CN115449042A - Micro-spherical phenolic resin and preparation method and application thereof - Google Patents
Micro-spherical phenolic resin and preparation method and application thereof Download PDFInfo
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- CN115449042A CN115449042A CN202110645648.4A CN202110645648A CN115449042A CN 115449042 A CN115449042 A CN 115449042A CN 202110645648 A CN202110645648 A CN 202110645648A CN 115449042 A CN115449042 A CN 115449042A
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 87
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 86
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 25
- 238000003763 carbonization Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 16
- 239000007772 electrode material Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 239000003377 acid catalyst Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 18
- 239000004005 microsphere Substances 0.000 description 33
- 238000001994 activation Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 229910001868 water Inorganic materials 0.000 description 19
- 235000019256 formaldehyde Nutrition 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 239000003990 capacitor Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000001723 curing Methods 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000010000 carbonizing Methods 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000013007 heat curing Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009172 bursting Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- -1 polyoxymethylene Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- 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
-
- 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
-
- 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
- C01B32/336—Preparation characterised by gaseous activating agents
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- 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
- Y02E60/10—Energy storage using batteries
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- Microelectronics & Electronic Packaging (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a micro-spherical phenolic resin, a preparation method and an application thereof, wherein the sphericity of the micro-spherical phenolic resin is more than 0.5, and the average particle size is less than 10 microns. The microspherical phenolic resin prepared by the invention is insoluble in absolute ethyl alcohol at room temperature, particles are not deformed and are not melted under the pressure of 50 kilograms applied at 100 ℃, and the mutual adhesion ratio among the particles is not higher than 10%. The microspherical phenolic resin is particularly suitable for being used as a raw material to prepare microspherical carbon materials or microspherical activated carbon materials.
Description
Technical Field
The invention relates to a preparation method of a high polymer material, in particular to a micro-spherical phenolic resin in the presence of an acid catalyst and a surfactant, and a preparation method and application thereof.
Background
In recent years, with the development of rechargeable lithium batteries and super capacitors, due to their light weight and high energy density, rechargeable lithium batteries and super capacitors are widely used as power sources in the fields of home appliances, hybrid vehicles, electric vehicles, and the like.
In the field of hybrid vehicles and pure electric vehicles, researchers have been working on the performance of batteries in terms of high capacity, excellent low-temperature charge and discharge properties, rapid charge and discharge properties, and excellent resistance to the number of charge and discharge cycles, and the demand for carbon materials used as electrode materials has been increasing. For example, in order to realize high charge and discharge characteristics of lithium ion rechargeable batteries, high purity, small particle size, and narrow particle size distribution of electrode materials are increasingly required.
In the field of super capacitors, super capacitors are gaining increasing attention as small-capacity backup batteries due to their excellent charge-discharge cycle performance and rapid charge-discharge characteristics. However, due to the characteristics of the super capacitor, the super capacitor often has the disadvantage of generally small capacity, and particularly with the rapid development of hybrid electric vehicles in recent years, the requirement for high capacity of the super capacitor is more and more increased. In order to improve the characteristic of small capacity of the super capacitor, one of the most direct and effective methods is to reduce the thickness of the electrode as much as possible and increase the capacity of the super capacitor on the premise of not greatly increasing the volume of the super capacitor, so that carbon powder used as an electrode material is increasingly required to have the characteristics of high purity, small particle size and narrow particle size distribution.
Industrial synthetic phenolic resins have high carbon residue and high purity, and are receiving increasing attention as raw materials of carbon materials.
At present, the manufacturing method of the cathode material is mainly to grind carbon materials or active carbon into powder by a mechanical grinding method, and then obtain electrode materials with required small particle size by classification. Due to the limitation of mechanical crushing equipment, electrode materials with the particle size of less than 20 microns need to be ground in a grading manner for multiple times, and the efficiency is very low; thus resulting in high cost. In addition, for preparing the electrode material with ultra-small particle size of about 2 microns, mechanical crushing is extremely difficult, and even if the mechanical crushing is realized, the obtained powdery carbon material has different shapes, and the surface area of single particles is large and uneven, so that when the powdery carbon material is used as the electrode material, the filling density per unit volume is low, the particles cannot be in close contact, a large number of gaps among the particles are generated, and the electrical conductivity among the particles is greatly reduced. In addition, due to the uneven particle shape of the powdery carbon material, in the transportation and use process, the particles are broken by mutual friction and collision to generate a large amount of nano-scale fine dust, which is particularly easy to happen on activated carbon, and the fine dust generated by mutual collision and breakage among the particles can block micropores of the activated carbon, so that the optimal performance of the electrode cannot be exerted.
