CN111540618A - Non-hydroformylation preparation method of nitrogen-oxygen co-doped carbon-based supercapacitor electrode material - Google Patents
Non-hydroformylation preparation method of nitrogen-oxygen co-doped carbon-based supercapacitor electrode material Download PDFInfo
- Publication number
- CN111540618A CN111540618A CN202010377411.8A CN202010377411A CN111540618A CN 111540618 A CN111540618 A CN 111540618A CN 202010377411 A CN202010377411 A CN 202010377411A CN 111540618 A CN111540618 A CN 111540618A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- oxygen
- carbon
- electrode material
- supercapacitor electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000007772 electrode material Substances 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000011282 treatment Methods 0.000 claims abstract description 22
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000004880 explosion Methods 0.000 claims abstract description 12
- 229960001031 glucose Drugs 0.000 claims abstract description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 6
- -1 D-anhydrous glucose Chemical compound 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000000935 solvent evaporation Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000003990 capacitor Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a nitrogen-oxygen co-doped carbon-based supercapacitor electrode material non-hydroformylation preparation method, which takes melamine (nitrogen source), D-anhydrous glucose (carbon source), sodium bicarbonate (pore-forming agent) and magnesium hydroxide (pore-expanding agent) as raw materials and adopts the treatments of resonance sound mixing, microwave-assisted solvent evaporation reaction, steam explosion treatment of resin, high-temperature anaerobic carbonization, nitrogen filling micronization ball milling, cleaning, vacuum drying and the like to obtain the nitrogen-oxygen co-doped carbon-based supercapacitor electrode material. The specific surface area of the nitrogen-oxygen co-doped carbon-based supercapacitor electrode material can reach 700-800m2The specific capacitance can reach 160-170F/g (the current density is 1A/g).
Description
Technical Field
The invention belongs to the technical field of super capacitors, and relates to a non-hydroformylation preparation method of a nitrogen-oxygen co-doped carbon-based super capacitor electrode material.
Background
Supercapacitors, also known as electrochemical capacitors, are widely used in energy storage devices to replace batteries and fuel cells due to their fast charge and discharge speed, long cycle life and high power density. Supercapacitors can be divided into three main categories according to the difference of energy storage mechanism. Electric Double Layer Capacitor (EDLC): electrical energy is stored by the electric double layer effect, and an electric storage phenomenon occurs at an interface between a conductive electrode and an adjacent liquid electrolyte. Electrochemical pseudocapacitor: the energy storage mechanism of the pseudo capacitor is completely different from that of a double electric layer capacitor, and the electrode material of the pseudo capacitor stores and releases energy through rapid and reversible chemical adsorption and desorption or Faraday redox reaction. Hybrid capacitor: usually consisting of a cell-type electrode where the faradaic process takes place and an electrode based on capacitive behavior.
The porous carbon material refers to a carbon material with a certain pore structure, and the size, the number and the distribution of pores determine the performance of the porous material. The porous carbon-based supercapacitor electrode material mainly comprises: activated Carbon (AC), Carbon Nanotubes (CNT), carbon nanofibers, graphene, and template carbon. Due to its adjustable porous structure, good electrical conductivity, good stability and high specific surface area, it is widely used in electrochemical double-layer capacitor electrode materials. There are many factors affecting the electric double layer capacitor of the porous carbon material, such as specific surface area of the electrode material, pore structure characteristics, electrical conductivity, electrolyte, surface properties, and the like. The microporous structure of the carbon material can provide rich adsorption capacity, and the position of active ions can improve electrochemical capacitance; and the carbon material mesoporous structure with higher specific surface area is beneficial to the loading and transmission of ionic charges.
