CN115215337B - Method for synthesizing phenolic resin and preparing carbon material - Google Patents
Method for synthesizing phenolic resin and preparing carbon material Download PDFInfo
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- CN115215337B CN115215337B CN202210568232.1A CN202210568232A CN115215337B CN 115215337 B CN115215337 B CN 115215337B CN 202210568232 A CN202210568232 A CN 202210568232A CN 115215337 B CN115215337 B CN 115215337B
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- phenolic resin
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- carbon material
- furfural
- pentahydroxymethyl
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 63
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 63
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 36
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000227 grinding Methods 0.000 claims abstract description 27
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 23
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 23
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 23
- 229940033123 tannic acid Drugs 0.000 claims abstract description 23
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 23
- 229920002258 tannic acid Polymers 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a synthetic phenolic resin and a method for preparing a carbon material by using the phenolic resin, wherein the specific preparation method of the phenolic resin comprises the following steps: (a) Fully grinding and mixing tannic acid, pentahydroxymethyl furfural and nano magnesium oxide by using a mortar according to a mass ratio, adding a small amount of dilute sulfuric acid in the grinding process for catalysis, and continuously grinding until the materials are uniform; (b) And collecting the uniformly ground sample into a polytetrafluoroethylene lining, transferring the sample into a hydrothermal kettle, and reacting to obtain the phenolic resin-based material. The invention replaces common raw materials phenol and formaldehyde with tannic acid and pentahydroxymethyl furfural. The tannic acid and the pentahydroxymethyl furfural are used as raw materials for producing the phenolic resin, so that pollution and harm to human bodies caused by the preparation process can be effectively reduced. The phenolic resin carbon material prepared by the invention has larger specific surface area, reasonable pore distribution and good morphology distribution, and the specific surface area of the material can reach 950.40m 2/g.
Description
Technical Field
The invention relates to the field of phenolic resin, in particular to synthetic phenolic resin and a method for preparing a carbon material by using the phenolic resin.
Technical Field
The phenolic resin has good acid resistance, mechanical property and heat resistance, and is widely applied to corrosion resistance, adhesives, flame-retardant materials and the like; and the phenolic resin has high carbon residue rate, the phenolic resin can generate very high carbon residue under the condition of inert gas at 1000 ℃, and the generated carbon material can be used as a cathode material of a zinc ion supercapacitor.
The current preparation principle of phenolic resin is that phenols and aldehydes react to generate phenolic resin through polycondensation under the action of an acidic or alkaline catalyst. The raw materials used for the phenolic resin are generally phenol, formaldehyde, and the like. Phenol is toxic, and a concentrated solution thereof has strong corrosiveness to skin and has great risk in use; formaldehyde is also harmful to the human body.
Disclosure of Invention
In order to solve the problems, the invention uses tannic acid and pentahydroxymethyl furfural instead of phenol and formaldehyde which are commonly used as raw materials, wherein the tannic acid is a biomass raw material, is commonly existing in plants such as grape, tea and the like, and contains a large amount of phenolic hydroxyl groups; pentahydroxy methyl furfural is a chemical substance formed by dehydration of glucose or fructose, and the molecule of the pentahydroxy methyl furfural contains high-activity aldehyde groups. The tannic acid and the pentahydroxymethyl furfural are used as raw materials for producing the phenolic resin, so that pollution and harm to human bodies caused by the preparation process can be effectively reduced. The prepared phenolic resin-based carbon material can be used as a carbon cathode of a zinc ion supercapacitor and has better performance. Electrode tests of the zinc ion mixed super capacitor with the carbon material serving as the carbon cathode show that when the power density reaches 731W/kg, the specific capacitance reaches 90.7 mAh/g, and the energy density reaches 79 Wh/kg.
The preparation method of the phenolic resin comprises the following steps:
(a) And fully grinding and mixing tannic acid, pentahydroxymethyl furfural and nano magnesium oxide by using a mortar according to the mass ratio, adding a small amount of dilute sulfuric acid in the grinding process for catalysis, and continuously grinding until the materials are uniform.
(B) And collecting the uniformly ground sample into a polytetrafluoroethylene lining, transferring the sample into a hydrothermal kettle, and reacting to obtain the phenolic resin-based material.
Further, tannic acid: pentahydroxymethyl furfural: the mass ratio of the nano magnesium oxide is 1:1:2.