In order to solve the above problems, researchers have been devoted to studies on the direct preparation of microspherical phenolic resins as raw materials of negative electrode carbon materials in a synthetic manner, and some results of studies on the influence of various parameters and methods on the resins are as follows. For example:
in the chinese patent application No. cn200410012346.X, it is mentioned that a phenolic resin is prepared by mixing a linear phenolic resin with hexamethylenetetramine, dissolving the mixture in methanol or ethanol to form a phenolic resin solution, preparing a surfactant and water into a solution, dispersing the phenolic resin alcohol solution into water containing the surfactant, dispersing the solution into a sphere, curing, suction filtering, washing with water, and drying.
In the chinese invention patent application No. CN200810079389.8, it is mentioned that the spherical phenolic resin is obtained by adding the linear phenolic resin, the curing agent, the industrial alcohol, the surfactant and the water into a reaction kettle in a certain mass ratio, then mechanically stirring at a certain speed, heating to a high temperature, and reacting for a period of time at a constant temperature.
In the Chinese invention patent application No. CN20710030439.2, commercial resol, a surfactant and a dispersion liquid are added into a reaction vessel according to the mass ratio of 0.05-10, the stirring speed is kept at a certain value, and the temperature is increased for a certain time; adding an acidic substance to adjust the pH value, reacting at constant temperature for a certain time, separating out the phenolic resin microspheres from the solvent, pouring out the supernatant, and washing and drying to obtain the spherical phenolic resin microspheres.
In the chinese patent application No. CN20110202143.7, there is a proposal to prepare phenolic resin microspheres by mixing resorcinol, phenol, formaldehyde, sodium carbonate, sodium bicarbonate and water, stirring, heating in an oil bath for reaction, filtering, washing with water, and drying.
In the Chinese patent application nos. cn200410012346.X and CN20710030439.2, the linear phenolic resin is used as the raw material, and when the granular phenolic resin is prepared by dispersion, the phenolic resin microspheres with a larger particle size of more than 100 microns can only be prepared due to the problems of solubility and the like, and the whole reaction is reacted in an aqueous solution, so that the prepared phenolic resin microspheres cannot be fully cured, and the problems of particle adhesion, particle bursting and the like can be generated in the curing, carbonizing and activating processes, and the high-precision microspherical carbon material cannot be prepared by using the linear phenolic resin as the raw material.
In the chinese patent application CN20710030439.2, the resol resin is used as a raw material, and the dispersion below 20 μm cannot be achieved by mechanical stirring, so that only the phenolic resin microspheres with a larger particle size can be prepared, and the whole reaction is carried out in an aqueous solution, so that the prepared phenolic resin microspheres cannot be sufficiently cured, and the problems of particle adhesion, particle bursting and the like are also generated in the curing, carbonizing and activating processes, and thus the high-precision microspherical carbon material cannot be prepared by using the resol resin as a raw material.
In the Chinese invention patent application No. CN20110202143.7, resorcinol is taken as a raw material, and when the produced microspherical phenolic resin is carbonized and activated, the yield of the prepared carbon material is low due to the low carbon residue rate of the resorcinol resin, so that the cost is high and the microspherical phenolic resin does not have high commercial value.
Therefore, the above techniques all have various disadvantages in the preparation of microspherical phenolic resins used as raw materials of carbon materials.
Disclosure of Invention
The invention aims at providing a micro-spherical phenolic resin.
The second invention of the present application is to provide a method for producing the microspherical phenolic resin.
A third object of the present invention is to provide a carbon material using the above microspherical phenolic resin as a raw material.
A fourth object of the present invention is to provide an activated carbon material using the above-mentioned carbon material as a raw material.
The technical scheme of the invention comprises the following steps:
a microspherical phenol resin having a sphericity of 0.5 or more and an average particle diameter of 10 μm or less.
Preferably, the sphericity is 0.5-1 and the average particle size is 0.5-5 microns.
