CN115295327A - Self-doped porous carbon material and preparation method and application thereof - Google Patents
Self-doped porous carbon material and preparation method and application thereof Download PDFInfo
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- CN115295327A CN115295327A CN202211005339.1A CN202211005339A CN115295327A CN 115295327 A CN115295327 A CN 115295327A CN 202211005339 A CN202211005339 A CN 202211005339A CN 115295327 A CN115295327 A CN 115295327A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 235000019764 Soybean Meal Nutrition 0.000 claims abstract description 79
- 239000004455 soybean meal Substances 0.000 claims abstract description 79
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- 238000000197 pyrolysis Methods 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011148 porous material Substances 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000010000 carbonizing Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000003213 activating effect Effects 0.000 claims abstract description 11
- 239000012190 activator Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000007772 electrode material Substances 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 6
- 150000008041 alkali metal carbonates Chemical group 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 26
- 238000003763 carbonization Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 8
- 244000046052 Phaseolus vulgaris Species 0.000 abstract description 7
- 235000010627 Phaseolus vulgaris Nutrition 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 60
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 238000000227 grinding Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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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
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention belongs to the technical field of electrode materials, and particularly relates to a self-doped porous carbon material and a preparation method and application thereof. The preparation method of the self-doped porous carbon material provided by the invention comprises the following steps: heating and carbonizing the soybean meal to obtain a soybean meal carbonized product; mixing the soybean meal carbonized product with an activating agent, heating, and carrying out pyrolysis reaction in a protective gas atmosphere to obtain the self-doped porous carbon material; the activator is an alkali metal carbonate. According to the preparation method provided by the invention, the nitrogenous material bean pulp is used as a nitrogen source carbon source, the carbonized product of the bean pulp and the alkali carbonate activator are directly mixed and heated for carrying out pyrolysis reaction, and the obtained self-doped porous carbon material has the advantages of developed pore structure, large pore volume, high specific surface area, high specific capacitance, stable electrochemical performance and capability of being used in constant-current charge and discharge tests when current flowsThe specific capacitance can reach 310.70 F.g when the density is 1A/g ‑1 . The preparation method provided by the invention has the advantages of easily available raw materials, simple and convenient operation and low energy consumption.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a self-doped porous carbon material and a preparation method and application thereof.
Background
In the research on energy storage devices, the super capacitor has the advantages of reproducibility and environmental protection, and has high power density and high stability, so the super capacitor is very concerned. The choice of electrode material has a critical influence on the performance of the supercapacitor. In recent years, porous carbon materials are widely researched as electrode materials to be applied to electrodes of the super capacitor, because the specific surface area of the porous carbon materials is higher than that of common materials, the porous carbon materials are low in price and excellent in conductivity, and the porous carbon materials are ideal materials for the electrodes of the super capacitor. However, the specific capacitance of the current porous carbon material used as the electrode material of the supercapacitor is still lower, less than 180F/g, and the application of the porous carbon material in the supercapacitor is limited.
The annual yield of the soybean meal in China in 2021 year is reported to be 7972 ten thousand tons, and the soybean meal as a byproduct after soybean oil pressing is rich in yield and wide in source. At present, most of the soybean meal is used as feed for processing and used in the animal husbandry industry due to the high protein content in the soybean meal, so that the utilization value of the soybean meal is low.
Disclosure of Invention
The invention aims to provide a self-doped porous carbon material, and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a self-doped porous carbon material, which comprises the following steps:
heating and carbonizing the soybean meal to obtain a soybean meal carbonized product;
mixing the soybean meal carbonized product with an activating agent, heating, and carrying out pyrolysis reaction in a protective gas atmosphere to obtain the self-doped porous carbon material; the activator is an alkali metal carbonate.
Preferably, the activator is K 2 CO 3 。
Preferably, the mass ratio of the soybean meal carbonized product to the activating agent is 1 (2-4).
Preferably, the temperature of the pyrolysis reaction is 500-800 ℃, and the heat preservation time of the pyrolysis reaction is 1-3 h.
