark and the surface layers of the seeds are faded, cleaning the seeds with deionized water until the seeds are soaked in the deionized water for 2 hours, testing the water solution to be neutral, and drying the seeds to obtain the pretreated biomass raw material.
S2, preparing a mixed solution: mixing the biomass raw material pretreated in the step S1 with melamine to obtain a mixed solution; the mass ratio of the biomass raw material to the urea in the mixed solution is 1: 1.
S3, preparing a nitrogen-doped carbon material: and (4) adding the mixed solution obtained in the step S2 into a high-pressure reaction kettle, reacting for 12 hours at 300 ℃, and then drying for 10 hours to obtain the nitrogen-doped carbon material.
S4, preparing the porous nitrogen-doped carbon material: and (3) mixing the nitrogen-doped carbon material obtained in the step (S3) with potassium hydroxide according to the mass ratio of 1:4, putting the mixture into a tubular furnace for high-temperature activation, introducing nitrogen into the tubular furnace, activating at the temperature of 700 ℃, preserving heat for 1h to obtain a black porous solid, ultrasonically cleaning the black porous solid, continuously washing with deionized water until the supernatant is neutral, and then carrying out vacuum drying to obtain the porous nitrogen-doped carbon material. In the process, the temperature rise rate of the tube furnace is 5 ℃/min when the temperature is 0-400 ℃, and the temperature rise rate is 2 ℃/min when the temperature is more than 400 ℃.
Example 4:
s1, pretreatment of the biomass raw material: cleaning fresh illicium verum seeds, soaking the seeds in a mixed solution of ethanol and water in a mass ratio of 1:2, soaking for 1.5h, taking out the illicium verum seeds, soaking the seeds in a hydrochloric acid solution until the solution is dark and the surface layers of the seeds are faded, cleaning the seeds with deionized water until the seeds are soaked in the deionized water for 2h, testing the water solution to be neutral, and drying the seeds to obtain the pretreated biomass raw material.
S2, preparing a mixed solution: mixing the biomass raw material pretreated in the step S1 with melamine to obtain a mixed solution; the mass ratio of the biomass raw material to the urea in the mixed solution is 1: 3.
S3, preparing a nitrogen-doped carbon material: and (4) adding the mixed solution obtained in the step S2 into a high-pressure reaction kettle, reacting for 12 hours at 300 ℃, and then drying for 13 hours to obtain the nitrogen-doped carbon material.
S4, preparing the porous nitrogen-doped carbon material: and (3) mixing the nitrogen-doped carbon material obtained in the step (S3) with potassium hydroxide according to the mass ratio of 1:4, putting the mixture into a tubular furnace for high-temperature activation, introducing nitrogen into the tubular furnace, activating at the temperature of 600 ℃, preserving heat for 1h to obtain a black porous solid, ultrasonically cleaning the black porous solid, continuously washing with deionized water until the supernatant is neutral, and then carrying out vacuum drying to obtain the porous nitrogen-doped carbon material. In the process, the temperature rise rate of the tube furnace is 5 ℃/min when the temperature is 0-400 ℃, and the temperature rise rate is 2 ℃/min when the temperature is more than 400 ℃.
Example 5:
mixing the porous nitrogen-doped carbon material obtained in the examples 1 to 4, a conductive agent and PVDF according to a mass ratio of 7:2:1, using N-methyl pyrrolidone as a dispersion to form a slurry, uniformly coating the slurry on foamed nickel, wherein the coating area is 1 x 1cm2. The electrochemical performance was measured in a three-electrode mode (reference electrode was mercuric oxide and reference electrode was platinum sheet) with an electrolyte of 6M KOH. The specific surface area can reach 1500-2500 m2The specific capacitance can reach 200-300F/g, and the energy density can reach 20-30 Wh/kg.
The invention is a technical scheme which is set on the basis of the experimental evidence that the optimal porous carbon material is obtained by pre-carbonization at 300 ℃ and activation with potassium hydroxide at high temperature of 600 ℃. The obtained carbon material has rich mesopores and macropores and is similar to a thin honeycomb. Compared with a pure activated carbon material, the porous carbon material has higher energy density and long cycling stability, but has poor wettability. Through calculation, the specific capacitance of the porous carbon material carbonized at 300 ℃ and activated at 600 ℃ reaches 121.636F/g, and the energy density reaches 20.44 Wh/kg.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a biomass-based porous nitrogen-doped carbon material is characterized by comprising the following steps:
s1, pretreatment of the biomass raw material: cleaning fresh illicium verum seeds, soaking the seeds in a mixed solution of ethanol and water, taking out the illicium verum seeds after soaking for a period of time, soaking the seeds in a hydrochloric acid solution again until the seeds fade, cleaning the seeds with deionized water until the seeds are soaked in the deionized water for 1-2 hours, and then drying the seeds to obtain a pretreated biomass raw material;
s2, preparing a mixed solution: mixing the biomass raw material pretreated in the step S1 with a nitrogen source material to obtain a mixed solution; the mass ratio range of the biomass raw material to the nitrogen source material in the mixed solution is 1: 1-1: 5;
s3, preparing a nitrogen-doped carbon material: adding the mixed solution obtained in the step S2 into a high-pressure reaction kettle, reacting for 12 hours at 300 ℃, and then drying to obtain a nitrogen-doped carbon material;
s4, preparing the porous nitrogen-doped carbon material: and (4) mixing the nitrogen-doped carbon material obtained in the step (S3) with an activating agent according to the mass ratio of 1:4, putting the mixture into a tubular furnace for high-temperature activation to obtain a black porous solid, washing the black porous solid, continuously washing the black porous solid with deionized water until the supernatant is neutral, and then carrying out vacuum drying to obtain the porous nitrogen-doped carbon material.
2. The method of claim 1, wherein in step S1, the mass ratio of ethanol to water is 1: 2; the soaking time is 1-2 h.
3. The method of claim 1, wherein in step S2, the nitrogen source material comprises one of melamine and urea.
4. The method of claim 1, wherein in step S3, the drying time is 10-13 h.
5. The method of claim 1, wherein in step S4, the activator comprises one of zinc chloride and potassium hydroxide.
6. The method of claim 1, wherein the step S4, the high temperature activation includes introducing nitrogen into a tube furnace, activating at 500-700 ℃ and maintaining the temperature for a certain period of time.
7. The method of claim 6, wherein the holding time is 1 h.
8. The method of claim 1, wherein the cleaning in step S4 is ultrasonic cleaning.
9. The method of claim 1, wherein in step S4, the temperature in the tube furnace is increased at a rate of 5 ℃/min between 0 ℃ and 400 ℃ and at a rate of 2 ℃/min above 400 ℃.
10. The application of the biomass-based porous nitrogen-doped carbon material is characterized in that the biomass-based porous nitrogen-doped carbon material prepared by the method in any one of claims 1 to 9 is applied to preparation of an electrode in a supercapacitor.
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