According to the invention, the micro-spherical phenolic resin is insoluble in absolute ethyl alcohol at room temperature, particles are not deformed and are not melted under the pressure of 50 kilograms applied at 100 ℃, and the mutual adhesion ratio of the particles is not higher than 10%. The ratio of mutual adhesion between particles is preferably not more than 5%.
The invention also provides a preparation method of the phenolic resin microsphere, which comprises the following steps:
reacting a phenol monomer and a formaldehyde monomer at an elevated temperature in the presence of a strong acid catalyst and a surfactant, and adding an alkali into the obtained reaction solution for neutralization to prepare the microspherical phenolic resin.
According to the invention, the molar ratio between the formaldehyde-based monomer and the phenol-based monomer is greater than 1, preferably between 2 and 10, more preferably between 4 and 10. When the molar ratio of the formaldehydes to the phenols is less than 1, microspheres having a high sphericity cannot be obtained, and when the molar ratio is more than 10, the production efficiency is deteriorated and the production cost is increased.
According to the present invention, the phenolic monomer includes, but is not limited to, at least one of phenol or resorcinol, etc.
According to the present invention, the formaldehyde-based monomer includes, but is not limited to, at least one of formaldehyde or polyoxymethylene, and the like.
According to the present invention, the strong acid catalyst is at least one selected from sulfuric acid, hydrochloric acid, nitric acid, and the like.
According to the present invention, the concentration of the strong acid catalyst is 1.0 to 2.0 mol/l, preferably 1.5 to 2.0 mol/l, and the use amount of the strong acid catalyst exceeding 2 mol/l causes severe corrosion of production equipment, and is not suitable for mass production. When the amount of the strong acid catalyst is less than 1.0 mol/L, the reaction is carried out at a relatively high temperature in order to maintain a certain reaction rate, and thus the produced phenolic resin microspheres have large particle size, poor sphericity, easy adhesion to each other, and even no spherical structure.
According to the invention, ammonia, sodium hydroxide or potassium hydroxide can be used as the alkali. The amount of the alkali to be used is not limited, and may be adjusted so that the pH of the reaction solution is about 7.
According to the present invention, the surfactant is at least one of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and the like. For example: polyvinyl alcohol, sodium carboxymethylcellulose, alkyl quaternary ammonium salt and the like. The quaternary alkyl ammonium salt may be, for example, dioctadecyldimethylammonium chloride.
According to the present invention, the amount of the surfactant to be used is not particularly limited, and is adjusted depending on the raw material to be used and the particle size of the microsphere to be synthesized. For example, the surfactant is present in an amount of 20% by weight or less, preferably 15% by weight or less, based on the weight of the phenol monomer. When the surfactant is excessively added, more wastewater is generated in the washing process, the overall manufacturing cost is increased, and the environmental burden is increased. When the amount of the activating agent is too small, the particles are adhered, and the desired microspherical phenolic resin cannot be obtained.
According to the invention, the reaction temperature is between 15 ℃ and 100 ℃. For example, the polycondensation reaction is carried out at 15 to 50 ℃ and, after the completion of the polycondensation reaction, the curing reaction is carried out at 50 to 100 ℃. The polycondensation reaction temperature is too low, the reaction efficiency is poor, the temperature is too high, the particle size of the prepared microsphere is large, the particle size distribution is wide, and severe corrosion can be caused to production equipment. If the curing temperature is too low, the treatment effect cannot be achieved, and if the curing temperature is too high, equipment is easily corroded due to the strong acidic substance contained in the reaction system.
According to the invention, the preparation method of the microspherical phenolic resin comprises the following steps:
(1) Performing polycondensation reaction on a phenol monomer and a formaldehyde monomer in the presence of a strong acid catalyst and a surfactant, and neutralizing with alkali to prepare a microspherical phenolic resin suspension;
(2) And (3) heating and curing the suspension in the step (1) to prepare the microspherical phenolic resin.
According to the invention, in step (1), the temperature of the polycondensation reaction is 15 to 50 ℃, preferably 20 to 45 ℃. When the reaction temperature is too low, the reaction efficiency becomes poor, and when the reaction temperature is too high, the particle size of the prepared microspheres is large, the distribution is too wide, and severe corrosion can be caused to production equipment.
According to the invention, in step (2), the curing temperature is from 50 to 100 ℃ and preferably from 70 to 100 ℃.