Preferably, the heating rate from room temperature to the temperature of the pyrolysis reaction is 1-10 ℃/min.
Preferably, the carbonization temperature is 350-450 ℃, and the carbonization heat preservation time is 1-3 h.
Preferably, the heating rate from room temperature to the carbonization temperature is 1-10 ℃/min.
Preferably, before the carbonization, the method further comprises drying the soybean meal, and carbonizing the dried soybean meal; the drying temperature is 60-100 ℃.
The invention provides the self-doped porous carbon material prepared by the preparation method in the technical scheme, the self-doped porous carbon material is a self-nitrogen-doped porous carbon material, and nitrogen accounts for more than 1.5% of the self-doped porous carbon material in percentage by mass; the pore volume of the self-doped porous carbon material is more than 0.5cm 3 /g。
The invention provides an application of the self-doped porous carbon material in the technical scheme as an electrode material of a super capacitor.
The invention provides a preparation method of a self-doped porous carbon material, which comprises the following steps: heating and carbonizing the soybean meal to obtain a soybean meal carbonized product; mixing the soybean meal carbonized product with an activating agent, heating, and carrying out pyrolysis reaction in a protective gas atmosphere to obtain the self-doped porous carbon material; the activator is an alkali metal carbonate. The preparation method provided by the invention takes the nitrogen-containing material bean pulp as a nitrogen source carbon source, directly mixes and heats the carbonized product of the bean pulp and the alkali carbonate activator for carrying out the pyrolysis reaction, and generates various products in the carbonized product of the bean pulp in the temperature rise process of the pyrolysis reactionPhysically activating the carbon framework material by using small gas molecules, forming a large number of macropores in a carbonized product of the soybean meal, and preliminarily forming the nitrogen-doped carbon framework material; in the thermal insulation process of the pyrolysis reaction, the activating agent carries out redox reaction pore-forming to form a large number of micropores, and meanwhile, nitrogen atoms doped in the carbon frame material promote partial micropores to be converted into mesopores, so that the generation of a developed pore structure of the carbon frame material is facilitated. The self-doped porous carbon material prepared by the preparation method provided by the invention has the advantages of developed pore structure, large pore capacity, high specific surface area, high specific capacitance and stable electrochemical performance, and the specific capacitance can reach 310.7 Fg when the current density is 1A/g in a constant current charge and discharge test -1 . The preparation method provided by the invention has the advantages of easily available raw materials, simple and convenient operation and low energy consumption, can be used for realizing green, environment-friendly and efficient utilization of the soybean meal, and improves the additional value of the industrial production of the soybean meal.
Further, the temperature of the pyrolysis reaction is 500-800 ℃, and the heat preservation time of the pyrolysis reaction is 1-3 h. According to the temperature of the pyrolysis reaction and the heat preservation time of the pyrolysis reaction, the collapse of pore channels of the porous carbon material can be effectively avoided while the pyrolysis reaction is fully performed, and the obtained self-doped porous carbon material with a developed pore structure and a stable pore structure is obtained.
The invention provides the self-doped porous carbon material prepared by the preparation method in the technical scheme, the self-doped porous carbon material is a nitrogen-doped porous carbon material, and the nitrogen element accounts for more than 1.5% of the self-doped porous carbon material in percentage by mass; the pore volume of the self-doped porous carbon material is more than 0.5cm 3 (ii) in terms of/g. The self-doped porous carbon material provided by the invention has the advantages of developed pore structure, large pore volume, high specific surface area, high specific capacitance and stable electrochemical performance, and the specific capacitance can reach 310.70 Fg when the current density is 1A/g in a constant current charge-discharge test -1 。
Drawings
FIG. 1 is a charge/discharge curve diagram of a self-doped porous carbon material prepared in example 1 of the present invention at a current density of 1A/g;
FIG. 2 is a charge-discharge curve diagram of the self-doped porous carbon material prepared in example 2 of the present invention at a current density of 1A/g;
FIG. 3 is a charge/discharge curve diagram of the self-doped porous carbon material prepared in example 3 of the present invention at a current density of 1A/g;
FIG. 4 is a charge-discharge curve diagram of the self-doped porous carbon material prepared in example 4 of the present invention at a current density of 1A/g;
FIG. 5 is a charge/discharge curve diagram of the self-doped porous carbon material prepared in example 5 of the present invention at a current density of 1A/g;
FIG. 6 is a charge/discharge curve diagram of the self-doped porous carbon material prepared in example 6 of the present invention at a current density of 1A/g;
FIG. 7 is a graph showing the charging and discharging curves of the self-doped porous carbon material prepared in example 7 of the present invention at a current density of 1A/g.