In previous researches, a resin (serving as a precursor substance) is generally synthesized and then the synthesized resin is correspondingly carbonized to obtain the electrode material with a certain microscopic morphology and good electrochemical performance. The resin types commonly used as the carbon precursor of the electrode material of the supercapacitor include urea-formaldehyde resin, phenol-formaldehyde resin, melamine-formaldehyde resin and the like. For example, melamine formaldehyde resins are the methylolation and methyl etherification products of melamine with formaldehyde, methanol, and phenolic resins are the foams of phenol and formaldehyde; the formaldehyde is inevitably volatilized in the resin synthesis process, and the synthesized resin also has some free formaldehyde. In the research and development and production processes of the electrode material of the super capacitor, formaldehyde causes great pollution to the environment and is unfavorable for human health and ecological environment. Along with the continuous enhancement of the green environmental protection consciousness and the health consciousness of people, the harm brought by the excessive formaldehyde emission is more and more concerned by people, so that the realization of non-hydroformylation research and development and production has great significance.
Numerous existing studies show that the capacitance of the carbon material can be significantly improved by doping with heteroatoms such as N, P, B, S, O. Different heteroatom doping has obvious difference on the improvement effect of the physicochemical property and the capacitive property of the carbon material. N doping can improve the conductivity and the hydrophilicity of the carbon material, and the capacitance of the carbon material can be increased by the pseudocapacitance introduced by the N-containing group; the O doping can obviously improve the hydrophilicity and the stability of the carbon material, so that the carbon material has a wider potential window and can provide a certain pseudo capacitance.
Disclosure of Invention
The invention aims to provide a non-hydroformylation preparation method of a nitrogen-oxygen co-doped carbon-based supercapacitor electrode material.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: a non-hydroformylation preparation method of a nitrogen-oxygen co-doped carbon-based supercapacitor electrode material comprises the following steps:
step 1: mixing melamine, D-anhydrous glucose, sodium bicarbonate and magnesium hydroxide according to the mass ratio of 1:1:1-5: 0-0.25, putting into a resonance sound mixing device, and treating for 10-15min under the conditions of frequency of 80-120Hz and amplitude of 1.0-2.0mm to obtain a mixed reaction raw material;
step 2: mixing the mixed reaction raw material obtained in the step 1 with deionized water according to a mass ratio of 1:10-20, uniformly stirring, and performing ultrasonic treatment for 15-30 min;
and step 3: and (3) placing the aqueous solution obtained in the step (2) into heating equipment with a steam condensation collecting device, heating to boiling, keeping the boiling state for 4-8h, and starting microwave treatment on the aqueous solution once at intervals of 25-30min in the boiling state, wherein the microwave frequency is 2450MHz, and the radiation intensity is 0.5-2.0W/cm2The microwave treatment time is 2.5-5.0min each time;
and 4, step 4: filtering the material obtained in the step (3), and collecting a solid material, namely resin; placing the resin in steam explosion equipment, and performing steam explosion treatment by adopting the parameters of water-material ratio of 1:5-7, pressure maintaining time of 300-;
and 5: putting the material obtained in the step (4) into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, heating to 700-900 ℃ at a heating rate of 2-5 ℃/min under the protection of nitrogen, and carrying out heat preservation carbonization treatment for 2-3h to obtain a carbon material;
step 6: putting the carbon material into a ball milling tank, extracting air in the ball milling tank, filling nitrogen, sealing the ball milling tank, and grinding the carbon material to the fineness of 25-250 mu m to obtain micronized carbon powder;
and 7: washing the micronized carbon powder with dilute hydrochloric acid or dilute sulfuric acid, then washing with deionized water, finally washing with ethanol, then filtering through filter paper with the aperture of 1-3 mu m, and collecting the trapped filter residue;
and 8: and (3) putting the filter residue into vacuum drying equipment, and carrying out vacuum drying for 10-14h under the conditions of vacuum gauge pressure of-0.08 to-0.10 MPa and temperature of 60-80 ℃, wherein the dried product is the nitrogen-oxygen co-doped carbon-based supercapacitor electrode material.