And (2) neutralizing the reaction liquid in the step (1) with alkali, filtering, cleaning, drying and curing the microspherical phenolic resin to obtain the microspherical phenolic resin with the average particle size of less than 10 microns, the sphericity of more than 0.5 and the mutual adhesion ratio of particles of not more than 10%.
The invention also provides the application of the microspherical phenolic resin, which is applied to carbon materials; more preferably an activated carbon material.
Preferably, the microspherical phenolic resin is applied to an electrode material of a secondary charging battery or a super capacitor, preferably, an anode material of the secondary charging battery or an active material for an electrode of the super capacitor; more preferably, the negative electrode hard carbon material for a secondary rechargeable battery.
The application also provides a method for preparing a carbon material by taking the phenolic resin microspheres as raw materials, which comprises the following steps: and carbonizing the microspherical phenolic resin to prepare the carbon material.
According to the invention, the carbonization is carried out in an inert atmosphere, for example a gas such as nitrogen, argon, carbon monoxide, etc.
According to the invention, the carbonization temperature is between 150 and 1800 ℃, preferably between 160 and 1200 ℃. The carbonization temperature is too low, so that elements such as oxygen, nitrogen and the like in the raw materials can be remained too much, the conductivity is reduced, the carbonization temperature is too high, the energy consumption is too high, and the production cost of the product is increased.
The carbonization may be performed sequentially in 1 or 2 or more temperature zones. Also, preferably, the temperatures of the temperature regions are different from each other, or carbonization may be performed at a temperature of which gradient is increased.
According to the invention, after carbonization, micro-spherical phenolic resin carbon materials with different grain diameters can be prepared by classification.
The application also provides a preparation method of the activated carbon material, which comprises the following steps: and (3) activating the carbon material to prepare the activated carbon material.
According to the invention, the carbon material can be directly or taken out and put into the activation furnace again, and the microspherical activated carbon material can be prepared by utilizing the activation method commonly used in the prior art.
According to the present invention, the activation is performed in an atmosphere of water vapor, carbon dioxide, or the like, and a conventional chemical activation method may be used. Preferably in a carbon dioxide atmosphere.
According to the invention, the activation temperature is 700 to 1200 ℃, preferably 800 to 1100 ℃.
The activated carbon prepared after activation can be classified to obtain the microsphere activated carbon with small particle size and narrow dispersion. The particles of the microspherical activated carbon are not adhered to each other and still keep a nearly spherical shape. The electrode material prepared by using the microspherical phenolic resin as a raw material can greatly improve the packing density of the unit volume of the electrode, the particles are more easily in close contact, and the electrical conduction characteristic is improved. In addition, nanometer-scale dust which reduces the electrode characteristics is not easy to generate among particles in the transportation and use processes of the electrode material.
The application also provides the application of the carbon material and the activated carbon, which are applied to electrode materials of a super capacitor, preferably used as active substances for electrodes of the super capacitor.
Beneficial effect
(1) The sphericity of the phenolic resin is more than 0.5, the average particle size is less than 10 microns, the particle size distribution is narrow, the phenolic resin is insoluble in absolute ethyl alcohol at room temperature, the particles are not deformed and are not melted under the pressure of 50 kilograms at 100 ℃, and the mutual adhesion ratio among the particles is not higher than 10%. The microspherical phenolic resin is particularly suitable for being used as a raw material to prepare microspherical carbon materials or microspherical activated carbon materials.
(2) The electrode material prepared by taking the micro-spherical phenolic resin as the raw material can greatly improve the packing density of the unit volume of the electrode, the particles are in close contact more easily, and the electrical conduction characteristic is improved. In addition, nanometer-scale dust which reduces the electrode characteristics is not easy to generate among particles in the transportation and use processes of the electrode material.
Drawings
FIG. 1 is an SEM image of a microspherical phenolic resin prepared in example 1;
FIG. 2 is a graph showing the particle size distribution of the microspherical phenolic resin prepared in example 1;
fig. 3 is an SEM image of the activated carbon material prepared in example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In this example, the average particle size was measured by taking a photograph of a microspherical phenolic resin using a JSM-6390 electron microscope manufactured by japan electronics, randomly selecting 50 microspheres from the photograph, measuring the diameter in the X direction, and averaging the diameters.