Detailed Description
The invention provides a preparation method of a self-doped porous carbon material, which comprises the following steps:
heating and carbonizing the soybean meal to obtain a soybean meal carbonized product;
mixing the soybean meal carbonized product with an activating agent, heating, and carrying out pyrolysis reaction in a protective gas atmosphere to obtain the self-doped porous carbon material; the activator is an alkali metal carbonate.
In the present invention, all the preparation starting materials/components are commercially available products well known to those skilled in the art unless otherwise specified.
The invention heats and carbonizes the soybean meal to obtain a carbonized product of the soybean meal.
The invention has no special requirements on the source of the soybean meal.
In a specific embodiment of the present invention, the soybean meal is a byproduct soybean meal of a soybean oil production enterprise.
In the invention, before the carbonization, the invention preferably further comprises drying the soybean meal, and carbonizing the dried soybean meal; the drying temperature is 60-100 ℃.
In the present invention, the drying is preferably performed in a forced air drying oven.
In the present invention, the temperature of the drying is preferably 60 to 100 ℃, more preferably 65 to 100 ℃.
The invention has no special requirement on the drying heat preservation time, and the bean pulp is dried to constant weight. In the invention, the constant weight is particularly preferably constant weight 12h without change in mass.
In the present invention, the carbonization is preferably performed in a box furnace or a tube furnace.
In the present invention, the temperature of the carbonization is preferably 350 to 450 ℃, and more preferably 400 ℃.
In the present invention, the incubation time for the carbonization is preferably 1 to 3 hours, and more preferably 2 hours.
In the present invention, the rate of temperature increase from room temperature to the carbonization temperature is preferably 1 to 10 ℃/min, and more preferably 5 ℃/min.
In the invention, the carbonization reaction is carried out to obtain a carbonized product, and the carbonized product is preferably ground to obtain the soybean meal carbonized product. The invention has no special requirements for the specific implementation process of the grinding.
After a soybean meal carbonized product is obtained, the soybean meal carbonized product and an activating agent are mixed and heated, and a pyrolysis reaction is carried out in a protective gas atmosphere to obtain the self-doped porous carbon material; the activator is an alkali metal carbonate.
In the present invention, the activator is particularly preferably K 2 CO 3 。
In the invention, the mass ratio of the soybean meal carbonized product to the activating agent is preferably 1 (2-4), more preferably 1.
In the present invention, the pyrolysis reaction is preferably carried out in a tube furnace.
In the present invention, the temperature of the pyrolysis reaction is preferably 500 to 800 ℃, more preferably 550 to 750 ℃, and further preferably 650 ℃.
In the present invention, the holding time for the pyrolysis reaction is preferably 1 to 3 hours, more preferably 2 hours.
In the present invention, the rate of temperature increase from room temperature to the temperature of the pyrolysis reaction is preferably 1 to 10 ℃/min, more preferably 5 ℃/min.
In the present invention, the pyrolysis reaction is preferably performed in a protective gas atmosphere, and more preferably in a nitrogen atmosphere.