The preferable technical scheme is as follows: the mass ratio of the melamine to the D-anhydrous glucose to the sodium bicarbonate to the magnesium hydroxide is 1:1:2: 0.15-0.25.
The preferable technical scheme is as follows: the ultrasonic frequency of ultrasonic treatment is 25-35KHz, and the power density is 0.4-0.5W/cm2。
The preferable technical scheme is as follows: the concentration of the dilute hydrochloric acid and the dilute sulfuric acid is 0.05-0.10 mol/L.
Due to the application of the technical scheme, compared with the prior art, the invention has the advantages that:
1. the invention adopts the resonance sound mixed raw materials, so that the nitrogen source raw material, the carbon source raw material, the pore-forming agent and the pore-expanding agent are quickly and fully mixed, and the speed and the effect of the subsequent reaction are improved.
2. The invention adopts the microwave-assisted solvent evaporation method to treat the raw material aqueous solution, so that the resin is formed more quickly and fully.
3. The invention adopts steam explosion to treat resin, which is beneficial to the increase of porous structure and the enlargement of pores.
4. The nitrogen-oxygen co-doped carbon-based supercapacitor electrode material prepared by the method has the specific surface area of 700-800m2The specific capacitance can reach 160-170F/g (the current density is 1A/g).
Drawings
FIG. 1 is an XRD pattern of the porous carbon material prepared in example 1.
FIG. 2 is a nitrogen isothermal adsorption-desorption curve of the porous carbon material prepared in example 1.
FIG. 3 is a pore size distribution curve of the porous carbon material prepared in example 1.
FIG. 4 is a graph of the specific capacitance of the porous carbon material in a 6mol/L KOH electrolyte.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Please refer to fig. 1-4. It should be understood that the structures, ratios, sizes, and the like shown in the drawings and described in the specification are only used for matching with the disclosure of the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions under which the present invention can be implemented, so that the present invention has no technical significance, and any structural modification, ratio relationship change, or size adjustment should still fall within the scope of the present invention without affecting the efficacy and the achievable purpose of the present invention. In addition, the terms "upper", "lower", "left", "right", "middle" and "one" used in the present specification are for clarity of description, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the terms is not to be construed as a scope of the present invention.
Example 1: non-hydroformylation preparation method of nitrogen-oxygen co-doped carbon-based supercapacitor electrode material
A non-hydroformylation preparation method of a nitrogen-oxygen co-doped carbon-based supercapacitor electrode material comprises the following steps:
step 1: mixing melamine, D-anhydrous glucose, sodium bicarbonate and magnesium hydroxide, placing into a resonance sound mixing device, and treating for 12min under the conditions of frequency of 100Hz and amplitude of 1.5mm to obtain a mixed reaction raw material; specifically, 1.5 g of D-anhydrous glucose, 1.5 g of melamine and 3.0 g of sodium bicarbonate are weighed respectively.
Step 2: mixing the mixed reaction raw material obtained in the step 1 with deionized water according to a mass ratio, uniformly stirring, and performing ultrasonic treatment for 20 min; the volume of deionized water is 100 mL
And step 3: placing the water solution obtained in the step 2 into heating equipment with a steam condensation collecting device, heating to boiling, keeping the boiling state for 8h, and starting microwave treatment on the water solution once at intervals of 28min in the boiling state, wherein the microwave frequency is 2450MHz, and the radiation intensity is 1.0W/cm2The microwave treatment time is 4min each time;
and 4, step 4: filtering the material obtained in the step (3), and collecting a solid material, namely resin; placing the resin in steam explosion equipment, and performing steam explosion treatment by adopting parameters of a water-material ratio of 1:6, a pressure maintaining time of 350s and a steam pressure of 2.6 MPa;
and 5: putting the material obtained in the step (4) into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, heating to 900 ℃ at a heating rate of 3.5 ℃/min under the protection of nitrogen, and carrying out heat preservation carbonization treatment for 2h to obtain a carbon material;
step 6: putting the carbon material into a ball milling tank, extracting air in the ball milling tank, filling nitrogen, sealing the ball milling tank, and grinding the carbon material to the fineness of 25-250 mu m to obtain micronized carbon powder;
and 7: washing the micronized carbon powder with dilute hydrochloric acid or dilute sulfuric acid, then washing with deionized water, finally washing with ethanol, then filtering with filter paper with the aperture of 2 mu m, and collecting the trapped filter residue;
and 8: and (3) putting the filter residue into vacuum drying equipment, and carrying out vacuum drying for 12h under the conditions of vacuum gauge pressure of-0.09 MPa and temperature of 70 ℃, wherein the dried product is the nitrogen-oxygen co-doped carbon-based supercapacitor electrode material.