The measurement of insolubility and insolubility in this example was carried out by the following method:
insolubility: taking 10 g of phenolic microspheres, placing into 500 g of absolute ethyl alcohol, circulating for one hour, filtering, washing dissolved residues with 200 g of absolute ethyl alcohol, placing into a 100 ℃ oven, heating for 1 hour, weighing the weight of the residues, and calculating the percentage of the residual weight of the residues.
Infusibility: taking 1 g of phenolic resin microspheres, putting the phenolic resin microspheres into a simple flat plate die, putting the phenolic resin microspheres into a hot press at 100 ℃, keeping the phenolic resin microspheres under the pressure of 50 kg for 2 minutes, taking the phenolic resin microspheres out, and observing whether the microspheres deform and adhere to each other.
The particle adhesion ratio: the obtained phenolic resin microspheres were photographed by a JSM-6390 electron microscope manufactured by Japan Electron, and the number of particles adhering to each other was observed in an area of 150. Mu.m.150. Mu.m, and then the total number of particles in the area was divided to determine the particle adhesion ratio.
Example 1
A preparation method of micro-spherical phenolic resin comprises the following specific steps:
in a 1 liter reactor equipped with a thermometer stirrer, 170 g of water, 270 g of 37% formaldehyde (3.33 mol), 140 g of 37% hydrochloric acid (1.42 mol), and 50 g of 2% sodium carboxymethylcellulose were sequentially charged, stirred and heated to 40 ℃, and 100 g (0.39 mol) of an aqueous 37% phenol solution was slowly added dropwise to the reactor, followed by reaction for 1 hour.
The temperature of the system was raised to 80 ℃ and maintained for 1 hour, then cooled to 40 ℃ and 2000 g of 2.5% ammonia solution was added for neutralization.
The phenolic resin microsphere dispersion was filtered and then washed again with 1000 g of water. The resultant was put into an oven at 100 ℃ and heated for 10 hours to obtain 100 g of a microspherical phenol resin.
Carbonizing
The prepared phenolic resin microspheres are subjected to deep heat curing treatment at 160 ℃ for 5 hours and 200 ℃ for 5 hours, then put into a carbonization furnace, and subjected to carbonization treatment at 300 ℃ for 2 hours, 500 ℃ for 3 hours and 900 ℃ for 2 hours under the protection of nitrogen.
Activation of
After the carbonization process is finished, carbon dioxide activation is continuously carried out at 900 ℃, and after the activation process lasts for 5 hours, the microspherical activated carbon material is prepared.
Example 2
In a 1 liter reactor equipped with a thermometer stirrer, 170 g of water, 270 g of 37% formaldehyde (3.33 mol), 140 g of 37% concentrated hydrochloric acid (1.42 mol), and 100 g of 2% sodium carboxymethylcellulose were sequentially charged, stirred and heated to 40 ℃, 100 g (0.39 mol) of a 37% aqueous phenol solution was slowly dropped into the reactor, and then reacted for 1 hour.
The temperature of the system was raised to 80 ℃ and maintained for 1 hour, then cooled to 40 ℃ and 2000 g of 2.5% ammonia solution was added for neutralization.
The phenolic resin microsphere dispersion was filtered and then washed again with 1000 g of water. The obtained product is put into an oven at 100 ℃ to be heated for 10 hours, and then 100 grams of microspherical phenolic resin is prepared.
Carbonizing
The prepared phenolic resin microspheres are subjected to deep heat curing treatment at 160 ℃ for 5 hours and 200 ℃ for 5 hours, then put into a carbonization furnace, and subjected to carbonization treatment at 300 ℃ for 2 hours, 500 ℃ for 3 hours and 900 ℃ for 2 hours under the protection of nitrogen.
Activation of
After the carbonization process is finished, the carbon dioxide activation is continued at 900 ℃, and after the activation process lasts for 5 hours, the microspherical activated carbon material is prepared.
Example 3
In a 1 liter reactor equipped with a thermometer stirrer, 170 g of water, 270 g of 37% formaldehyde (3.33 mol), 400 g of 37% sulfuric acid (1.51 mol), and 50 g of 2% sodium carboxymethylcellulose were sequentially charged, stirred and heated to 40 ℃, 100 g (0.39 mol) of an aqueous 37% phenol solution was slowly dropped into the reactor, and then reacted for 1 hour.