In the invention, the pyrolysis reaction is carried out to obtain a pyrolysis product, and the pyrolysis product is preferably subjected to post-treatment to obtain the self-doped porous carbon material. In the present invention, the post-treatment preferably comprises: washing, drying and grinding are sequentially carried out. In the present invention, the washing is preferably: the pyrolysis product is sequentially subjected to hydrochloric acid washing and water washing, and the molar concentration of hydrochloric acid used in the hydrochloric acid washing is preferably 1 mol.L -1 The water used for washing is preferably distilled water, the frequency of the hydrochloric acid washing and the frequency of the water washing are not particularly required, and the pyrolysis product is washed until the pH value is 7 +/-0.5. The washed pyrolysis product is preferably dried by the present invention, and the present invention has no special requirement on the specific implementation process of the drying. The invention preferably mills the dried pyrolysis product, and the invention has no particular requirement on the specific implementation of the milling process.
The invention provides the self-doped porous carbon material prepared by the preparation method in the technical scheme, the self-doped porous carbon material is a self-nitrogen-doped porous carbon material, and the mass percentage of nitrogen element in the self-doped porous carbon material is more than 1.5%; the pore volume of the self-doped porous carbon material is more than 0.5cm 3 /g。
In the self-doped porous carbon material, the content of nitrogen element in the self-doped porous carbon material is more than 1.5% by mass, and preferably 1.67-8.2% by mass.
In a specific embodiment of the present invention, the content of the nitrogen element in the self-doped porous carbon material by mass percentage is specifically and preferably 1.67%, 2.82%, 5.24%, 7.25%, 8.2%, 5.12% or 5.04%.
In the present invention, in the self-doped porous carbon material, the content of carbon element in the self-doped porous carbon material is preferably 68.27 to 88.1% by mass.
In a specific embodiment of the present invention, the content of the carbon element in the self-doped porous carbon material is specifically and preferably 68.27%, 74.35%, 80.74%, 86.33%, 88.1%, 76.39% or 78.52% by mass.
In the present invention, the pore volume of the self-doped porous carbon material is more than 0.5cm 3 A concentration of 0.567 to 1.8614cm 3 (ii) in terms of/g. In a specific embodiment of the present invention, the pore volume of the self-doped porous carbon material is preferably 0.567cm 3 /g、0.8964cm 3 /g、1.091cm 3 /g、1.5428cm 3 /g、1.8614cm 3 /g、0.9639cm 3 Per g or 0.9426cm 3 /g。
In the present invention, the specific surface area of the self-doped porous carbon material is preferably 926.1446 to 2183.2158m 2 In the specific embodiment of the invention, the specific surface area of the self-doped porous carbon material is 1427.24m 2 /g、1506.37m 2 /g、2183.2158m 2 /g、1806.4823m 2 /g、1641.34m 2 /g、1349.455m 2 G or 926.1446m 2 /g。
In the present invention, the specific capacitance of the self-doped porous carbon material is preferably 182.41 to 310.7F/g, and in a specific embodiment of the present invention, the specific capacitance of the self-doped porous carbon material is preferably 209.4F/g, 271.2F/g, 310.7F/g, 263F/g, 182.41F/g, 303F/g, or 293.40F/g.
In order to further illustrate the present invention, the following detailed description of the technical solutions provided by the present invention is made with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
And (3) putting the soybean meal into a culture dish, heating and drying the soybean meal in an oven at the temperature of 60 ℃ until the weight is constant, and keeping the quality unchanged for 12 hours to obtain the solid particles of the soybean meal. And (3) carbonizing the solid soybean meal particles in a tubular furnace at 400 ℃ for 2h, and grinding to obtain a carbonized product of the soybean meal. Taking 1g of the above carbonized product of soybean meal, 3g of K 2 CO 3 Mixing in porcelain boat, and placing in tubeHeating to 500 ℃ at a heating rate of 5 ℃/min in a furnace in a nitrogen atmosphere, carrying out high-temperature pyrolysis for 2h at 550 ℃, and sequentially and respectively using 1 mol. L of products after reaction -1 And washing the product with hydrochloric acid solution and distilled water until the pH value of the product is about 7, and drying and grinding the product to obtain the self-doped porous carbon material. The pore structure and the electrochemical performance of the prepared self-doped porous carbon material at the current density of 1A/g are tested, and the charge-discharge curve of the self-doped porous carbon material prepared in the embodiment at the current density of 1A/g is shown in FIG. 1; according to the test results, the doping amount of nitrogen of the self-doping porous carbon material prepared by the embodiment of the invention is 8.20%, and the pore capacity is 0.567cm 3 Per g, specific surface area 926.1446m 2 The specific capacitance was 209.4F/g, and the carbon content was 68.27%.