The preferred embodiment is: the ultrasonic frequency of ultrasonic treatment is 30 KHz, and the power density is 0.45W/cm2。
The preferred embodiment is: the concentration of the dilute hydrochloric acid and the dilute sulfuric acid is 0.06 mol/L.
Electrochemical tests show that the specific surface area of the prepared porous carbon material can reach 774 m2/g。
Examples 2 to 6: non-hydroformylation preparation method of nitrogen-oxygen co-doped carbon-based supercapacitor electrode material
Respectively weighing 5 groups of raw materials:
example 2: 1.5 g of D-anhydroglucose, 1.5 g of melamine, 3.0 g of sodium bicarbonate.
Example 3: 1.5 g of D-anhydroglucose, 1.5 g of melamine, 3.0 g of sodium bicarbonate.
Example 4: 1.5 g of D-anhydroglucose, 1.5 g of melamine, 3.0 g of sodium bicarbonate.
Example 5: 1.5 g of D-anhydrous glucose, 1.5 g of melamine, 3.0 g of sodium bicarbonate, 0.29 g of magnesium hydroxide.
Example 6: 1.5 g of D-anhydrous glucose, 1.5 g of melamine, 3.0 g of sodium bicarbonate, 0.58g of magnesium hydroxide. The nitrogen source raw material is melamine, the carbon source raw material is D-anhydrous glucose, the pore-forming agent is sodium bicarbonate, and the pore-expanding agent is magnesium hydroxide.
The difference from the embodiment 1 is that:
the five groups of carbonization methods are different: example 2 heat preservation at 700 ℃ for 2 h; example 3 the temperature is maintained at 800 ℃ for 2 h; example 4 the temperature is maintained at 900 ℃ for 2 h; example 5 adopts the method of preserving heat for 2 hours at 700 ℃; example 6 incubation was carried out for 2h at 700 ℃.
As shown in FIG. 4, it was tested that the specific capacitance of the porous carbon material prepared by adding 0.58g (carbonized at 700 ℃ C.) of magnesium hydroxide in 6mol/L KOH electrolyte was as high as 165F/g (current density of 1A/g). After the magnesium hydroxide is added, the proportion of holes in the electrode material can be further increased, so that the specific capacitance of the electrode material is increased.