Further, the amount of dilute sulfuric acid used was 0.5mol/L.
Further, the reaction conditions in step (b) are: the reaction was carried out at 180℃for 12 hours.
The method for preparing the phenolic resin carbon material by using the phenolic resin-based material comprises the following specific preparation steps:
① And (3) transferring the phenolic resin-based material into a graphite boat, heating to 900 ℃ under nitrogen atmosphere, and preserving heat for 1 hour to obtain a sample.
② And cleaning the sample by using hydrochloric acid, and placing the sample in an oven for drying after suction filtration to obtain the phenolic resin carbon material.
Further, the temperature rising speed in step ① is: 2 ℃/min.
Further, when hydrochloric acid is used to clean the sample in step ②, the hydrochloric acid used is: 1mol/L.
Further, the drying conditions in step ② are as follows: and placing the mixture in a baking oven at 60 ℃ for baking for 6 hours.
The invention has the beneficial effects that:
The invention uses tannic acid to replace phenol, wherein the tannic acid contains a large amount of phenolic hydroxyl groups, satisfies basic reaction, and is used as biomass raw material, and the tannic acid has rich sources and wide distribution; as a product of dehydration of saccharides, pentahydroxymethyl furfural is important in the field of biomass energy. The tannic acid and the pentahydroxymethyl furfural are used as raw materials for producing the phenolic resin, so that the harm to human bodies and the pollution to the environment in the production process can be greatly reduced.
The activated phenolic resin carbon material prepared by the invention has larger specific surface area, reasonable pore distribution and good morphology distribution, and the specific surface area of the activated material can reach 1603.40m 2/g. The activated phenolic resin carbon material has high specific capacitance and matched energy density and power density as a carbon cathode of the zinc ion supercapacitor, and electrode tests of the zinc ion supercapacitor show that when the power density reaches 731W/kg, the specific capacitance reaches 90.7 mAh/g and the energy density reaches 79 Wh/kg.
Drawings
FIG. 1 TGA and DTA graphs of example 1 phenolic resin based material; a) TGA curve, b) DTA curve
FIG. 2 example 1 Infrared Spectrum of phenolic resin-based Material
FIG. 3 is an electron micrograph of the phenolic carbon material of example 1 and example 2; electron micrograph a) SEM image, b) TEM image of example 2; electron micrograph c) SEM image, d) TEM image of example 1.
FIG. 4 TGA curves for control group 1 and control group 2; a) Control group 1, b) control group 2
FIG. 5 a) CV curve, b) GCD curve of example 1 sample.
Detailed Description
The invention is further illustrated and described by the following specific examples:
example 1: preparation of the phenolic resin-based carbon material
(1) Fully grinding and mixing 1g of tannic acid, 1g of pentahydroxy methyl furfural and 2g of nano magnesium oxide by using a mortar according to the mass ratio of 1:1:2, adding 5ml of sulfuric acid with the concentration of 0.5mol/L in the grinding process, and continuously grinding for 30min;
(2) Collecting a uniformly ground sample into a polytetrafluoroethylene lining, transferring the sample into a hydrothermal kettle, and reacting for 12 hours at 180 ℃ to obtain a phenolic resin-based material;
(3) Transferring the phenolic resin-based material into a graphite boat, heating up at a heating rate of 2 ℃/min under nitrogen atmosphere until the temperature reaches 900 ℃, and preserving the temperature for 1 hour to obtain a sample;
(4) And cleaning the sample by using 1mol of hydrochloric acid, filtering, and then placing the sample in a 60 ℃ oven for drying for 6 hours to obtain the phenolic resin carbon material.
Example 1 TGA and DTA profiles of phenolic resin based materials are shown in figure 1; in fig. 1, a) TGA curve, b) DTA curve. The infrared spectrum of the phenolic resin-based material is shown in figure 2.
The example 1 step (1) material refers to a sample that has not been thermally polymerized, and the example 1 step (2) material refers to a sample that has been thermally polymerized. As can be seen from fig. 1 and 2, the carbon yield of the material after polymerization changed significantly, indicating that tannic acid and penta-hydroxymethyl furfural undergo a crosslinking reaction at the polymerization temperature to produce a phenolic resin material.