Example 2
And (3) putting the soybean meal into a culture dish, heating and drying the soybean meal in an oven at 100 ℃ until the weight is constant, and keeping the quality unchanged for 12 hours to obtain the solid particles of the soybean meal. And (3) heating the solid soybean meal particles to 400 ℃ at the heating rate of 5 ℃/min in a tubular furnace, carbonizing for 2h at the temperature of 400 ℃, and grinding to obtain a carbonized product of the soybean meal. Taking 1g of the above carbonized product of soybean meal, 3g of K 2 CO 3 Mixing the raw materials evenly in a porcelain boat, placing the mixture in a tube furnace, heating the mixture to 600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, carrying out high-temperature pyrolysis for 2 hours at the temperature of 600 ℃, and sequentially and respectively using 1 mol.L of products after reaction -1 And washing the product with hydrochloric acid solution and distilled water until the pH value of the product is about 7, and drying and grinding the product to obtain the self-doped porous carbon material. The pore structure and the electrochemical performance of the nitrogen-doped porous carbon material prepared in the embodiment at the current density of 1A/g are tested, and the charge-discharge curve of the self-doped porous carbon material prepared in the embodiment at the current density of 1A/g is shown in fig. 2; according to the test results, the doping amount of nitrogen from the porous carbon material was 7.25%, and the pore volume was 0.8964cm 3 Per g, specific surface area 1349.455m 2 The specific capacitance is 271.2F/g, and the carbon content is 74.35%.
Example 3
Placing bean cake in cultureAnd heating and drying in a dish-keeping oven at 70 ℃ until the weight is constant, and keeping the weight unchanged for 12 hours to obtain the solid particles of the soybean meal. And (3) heating the solid soybean meal particles to 400 ℃ at the heating rate of 5 ℃/min in a tubular furnace, carbonizing for 2h at the temperature of 400 ℃, and grinding to obtain a carbonized product of the soybean meal. Taking 1g of the above soybean meal carbonized product, 3g of K 2 CO 3 Mixing the raw materials evenly in a porcelain boat, placing the mixture in a tube furnace, heating the mixture to 650 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, carrying out high-temperature pyrolysis for 2 hours at the temperature of 650 ℃, and sequentially and respectively using 1 mol.L of products after reaction -1 And washing the hydrochloric acid solution and the distilled water until the pH value of the product is about 7, and drying and grinding to obtain the nitrogen-doped porous carbon material. The pore structure and the electrochemical performance of the self-doped porous carbon material prepared in the embodiment at the current density of 1A/g are tested, and the charge-discharge curve of the self-doped porous carbon material prepared in the embodiment at the current density of 1A/g is shown in fig. 3; according to the test results, the doping amount of nitrogen of the porous carbon material was 5.24%, and the pore volume was 1.091cm 3 Per g, specific surface area of 1641.34m 2 The specific capacitance is 310.7F/g, and the carbon content is 80.74 percent.