The temperature of the system was raised to 80 ℃ and maintained for 1 hour, then cooled to 40 ℃ and 4400 g of 2.5% aqueous ammonia was added for neutralization.
The phenolic resin microsphere dispersion was filtered and then washed again with 1000 g of water. The resultant was put into an oven at 100 ℃ and heated for 10 hours to obtain 100 g of a microspherical phenol resin.
Carbonizing
The prepared phenolic resin microspheres are subjected to deep heat curing treatment at 160 ℃ for 5 hours and 200 ℃ for 5 hours, then put into a carbonization furnace, and subjected to carbonization treatment at 300 ℃ for 2 hours, 500 ℃ for 3 hours and 900 ℃ for 2 hours under the protection of nitrogen.
Activation of
After the carbonization process is finished, the carbon dioxide activation is continued at 900 ℃, and after the activation process lasts for 5 hours, the microspherical activated carbon material is prepared.
Comparative example 1
In a 1 liter reactor equipped with a thermometer stirrer, 170 g of water, 270 g of 37% formaldehyde (3.33 mol), 140 g of 37% hydrochloric acid (1.42 mol), and 50 g of 2% sodium carboxymethylcellulose were sequentially charged, stirred and heated to 40 ℃, 100 g (0.39 mol) of an aqueous 37% phenol solution was slowly dropped into the reactor, and then reacted for 1 hour. The temperature was reduced to 40 ℃ and 2000 g of 2.5% ammonia solution was added for neutralization.
The phenolic resin microsphere dispersion was filtered and then washed again with 1000 g of water. The obtained material is put into an oven at 100 ℃ to be heated for 10 hours, and then most of microspheres are softened and adhered to each other to prepare 100 g of block-shaped phenolic resin.
Carbonizing
The prepared block phenolic resin is subjected to deep heat curing treatment at 160 ℃ for 5 hours and 200 ℃ for 5 hours, then put into a carbonization furnace, and subjected to carbonization treatment at 300 ℃ for 2 hours, 500 ℃ for 3 hours and 900 ℃ for 2 hours under the protection of nitrogen.
Activation of
And after the carbonization process is finished, continuing activating carbon dioxide at 900 ℃, and after the activation process lasts for 5 hours, preparing the blocky activated carbon material.
Comparative example 2
In a 1 liter reactor equipped with a thermometer stirrer, 170 g of water, 270 g of 37% formaldehyde (3.33 mol), 14 g of 37% concentrated hydrochloric acid (0.142 mol), and 50 g of 2% sodium carboxymethylcellulose were sequentially charged, stirred and heated to 40 ℃, 100 g (0.39 mol) of a 37% aqueous phenol solution was slowly dropped into the reactor, and then reacted for 1 hour.
The temperature of the system is raised to 80 ℃, kept for 1 hour, then cooled to 40 ℃, and 200 g of 2.5% ammonia solution is added for neutralization.
The above mixed solution did not produce a solid product.
Comparative example 3
In a 1 liter reactor equipped with a thermometer stirrer, 170 g of water, 270 g of 37% formaldehyde (3.33 mol) and 140 g of 37% concentrated hydrochloric acid (1.42 mol) were sequentially charged, stirred and heated to 40 ℃, and 100 g (0.39 mol) of an aqueous 37% phenol solution was slowly added dropwise to the reactor and reacted for 1 hour.
The temperature of the system is raised to 80 ℃, kept for 1 hour, then cooled to 40 ℃, and 200 g of 2.5% ammonia solution is added for neutralization.
The phenolic resin generated in the mixed liquid is coagulated into blocks and attached to the wall of the reactor and the stirring paddle.
Carbonizing
The prepared phenolic resin microspheres are subjected to deep heat curing treatment at 160 ℃ for 5 hours and 200 ℃ for 5 hours, then put into a carbonization furnace, and subjected to carbonization treatment at 300 ℃ for 2 hours, 500 ℃ for 3 hours and 900 ℃ for 2 hours under the protection of nitrogen.
Activation of
After the carbonization process is finished, carbon dioxide activation is continuously carried out at 900 ℃, and after the activation process lasts for 5 hours, the microspherical activated carbon material is prepared.