Example 2:
(1) Fully grinding and mixing 1g of tannic acid and 1g of pentahydroxy methyl furfural by using a mortar according to the mass ratio of 1:1, adding 5ml of sulfuric acid with the concentration of 0.5mol/L in the grinding process, and continuously grinding for 30min;
(2) Collecting a uniformly ground sample into a polytetrafluoroethylene lining, transferring the sample into a hydrothermal kettle, and reacting for 12 hours at 180 ℃ to obtain a phenolic resin-based material;
(3) And (3) transferring the phenolic resin-based material into a graphite boat, heating at a heating rate of 2 ℃/min under the nitrogen atmosphere until the temperature reaches 900 ℃, and preserving the temperature for 1 hour to obtain a sample.
Scanning electron microscopy tests were performed on the phenolic resin carbon materials of example 1 and example 2, and scanning electron microscopy photographs are shown in fig. 3. As can be seen from a comparison of fig. 3 a) and c), the nano-magnesia acts as a template to increase the porosity of the carbon material, increase the adsorption sites, and promote the oxidation-reduction reaction in the subsequent electrochemistry.
Example 3:
(1) Fully grinding and mixing 1g of tannic acid, 1g of pentahydroxy methyl furfural and 4g of nano magnesium oxide by using a mortar according to the mass ratio of 1:1:4, adding 5 ml of sulfuric acid with the concentration of 0.5mol/L in the grinding process, and continuously grinding for 30min;
(2) Collecting a uniformly ground sample into a polytetrafluoroethylene lining, transferring the sample into a hydrothermal kettle, and reacting for 12 hours at 180 ℃ to obtain a phenolic resin-based material;
(3) Transferring the phenolic resin-based material into a graphite boat, heating up at a heating rate of 2 ℃/min under nitrogen atmosphere until the temperature reaches 900 ℃, and preserving the temperature for 1 hour to obtain a sample;
(4) And cleaning the sample by using 1mol of hydrochloric acid, filtering, and then placing the sample in a 60 ℃ oven for drying for 6 hours to obtain the phenolic resin carbon material.
Example 4:
(1) Fully grinding and mixing tannic acid 1g, pentahydroxy methyl furfural 1g and nano magnesium oxide 6g by using a mortar according to the mass ratio of 1:1:6, adding 5 ml of sulfuric acid with the concentration of 0.5mol/L in the grinding process, and continuously grinding for 30min;
(2) Collecting a uniformly ground sample into a polytetrafluoroethylene lining, transferring the sample into a hydrothermal kettle, and reacting for 12 hours at 180 ℃ to obtain a phenolic resin-based material;
(3) Transferring the phenolic resin-based material into a graphite boat, heating up at a heating rate of 2 ℃/min under nitrogen atmosphere until the temperature reaches 900 ℃, and preserving the temperature for 1 hour to obtain a sample;
(4) And cleaning the sample by using 1mol of hydrochloric acid, filtering, and then placing the sample in a 60 ℃ oven for drying for 6 hours to obtain the phenolic resin carbon material.
Control group 1: (substitution of 1g of Benzaldehyde for 1g of PentahydroxymethylFurfural in example 1)
(1) Fully grinding and mixing tannic acid 1g, benzaldehyde 1g and nano magnesium oxide 2g by using a mortar according to the mass ratio of 1:1:2, adding 5ml of sulfuric acid with the concentration of 0.5mol/L in the grinding process, and continuously grinding for 30min;
(2) Collecting a uniformly ground sample into a polytetrafluoroethylene lining, transferring the sample into a hydrothermal kettle, and reacting for 12 hours at 180 ℃ to obtain a phenolic resin-based material;
(3) Transferring the phenolic resin-based material into a graphite boat, heating up at a heating rate of 2 ℃/min under nitrogen atmosphere until the temperature reaches 900 ℃, and preserving the temperature for 1 hour to obtain a sample;
(4) And cleaning the sample by using 1mol of hydrochloric acid, filtering, and then placing the sample in a 60 ℃ oven for drying for 6 hours to obtain the phenolic resin carbon material.