Example 7: non-hydroformylation preparation method of nitrogen-oxygen co-doped carbon-based supercapacitor electrode material
A non-hydroformylation preparation method of a nitrogen-oxygen co-doped carbon-based supercapacitor electrode material comprises the following steps:
step 1: mixing melamine, D-anhydrous glucose, sodium bicarbonate and magnesium hydroxide according to the mass ratio of 1:1:1: 0.01, placing the mixture into a resonance sound mixing device, and treating for 10min under the conditions of frequency of 80Hz and amplitude of 1.0mm to obtain a mixed reaction raw material;
step 2: mixing the mixed reaction raw material obtained in the step 1 with deionized water according to a mass ratio of 1:10, uniformly stirring, and performing ultrasonic treatment for 15 min;
and step 3: placing the water solution obtained in the step 2 into heating equipment with a steam condensation collecting device, heating to boiling, keeping the boiling state for 4h, and starting microwave treatment on the water solution at intervals of 25min in the boiling state, wherein the microwave frequency is 2450MHz, and the radiation intensity is 0.5W/cm2The microwave treatment time is 2.5min each time;
and 4, step 4: filtering the material obtained in the step (3), and collecting a solid material, namely resin; placing the resin in steam explosion equipment, and performing steam explosion treatment by adopting parameters of a water-material ratio of 1:5, a pressure maintaining time of 300s and a steam pressure of 2.5 MPa;
and 5: putting the material obtained in the step (4) into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, heating to 700 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and carrying out heat preservation carbonization treatment for 2h to obtain a carbon material;
step 6: putting the carbon material into a ball milling tank, extracting air in the ball milling tank, filling nitrogen, sealing the ball milling tank, and grinding the carbon material to the fineness of 25 mu m to obtain micronized carbon powder;
and 7: washing the micronized carbon powder with dilute hydrochloric acid or dilute sulfuric acid, then washing with deionized water, finally washing with ethanol, then filtering with filter paper with the aperture of 1 mu m, and collecting the trapped filter residue;
and 8: and (3) putting the filter residue into vacuum drying equipment, and carrying out vacuum drying for 10h under the conditions of vacuum gauge pressure of-0.08 MPa and temperature of 60 ℃, wherein the dried product is the nitrogen-oxygen co-doped carbon-based supercapacitor electrode material.
The preferred embodiment is: the ultrasonic frequency of ultrasonic treatment is 25KHz, and the power density is 0.4W/cm2。
The preferred embodiment is: the concentration of the dilute hydrochloric acid and the dilute sulfuric acid is 0.05 mol/L.
Example 8: non-hydroformylation preparation method of nitrogen-oxygen co-doped carbon-based supercapacitor electrode material
A non-hydroformylation preparation method of a nitrogen-oxygen co-doped carbon-based supercapacitor electrode material comprises the following steps:
step 1: mixing melamine, D-anhydrous glucose, sodium bicarbonate and magnesium hydroxide according to the mass ratio of 1:1:5:0.25, putting into a resonance sound mixing device, and treating for 15min under the conditions of 120Hz frequency and 2.0mm amplitude to obtain a mixed reaction raw material;
step 2: mixing the mixed reaction raw material obtained in the step 1 with deionized water according to a mass ratio of 1: 20, uniformly stirring, and performing ultrasonic treatment for 30 min;
and step 3: placing the water solution obtained in the step 2 into heating equipment with a steam condensation collecting device, heating to boiling, keeping the boiling state for 8h, and starting microwave treatment on the water solution at intervals of 30min in the boiling state, wherein the microwave frequency is 2450MHz, and the radiation intensity is 2.0W/cm2The microwave treatment time is 5.0min each time;
and 4, step 4: filtering the material obtained in the step (3), and collecting a solid material, namely resin; placing the resin in steam explosion equipment, and performing steam explosion treatment by adopting parameters of a water-material ratio of 1:7, a pressure maintaining time of 400s and a steam pressure of 3.0 MPa;
and 5: putting the material obtained in the step (4) into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, heating to 900 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and carrying out heat preservation carbonization treatment for 3h to obtain a carbon material;
step 6: putting the carbon material into a ball milling tank, extracting air in the ball milling tank, filling nitrogen, sealing the ball milling tank, and grinding the carbon material to the fineness of 250 mu m to obtain micronized carbon powder;
and 7: washing the micronized carbon powder with dilute hydrochloric acid or dilute sulfuric acid, then washing with deionized water, finally washing with ethanol, then filtering with filter paper with the aperture of 3 mu m, and collecting the trapped filter residue;
and 8: and (3) putting the filter residue into vacuum drying equipment, and carrying out vacuum drying for 14h under the conditions of vacuum gauge pressure of-0.10 MPa and temperature of 80 ℃, wherein the dried product is the nitrogen-oxygen co-doped carbon-based supercapacitor electrode material.