Example 4
And (3) placing the soybean meal in a culture dish, heating and drying the soybean meal in an oven at 80 ℃ until the weight is constant, and keeping the quality unchanged for 12 hours to obtain the solid particles of the soybean meal. And (3) heating the solid soybean meal particles to 400 ℃ at the heating rate of 5 ℃/min in a tubular furnace, carbonizing for 2h at the temperature of 400 ℃, and grinding to obtain a carbonized product of the soybean meal. Taking 1g of the above carbonized product of soybean meal, 3g of K 2 CO 3 Mixing the raw materials in a porcelain boat uniformly, placing the mixture in a tube furnace, heating the mixture to 700 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, carrying out high-temperature pyrolysis for 2 hours at the temperature of 700 ℃, and sequentially and respectively using 0.1 mol.L of products after reaction -1 And washing the hydrochloric acid solution and the distilled water until the pH value of the product is about 7, and drying and grinding to obtain the nitrogen-doped porous carbon material. The pore structure and electrochemical performance of the autodoped porous carbon material prepared in this example at a current density of 1A/g were tested, and the autodoped porous carbon material prepared in this exampleThe charge-discharge curve of the porous carbon material at a current density of 1A/g is shown in FIG. 4; according to the test results, the porous carbon material had a nitrogen doping amount of 2.82% and a pore volume of 1.5428cm 3 Per gram, specific surface area 1806.4823m 2 (iv)/g, specific capacitance of 263F/g, carbon content of 86.33%.
Example 5
And (3) putting the soybean meal into a culture dish, heating and drying the soybean meal in an oven at 90 ℃ until the weight is constant, and keeping the heating and drying for 12 hours until the mass is unchanged to obtain the solid particles of the soybean meal. And (3) heating the solid soybean meal particles to 400 ℃ at the heating rate of 5 ℃/min in a tubular furnace, carbonizing for 2h at the temperature of 400 ℃, and grinding to obtain a carbonized product of the soybean meal. Taking 1g of the above soybean meal carbonized product, 3g of K 2 CO 3 Mixing the raw materials in a porcelain boat uniformly, placing the mixture in a tube furnace, heating the mixture to 750 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, carrying out high-temperature pyrolysis for 2 hours at the temperature of 750 ℃, and sequentially and respectively using 0.1 mol.L of products after reaction -1 And washing the product with hydrochloric acid solution and distilled water until the pH value of the product is about 7, and drying and grinding the product to obtain the nitrogen-doped porous carbon material. The pore structure and the electrochemical performance of the self-doped porous carbon material prepared in this embodiment at a current density of 1A/g were tested, and the charge-discharge curve of the self-doped porous carbon material prepared in this embodiment at a current density of 1A/g is shown in fig. 5; according to the test results, the nitrogen doping amount of the porous carbon material was 1.67%, and the pore volume was 1.8614cm 3 Per g, specific surface area 2183.2158m 2 The specific capacitance is 182.41F/g, and the carbon content is 88.10%.
Example 6
And (3) placing the soybean meal into a culture dish, heating and drying the soybean meal in an oven at 85 ℃ until the weight is constant, and keeping the quality unchanged for 12 hours to obtain the solid particles of the soybean meal. And (3) heating the solid soybean meal particles to 400 ℃ at the heating rate of 5 ℃/min in a tubular furnace, carbonizing for 2h at the temperature of 400 ℃, and grinding to obtain a carbonized product of the soybean meal. Taking 1g of the above carbonized product of soybean meal, 2g of K 2 CO 3 Mixing in porcelain boat, placing in tube furnace, heating to 650 deg.C at a heating rate of 5 deg.C/min in nitrogen atmospherePyrolyzing at 650 deg.C for 2h, and sequentially subjecting to 0.1 mol/L -1 And washing the product with hydrochloric acid solution and distilled water until the pH value of the product is about 7, and drying and grinding the product to obtain the nitrogen-doped porous carbon material. The pore structure and the electrochemical performance of the self-doped porous carbon material prepared in this example at a current density of 1A/g were tested, and the charge-discharge curve of the self-doped porous carbon material prepared in this example at a current density of 1A/g is shown in fig. 6; according to the test results, the porous carbon material had a nitrogen doping amount of 5.12% and a pore volume of 0.9639cm 3 Per gram, the specific surface area is 1506.37m 2 The specific capacitance is 303F/g, and the carbon content is 76.39%.