Comparative example 4
In a 1 liter reactor equipped with a thermometer stirrer, 170 g of water, 270 g of 37% formaldehyde (3.33 mol) and 140 g of concentrated phosphoric acid (1.42 mol) were sequentially charged, stirred and heated to 40 ℃, and 100 g (0.39 mol) of a 37% aqueous phenol solution was slowly added dropwise to the reactor, followed by a reaction for 1 hour.
The temperature of the system is raised to 80 ℃, kept for 1 hour, then cooled to 40 ℃, and 200 g of 2.5% ammonia solution is added for neutralization.
No solid product was produced in the above mixed solution.
Comparative example 5
In a 1 liter reactor equipped with a thermometer stirrer, 170 g of water, 270 g of 37% formaldehyde (3.33 mol) and 140 g of 37% concentrated hydrochloric acid (1.42 mol) were charged in this order, stirred and heated to 40 ℃, and 1000 g (3.9 mol) of a 37% phenol aqueous solution was charged into the reactor and reacted for 1 hour.
The temperature of the system is raised to 80 ℃, kept for 1 hour, then cooled to 40 ℃, and 200 g of 2.5% ammonia solution is added for neutralization.
No solid product was formed in the above-mentioned mixed solution.
The products of examples 1-3 and comparative examples 1-5 were tested, with the test parameters and results shown in table 1:
TABLE 1
By analyzing the data in table 1, it can be seen that in the presence of a high concentration strong acid catalyst and a surfactant, under the conditions of the present application in which the molar ratio of formaldehyde to phenol is 1 or more, a microspherical phenolic resin can be prepared, and the microspherical phenolic resin has the characteristics of small particle size and narrow distribution. The preparation method does not need processes such as mechanical crushing, suction filtration, water washing and the like with low efficiency, and is particularly suitable for large-scale industrial production.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A microspherical phenolic resin characterized in that the microspherical phenolic resin has a sphericity of 0.5 or more and an average particle diameter of 10 μm or less.
2. The microspherical phenolic resin of claim 1, wherein the microspherical phenolic resin has a sphericity of 0.5 to 1 and an average particle size of 0.5 to 5 microns.
Preferably, the micro-spherical phenolic resin is insoluble in absolute ethyl alcohol at room temperature, particles are not deformed and are not molten under the pressure of 50 kilograms at 100 ℃, and the mutual adhesion proportion among the particles is not higher than 10%. The ratio of mutual adhesion between particles is preferably not more than 5%.
3. The method for producing a microspherical phenol-formaldehyde resin according to any one of claims 1 to 2, wherein a phenol-type monomer and a formaldehyde-type monomer are reacted at an elevated temperature in the presence of a strong acid catalyst and a surfactant, and the resultant reaction solution is neutralized by adding a base to produce a microspherical phenol-formaldehyde resin.
4. The process according to claim 1, wherein the molar ratio between the formaldehyde-based monomer and the phenol-based monomer is greater than 1, preferably between 2 and 10, and more preferably between 4 and 10.
Preferably, the concentration of the strong acid catalyst is 1.0 to 2.0 moles/liter, preferably 1.5 to 2.0 moles/liter; the strong acid catalyst is at least one selected from sulfuric acid, hydrochloric acid, nitric acid and the like.
5. The method of claim 1, wherein the reaction temperature is 15 ℃ to 100 ℃.
6. Use of the microspheroidal phenolic resin according to any one of claims 1 to 2 in a carbonaceous material; more preferably in activated carbon materials.
7. The use according to claim 6, characterized in that the microspheroidal phenolic resin is applied to an electrode material of a secondary rechargeable battery or a supercapacitor, preferably, to an active material for an electrode of a secondary rechargeable battery or a supercapacitor; more preferably, the negative electrode hard carbon material for a secondary rechargeable battery.
8. A process for producing a microspherical phenolic resin carbonaceous material, characterized in that the microspherical phenolic resin according to any one of claims 1 to 2 is carbonized to produce the carbonaceous material.
Preferably, the carbonization is carried out in an inert atmosphere, which is nitrogen, argon or carbon monoxide.
9. A method for preparing an activated carbon material, characterized in that the activated carbon material is prepared by activating the carbon material prepared by the preparation method of claim 8.
Preferably, the activation temperature is 700-1200 ℃.
10. The activated carbon material of claim 9, wherein the activated carbon, when classified, results in a small particle size, narrow dispersion of activated carbon; the particles of the microspherical activated carbon are not adhered to each other and still keep a nearly spherical shape.
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