The preferred embodiment is: the ultrasonic frequency of ultrasonic treatment is 35KHz, and the power density is 0.5W/cm2。
The preferred embodiment is: the concentration of the dilute hydrochloric acid and the dilute sulfuric acid is 0.10 mol/L.
The foregoing is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting thereof in any way, and any modifications or variations thereof that fall within the spirit of the invention are intended to be included within the scope thereof.
Claims (4)
1. A nitrogen-oxygen co-doped carbon-based supercapacitor electrode material hydroformylation-free preparation method is characterized by comprising the following steps: comprises the following steps:
step 1: mixing melamine, D-anhydrous glucose, sodium bicarbonate and magnesium hydroxide according to the mass ratio of 1:1:1-5: 0-0.25, putting into a resonance sound mixing device, and treating for 10-15min under the conditions of frequency of 80-120Hz and amplitude of 1.0-2.0mm to obtain a mixed reaction raw material;
step 2: mixing the mixed reaction raw material obtained in the step 1 with deionized water according to a mass ratio of 1:10-20, uniformly stirring, and performing ultrasonic treatment for 15-30 min;
and step 3: placing the aqueous solution obtained in the step 2 into a heating device with a steam condensation collecting deviceHeating to boiling, maintaining at boiling state for 4-8 hr, and starting microwave treatment once at interval of 25-30min for the water solution with microwave frequency of 2450MHz and radiation intensity of 0.5-2.0W/cm2The microwave treatment time is 2.5-5.0min each time;
and 4, step 4: filtering the material obtained in the step (3), and collecting a solid material, namely resin; placing the resin in steam explosion equipment, and performing steam explosion treatment by adopting the parameters of water-material ratio of 1:5-7, pressure maintaining time of 300-;
and 5: putting the material obtained in the step (4) into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, heating to 700-900 ℃ at a heating rate of 2-5 ℃/min under the protection of nitrogen, and carrying out heat preservation carbonization treatment for 2-3h to obtain a carbon material;
step 6: putting the carbon material into a ball milling tank, extracting air in the ball milling tank, filling nitrogen, sealing the ball milling tank, and grinding the carbon material to the fineness of 25-250 mu m to obtain micronized carbon powder;
and 7: washing the micronized carbon powder with dilute hydrochloric acid or dilute sulfuric acid, then washing with deionized water, finally washing with ethanol, then filtering through filter paper with the aperture of 1-3 mu m, and collecting the trapped filter residue;
and 8: and (3) putting the filter residue into vacuum drying equipment, and carrying out vacuum drying for 10-14h under the conditions of vacuum gauge pressure of-0.08 to-0.10 MPa and temperature of 60-80 ℃, wherein the dried product is the nitrogen-oxygen co-doped carbon-based supercapacitor electrode material.
2. The non-hydroformylation preparation method of the nitrogen-oxygen co-doped carbon-based supercapacitor electrode material according to claim 1, characterized in that: the mass ratio of the melamine to the D-anhydrous glucose to the sodium bicarbonate to the magnesium hydroxide is 1:1:2: 0.15-0.25.