Control group 2: (substitution of 1g of PentahydroxymethylFurfural in example 1 with 1g of terephthalaldehyde)
(1) Fully grinding and mixing 1g of tannic acid, 1g of terephthalaldehyde and 2g of nano magnesium oxide by using a mortar according to the mass ratio of 1:1:2, adding 5ml of sulfuric acid with the concentration of 0.5mol/L in the grinding process, and continuously grinding for 30min;
(2) Collecting a uniformly ground sample into a polytetrafluoroethylene lining, transferring the sample into a hydrothermal kettle, and reacting for 12 hours at 180 ℃ to obtain a phenolic resin-based material;
(3) Transferring the phenolic resin-based material into a graphite boat, heating up at a heating rate of 2 ℃/min under nitrogen atmosphere until the temperature reaches 900 ℃, and preserving the temperature for 1 hour to obtain a sample;
(4) And cleaning the sample by using 1mol of hydrochloric acid, filtering, and then placing the sample in a 60 ℃ oven for drying for 6 hours to obtain the phenolic resin carbon material.
From examples 1,3 and 4 of the invention, the phenolic resin-based material can be successfully prepared from tannic acid and the pentahydroxymethyl furfural after acid catalysis and heat treatment. Phenolic resins can still be prepared by replacing aldehydes in the control group 1 and the control group 2.
The invention uses tannic acid and the pentahydroxymethyl furfural as raw materials for producing phenolic resin, which can greatly reduce the harm to human body and the pollution to environment caused in the production process.
The phenolic resin carbon material prepared by the invention has larger specific surface area, reasonable pore distribution and good morphology distribution, and the specific surface area of the material can reach 950.40m 2/g. The phenolic resin carbon material has high specific capacitance and matched energy density and power density as a carbon cathode of the zinc ion supercapacitor, and electrode tests of the zinc ion supercapacitor show that when the power density reaches 731W/kg, the specific capacitance reaches 90.7 mAh/g and the energy density reaches 79 Wh/kg.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (5)
1. The preparation method of the phenolic resin-based material is characterized by comprising the following specific preparation steps:
(a) Fully grinding and mixing tannic acid, pentahydroxymethyl furfural and nano magnesium oxide by using a mortar according to a mass ratio, adding a small amount of dilute sulfuric acid in the grinding process for catalysis, and continuously grinding until the materials are uniform;
(b) Collecting a uniformly ground sample into a polytetrafluoroethylene lining, transferring the sample into a hydrothermal kettle, and reacting to obtain a phenolic resin-based material;
Tannic acid: pentahydroxymethyl furfural: the mass ratio of the nano magnesium oxide is 1:1:2;
The dosage of the dilute sulfuric acid is 0.5 mol/L;
the reaction conditions in step (b) are: the reaction was carried out at 180℃for 12 hours.
2. A method for preparing a phenolic resin carbon material by using the phenolic resin-based material as claimed in claim 1, which is characterized by comprising the following specific preparation steps:
① Transferring the phenolic resin-based material into a graphite boat, heating to 900 ℃ under nitrogen atmosphere, and preserving heat for 1 hour to obtain a sample;
② And cleaning the sample by using hydrochloric acid, and placing the sample in an oven for drying after suction filtration to obtain the phenolic resin carbon material.
3. The method of preparing a phenolic resin carbon material of claim 2 wherein step ① is performed at a rate of temperature rise of: 2 ℃/min.
4. The method of preparing a phenolic carbon material of claim 2 wherein in step ②, hydrochloric acid is used to clean the sample by: 1mol/L.
5. The method of preparing a phenolic resin carbon material as claimed in claim 2, wherein the drying conditions of step ② are: and placing the mixture in a baking oven at 60 ℃ for baking for 6 hours.
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| CN102923687A (en) * | 2011-08-11 | 2013-02-13 | 北京大学 | Middle-pore carbon material and its preparation method |
| CN111943166A (en) * | 2020-07-17 | 2020-11-17 | 中国科学院兰州化学物理研究所 | Preparation of solvent-free hydrothermal carbon material |
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| WO2016150406A1 (en) * | 2015-03-26 | 2016-09-29 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere, and preparation and application thereof |
| CN110128784B (en) * | 2019-04-30 | 2021-11-09 | 中国林业科学研究院林产化学工业研究所 | Preparation method of water-based carbon hybrid material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102923687A (en) * | 2011-08-11 | 2013-02-13 | 北京大学 | Middle-pore carbon material and its preparation method |
| CN111943166A (en) * | 2020-07-17 | 2020-11-17 | 中国科学院兰州化学物理研究所 | Preparation of solvent-free hydrothermal carbon material |
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