Example 7
And (3) placing the soybean meal in a culture dish, heating and drying the soybean meal in an oven at 75 ℃ until the weight is constant, and keeping the quality unchanged for 12 hours to obtain the solid particles of the soybean meal. And (3) heating the solid soybean meal particles to 400 ℃ at the heating rate of 5 ℃/min in a tubular furnace, carbonizing for 2h at the temperature of 400 ℃, and grinding to obtain a carbonized product of the soybean meal. Taking 1g of the above carbonized product of soybean meal, 4g of K 2 CO 3 Mixing the raw materials in a porcelain boat uniformly, placing the mixture in a tube furnace, heating the mixture to 650 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, carrying out high-temperature pyrolysis for 2 hours at 650 ℃, and sequentially and respectively using 0.1 mol.L of products after reaction -1 And washing the hydrochloric acid solution and distilled water until the pH value of the product is about 7, and drying and grinding to obtain the self-doped porous carbon material. The pore structure and the electrochemical performance of the self-doped porous carbon material prepared in this embodiment at a current density of 1A/g were tested, and the charge-discharge curve of the self-doped porous carbon material prepared in this embodiment at a current density of 1A/g is shown in fig. 7; according to the test results, the porous carbon material had a nitrogen doping amount of 5.04% and a pore volume of 0.9426cm 3 Per gram, specific surface area 1427.24m 2 The specific capacitance is 293.40F/g, and the carbon content is 78.52%.
Comparative example 1
The preparation method is basically the same as that of example 3, except that: k in example 3 2 CO 3 Is replaced byKOH. The self-doped porous carbon material prepared in the comparative example was tested for electrochemical performance at a current density of 1A/g, and according to the test results, the specific capacitance of the porous carbon material was 273.5F/g.
Comparative example 2
The preparation method is basically the same as that of example 3, except that: the high-temperature pyrolysis temperature is 900 ℃, the pore structure of the obtained self-doped porous carbon material collapses, and the porous carbon material cannot be prepared.
Comparative example 3
The preparation method is basically the same as that of example 3, except that: the temperature of high-temperature pyrolysis during heat preservation is 4h, the pore structure of the obtained self-doped porous carbon material collapses, and the carbon material with the porous structure cannot be prepared.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A preparation method of a self-doped porous carbon material is characterized by comprising the following steps:
heating and carbonizing the soybean meal to obtain a soybean meal carbonized product;
mixing the soybean meal carbonized product with an activating agent, heating, and carrying out pyrolysis reaction in a protective gas atmosphere to obtain the self-doped porous carbon material; the activator is an alkali metal carbonate.
2. The method of claim 1, wherein the activator is K 2 CO 3 。
3. The preparation method according to claim 1 or 2, characterized in that the mass ratio of the soybean meal carbonized product to the activating agent is 1 (2-4).
4. The preparation method according to claim 1, wherein the temperature of the pyrolysis reaction is 500 to 800 ℃, and the holding time of the pyrolysis reaction is 1 to 3 hours.
5. The method according to claim 4, wherein the rate of temperature increase from room temperature to the temperature of the pyrolysis reaction is 1 to 10 ℃/min.
6. The preparation method of claim 1, wherein the carbonization temperature is 350-450 ℃, and the carbonization heat preservation time is 1-3 h.
7. The method according to claim 6, wherein the rate of temperature increase from room temperature to the carbonization temperature is 1 to 10 ℃/min.
8. The preparation method according to claim 1, further comprising drying the soybean meal before the carbonization; the drying temperature is 60-100 ℃.
9. The self-doped porous carbon material prepared by the preparation method of any one of claims 1 to 8, wherein the self-doped porous carbon material is a self-nitrogen-doped porous carbon material, and the mass percentage of nitrogen element in the self-doped porous carbon material is more than 1.5%; the pore volume of the self-doped porous carbon material is more than 0.5cm 3 /g。
10. Use of the self-doped porous carbon material of claim 9 as an electrode material for a supercapacitor.
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