3. The non-hydroformylation preparation method of the nitrogen-oxygen co-doped carbon-based supercapacitor electrode material according to claim 1, characterized in that: the ultrasonic frequency of ultrasonic treatment is 25-35KHz, and the power density is 0.4-0.5W/cm2。
4. The non-hydroformylation preparation method of the nitrogen-oxygen co-doped carbon-based supercapacitor electrode material according to claim 1, characterized in that: the concentration of the dilute hydrochloric acid and the dilute sulfuric acid is 0.05-0.10 mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010377411.8A CN111540618B (en) | 2020-05-07 | 2020-05-07 | Non-hydroformylation preparation method of nitrogen-oxygen co-doped carbon-based supercapacitor electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010377411.8A CN111540618B (en) | 2020-05-07 | 2020-05-07 | Non-hydroformylation preparation method of nitrogen-oxygen co-doped carbon-based supercapacitor electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111540618A true CN111540618A (en) | 2020-08-14 |
| CN111540618B CN111540618B (en) | 2021-10-22 |
Family
ID=71977490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010377411.8A Active CN111540618B (en) | 2020-05-07 | 2020-05-07 | Non-hydroformylation preparation method of nitrogen-oxygen co-doped carbon-based supercapacitor electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111540618B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112938932A (en) * | 2021-04-01 | 2021-06-11 | 福州大学 | Method for regulating and controlling porous carbon prepared by high internal phase emulsion template method through aldose |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004193522A (en) * | 2002-12-13 | 2004-07-08 | Kobe Steel Ltd | Impurity doped diamond |
| CN104795565A (en) * | 2015-05-11 | 2015-07-22 | 内蒙古民族大学 | Porous graphene powder rich in heteroatom and preparation method and application thereof |
| CN106082210A (en) * | 2016-06-20 | 2016-11-09 | 山东欧铂新材料有限公司 | A kind of compound active fruit shell carbon and preparation method thereof, application |
| CN106629724A (en) * | 2017-01-06 | 2017-05-10 | 安徽大学 | Nitrogen-doped porous carbon, preparation method and application of nitrogen-doped porous carbon as electrode material of supercapacitor |
| CN107010622A (en) * | 2017-04-17 | 2017-08-04 | 南京林业大学 | Medium barrier plasma is modified microwave activation lignin-base carbon resistance rod preparation method |
| CN107746049A (en) * | 2017-10-13 | 2018-03-02 | 齐齐哈尔大学 | Melamine route for steam synthesizes rich nitrogen ordered mesoporous carbon material |
| CN110342489A (en) * | 2019-08-21 | 2019-10-18 | 河南师范大学 | A kind of preparation method of the porous carbon-based energy storage material of nonmetal doping |
| US10590277B2 (en) * | 2014-03-14 | 2020-03-17 | Group14 Technologies, Inc. | Methods for sol-gel polymerization in absence of solvent and creation of tunable carbon structure from same |
-
2020
- 2020-05-07 CN CN202010377411.8A patent/CN111540618B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004193522A (en) * | 2002-12-13 | 2004-07-08 | Kobe Steel Ltd | Impurity doped diamond |
| US10590277B2 (en) * | 2014-03-14 | 2020-03-17 | Group14 Technologies, Inc. | Methods for sol-gel polymerization in absence of solvent and creation of tunable carbon structure from same |
| CN104795565A (en) * | 2015-05-11 | 2015-07-22 | 内蒙古民族大学 | Porous graphene powder rich in heteroatom and preparation method and application thereof |
| CN106082210A (en) * | 2016-06-20 | 2016-11-09 | 山东欧铂新材料有限公司 | A kind of compound active fruit shell carbon and preparation method thereof, application |
| CN106629724A (en) * | 2017-01-06 | 2017-05-10 | 安徽大学 | Nitrogen-doped porous carbon, preparation method and application of nitrogen-doped porous carbon as electrode material of supercapacitor |
| CN107010622A (en) * | 2017-04-17 | 2017-08-04 | 南京林业大学 | Medium barrier plasma is modified microwave activation lignin-base carbon resistance rod preparation method |
| CN107746049A (en) * | 2017-10-13 | 2018-03-02 | 齐齐哈尔大学 | Melamine route for steam synthesizes rich nitrogen ordered mesoporous carbon material |
| CN110342489A (en) * | 2019-08-21 | 2019-10-18 | 河南师范大学 | A kind of preparation method of the porous carbon-based energy storage material of nonmetal doping |
Non-Patent Citations (2)
| Title |
|---|
| NAVALADIAN SUBRAMANIAN AND BALASUBRAMANIAN VISWANATHAN: "Nitrogen- and oxygen-containing activated carbons from sucrose for electrochemical supercapacitor applications", 《ROYAL SOCIETY OF CHEMISTRY》 * |
| ZHONGJIE ZHANG等: "Low temperature and highly efficient oxygen/sulfur dual-modification of nanoporous carbon under hydrothermal conditions for supercapacitor application", 《JOURNAL OF SOLID STATE ELECTROCHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112938932A (en) * | 2021-04-01 | 2021-06-11 | 福州大学 | Method for regulating and controlling porous carbon prepared by high internal phase emulsion template method through aldose |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111540618B (en) | 2021-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11952278B2 (en) | Lignin porous carbon nanosheet, preparation method therefor, and application thereof in supercapacitor electrode materials | |
| Chen et al. | Biomass‐based hierarchical porous carbon for supercapacitors: effect of aqueous and organic electrolytes on the electrochemical performance | |
| Jain et al. | Mesoporous activated carbons with enhanced porosity by optimal hydrothermal pre-treatment of biomass for supercapacitor applications | |
| Wang et al. | Hydrothermal preparation of highly porous carbon spheres from hemp (Cannabis sativa L.) stem hemicellulose for use in energy-related applications | |
| Wang et al. | Promising biomass-based activated carbons derived from willow catkins for high performance supercapacitors | |
| Xue et al. | Self-template synthesis of nitrogen-doped porous carbon derived from rice husks for the fabrication of high volumetric performance supercapacitors | |
| Yan et al. | Biomass‐derived activated carbon nanoarchitectonics with Hibiscus flowers for high‐performance supercapacitor electrode applications | |
| Xiong et al. | A novel synthesis of mesoporous carbon microspheres for supercapacitor electrodes | |
| Xu et al. | Sustainable nitrogen-doped porous carbon with high surface areas prepared from gelatin for supercapacitors | |
| Heimböckel et al. | Increase of porosity by combining semi-carbonization and KOH activation of formaldehyde resins to prepare high surface area carbons for supercapacitor applications | |
| Qiao et al. | Humic acids-based hierarchical porous carbons as high-rate performance electrodes for symmetric supercapacitors | |
| Chen et al. | Controllable fabrication of nitrogen-doped porous nanocarbons for high-performance supercapacitors via supramolecular modulation strategy | |
| Guo et al. | N-Doped hierarchical porous carbon prepared by simultaneous-activation of KOH and NH 3 for high performance supercapacitors | |
| Natalia et al. | Activated carbon derived from natural sources and electrochemical capacitance of double layer capacitor | |
| Liu et al. | Hierarchical flaky porous carbon derived from waste polyimide film for high‐performance aqueous supercapacitor electrodes | |
| CN111681887B (en) | Preparation method of ultrathin graphene-like carbon material for supercapacitor | |
| Chen et al. | The production of porous carbon from calcium lignosulfonate without activation process and the capacitive performance | |
| CN103723723B (en) | A kind of preparation method of Graphene modified activated carbon | |
| CN103723721A (en) | Preparation method of graphene-modified activated carbon for supercapacitor | |
| Feng et al. | Nitrogen-doped lignin-derived porous carbons for supercapacitors: Effect of nanoporous structure | |
| Zhang et al. | Schiff base reaction induced densification of chitosan-derived microporous carbon for compact capacitive energy storage | |
| Wu et al. | B, N-dual doped sisal-based multiscale porous carbon for high-rate supercapacitors | |
| Yuan et al. | Highly ordered mesoporous carbon synthesized via in situ template for supercapacitors | |
| CN110127695A (en) | A kind of preparation method of supercapacitor wood sawdust base porous charcoal | |
| CN111540618B (en) | Non-hydroformylation preparation method of nitrogen-oxygen co-doped carbon-based supercapacitor electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |