CN115449041A - Preparation method of micro-spherical phenolic resin - Google Patents
Preparation method of micro-spherical phenolic resin Download PDFInfo
- Publication number
- CN115449041A CN115449041A CN202110644479.2A CN202110644479A CN115449041A CN 115449041 A CN115449041 A CN 115449041A CN 202110644479 A CN202110644479 A CN 202110644479A CN 115449041 A CN115449041 A CN 115449041A
- Authority
- CN
- China
- Prior art keywords
- phenolic resin
- microspherical
- particles
- activated carbon
- particle size
- 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.)
- Pending
Links
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 97
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 30
- 239000011164 primary particle Substances 0.000 claims abstract description 25
- 239000011163 secondary particle Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 72
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 39
- 238000001994 activation Methods 0.000 claims description 24
- 238000003763 carbonization Methods 0.000 claims description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 11
- 238000000889 atomisation Methods 0.000 claims description 10
- 239000003990 capacitor Substances 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 16
- 239000007772 electrode material Substances 0.000 abstract description 11
- 239000002243 precursor Substances 0.000 abstract description 6
- 239000000428 dust Substances 0.000 abstract description 4
- 238000011049 filling Methods 0.000 abstract description 3
- 239000004005 microsphere Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 229910001868 water Inorganic materials 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 238000001723 curing Methods 0.000 description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007865 diluting 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 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
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Images
Classifications
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/122—Pulverisation by spraying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
- C08J2361/10—Phenol-formaldehyde condensates
-
- 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
Abstract
The invention discloses a preparation method of micro-spherical phenolic resin, wherein the particle size of micro-spherical phenolic resin secondary particles is more than 20 mu m, and the secondary particles are carbonized and/or activated and then cracked into primary particles less than 20 mu m. The electrode material prepared from the microspherical carbon material by using the microspherical phenolic resin as the precursor raw material can greatly improve the unit volume filling density of the electrode, the particles are more easily in close contact with each other, and the electrical conduction characteristic is improved. In addition, in the process of transporting and using the electrode material, nano-scale dust is not easy to generate among particles, so that the electrical characteristics of the electrode can not be reduced.
Description
Technical Field
The invention relates to a preparation method of a high polymer material, in particular to a preparation method of a micro-spherical phenolic resin in the presence of an alkaline catalyst and a surfactant.
Background
In recent years, with the development of rechargeable lithium batteries and super capacitors, due to their light weight and high energy density, secondary lithium batteries and super capacitors have been 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 charge and discharge cycles. For this reason, the demand for carbon materials used as electrode materials is also increasing. For example, in order to realize high charge/discharge characteristics of secondary lithium ion batteries, requirements for high purity, small particle size, and narrow particle size distribution of electrode materials are increasing.
In the field of supercapacitors, supercapacitors are gaining increasing attention as small capacity backup batteries due to their excellent charge-discharge cycling performance and rapid charge-discharge characteristics. However, due to its own characteristics, the super capacitor often has a disadvantage of generally small capacity, and particularly with the rapid development of hybrid vehicles in recent years, the high capacity requirement 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.
The industrial synthetic phenolic resin has the characteristics of high carbon residue rate and high purity, and is receiving more and more attention as a precursor of a carbon material.
At present, the manufacturing method of the cathode material is mainly to grind a carbon material or active carbon into powder by a mechanical grinding method, and then obtain the electrode material with the required small particle size by classification. Due to the limitation of mechanical crushing equipment, the electrode material with the particle size of less than 20 microns needs to be ground for multiple times in a grading manner, so that the efficiency is very low; thus resulting in high cost. In addition, for preparing an electrode material with an ultra-small particle size of about 2 microns, mechanical pulverization is extremely difficult, and even if the mechanical pulverization is realized, the obtained powdery carbon material has different shapes due to the mechanical pulverization, and the surface area of each particle is large and uneven, so that when the powdery carbon material is used as the electrode material, the unit volume filling density 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 addition, in the process of preparing a carbon material or an activated carbon material having a small particle size (particularly, 20 μm or less), the production efficiency and yield are greatly reduced due to scattering of the material during the production and transportation processes due to the process characteristics of the existing carbonization furnace and activation furnace, and the environment is easily contaminated by nano-substances, so that large-scale mass production cannot be realized.
In order to solve the above problems, researchers have been devoted to studies on the direct preparation of microspherical phenolic resin as a raw material of a precursor of a negative electrode carbon material in a synthetic manner, and the following are some of the results of the studies using various parameters and methods. For example:
in the chinese patent application No. cn200410012346.X, it is mentioned that a phenolic resin in the form of sphere 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 into a solution with water, dropping the phenolic resin in the form of 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 phenolic novolac resin, the curing agent, the industrial alcohol, the surfactant and the water are added into the reaction kettle in a certain mass ratio, and then mechanically stirred at a certain speed, heated to a high temperature, and reacted at a constant temperature for a period of time to obtain the spherical phenolic resin.
In the Chinese invention patent application No. CN20710030439.2, commercial resol, a surfactant and a dispersion are added into a reaction vessel according to the mass ratio of 0.05-10, and the mixture is stirred at a certain stirring speed and heated for a certain time, wherein the mass ratio of the commercial resol to the surfactant to the dispersion is from 5 to 50; 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 invention patent application No. CN20110202143.7, the phenolic resin microspheres are prepared by mixing resorcinol, phenol, formaldehyde, sodium carbonate, sodium bicarbonate and water, stirring, performing oil bath heating reaction, performing suction filtration, washing with water and drying.
In the Chinese invention patent application No. CN200410012346.X and No. CN20710030439.2, linear phenolic resin is used as a raw material, when granular phenolic resin is prepared by dispersion, 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 prepared phenolic resin microspheres cannot be fully cured due to the reaction of the whole reaction in an aqueous solution, so that the problems of particle adhesion, particle burst and the like can be generated in the curing, carbonizing and activating processes, and high-precision microspherical carbon materials cannot be prepared by using the phenolic resin as the raw material.
In the chinese patent application No. CN20710030439.2, the resol is used as a raw material, and the dispersion below 20 μm cannot be achieved by mechanical stirring, so that only large-particle size phenolic resin microspheres 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 also occur during the curing, carbonization and activation processes, and thus, the high-precision microspherical carbon material cannot be prepared by using the resol as a raw material.
In the Chinese invention patent application No. CN20110202143.7, resorcinol is used 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 cost does not have high commercial value.
In addition, when the micro-spherical phenolic resin is prepared, the processes of suction filtration, water washing, drying and the like are required, the production process is complex, a large amount of waste water is generated, the efficiency is low, and large-scale mass production cannot be realized.
Therefore, the above techniques have various disadvantages in the production of a microspherical phenolic resin used as a raw material of a precursor of a carbonaceous material.
Disclosure of Invention
The primary purpose of the present application is to provide a microspherical 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 carbon material as a raw material.
The technical scheme of the invention comprises the following steps:
a microspherical phenolic resin, which is a secondary particle having a particle diameter of 20 [ mu ] m or more, wherein the secondary particle is composed of a plurality of primary particles, and the phenolic resin is cracked into primary particles having a particle diameter of 20 [ mu ] m or less after carbonization and/or activation.
Preferably, the particle size of the phenolic resin secondary particles is 20-2000 μm.
Preferably, the phenolic resin secondary particles include at least one primary particle therein.
Preferably, the particle size of the dissociated primary particles after the microspheres of the phenolic resin secondary particles are carbonized is 0.1-20 μm.
The invention also provides a preparation method of the micro-spherical phenolic resin, which comprises the following specific steps: in the presence of an alkaline catalyst and a surfactant, a phenol monomer and a formaldehyde monomer are subjected to a pressure heating reaction to prepare a microspherical phenolic resin suspension containing primary particles, and the microspherical phenolic resin suspension containing the primary particles is subjected to atomization drying to prepare the microspherical phenolic resin.
According to the invention, the molar ratio of the formaldehyde monomer to the phenol monomer is 1-3:1. The inventor finds that when the molar ratio is too low, the softening point of the prepared microspherical phenolic resin is too low, and the microspherical phenolic resin is softened and crosslinked in a curing process, so that phenolic resin microspheres cannot be obtained; when the molar ratio is too high, the excess formaldehyde monomer adversely affects the subsequent process.
According to the invention, the formaldehyde monomer is selected from at least one of formaldehyde and polyformaldehyde.
According to the present invention, the phenolic monomer is selected from at least one of, but not limited to, phenol, resorcinol, and the like.
According to the present invention, the basic catalyst includes an amine catalyst selected from at least one of, but not limited to, ammonia, hexamethylenetetramine, triethylamine, and the like.
According to the invention, the surfactant is a nonionic surfactant, an anionic surfactant or a cationic surfactant. For example, the surfactant can be one of polyvinyl alcohol, sodium carboxymethyl cellulose, quaternary ammonium salt and the like; the quaternary ammonium salt may be, for example, dioctadecyldimethylammonium chloride.
According to the invention, the pressure of the reaction is greater than one standard atmosphere. Preferably 1.5-2.5atm.
According to the invention, the reaction temperature is between 10 and 150 ℃. For example, the polycondensation reaction is carried out at 40 to 90 ℃ and, after the polycondensation reaction is completed, the curing reaction is carried out at 90 to 150 ℃.
According to the invention, the preparation method of the microspherical phenolic resin comprises the following steps:
(1) Dissolving a surfactant in an aqueous solvent, performing polycondensation reaction on a phenol monomer and a formaldehyde monomer in the presence of an alkaline catalyst, and heating and curing at a temperature higher than 100 ℃ and a pressure higher than a standard atmospheric pressure to prepare a microspherical phenolic resin suspension containing primary particles;
(2) And drying the micro-spherical phenolic resin suspension containing the primary particles by an atomization drying method to prepare the micro-spherical phenolic resin containing the secondary particles.
According to the present invention, the particle diameter of the microspherical phenol resin containing the secondary particles is not smaller than the particle diameter of the microspherical phenol resin containing the primary particles.
According to the present invention, the aqueous solvent is preferably at least one of water, a water-soluble inorganic salt solution, and a water-soluble organic salt solution. For example, the water-soluble inorganic salt may be sodium chloride; the water-soluble organic salt solution may be sodium acetate.
According to the invention, the amount of the surfactant added is 1 to 30%, preferably 8 to 20% of the total mass of the raw materials. Wherein, the total raw materials comprise a surface active agent, a phenol monomer, a formaldehyde monomer and a basic catalyst.
According to the invention, the temperature of the polycondensation is less than 100 ℃ and preferably between 40 and 90 ℃. The reaction at this stage is not particularly pressure-critical.
According to the present invention, in step (1), curing is carried out at 100 ℃ or higher and elevated pressure, preferably at a curing temperature of 110 to 150 ℃, thereby allowing the monomers in the system to be completely reacted. The curing temperature is too low, the curing reaction can not be fully carried out, the curing temperature is too high, the requirements on equipment are too strict, and the implementation cost is too high. The curing pressure is more than 1atm, and may be, for example, 1.5atm, 2atm, 2.5atm, or the like.
According to the present invention, the spray drying method in step (2) includes, but is not limited to, an electrostatic spray drying method, an ultrasonic spray drying method, a fluid collision spray drying method, and the like, and is preferably an ultrasonic spray drying method.
According to the invention, in the step (2), the temperature of the suspension is controlled to be 10-80 ℃ during atomization drying. If the temperature is too high, the viscosity of the system is reduced, which is not beneficial to the stability of the liquid drops, and if the temperature is too low, the viscosity of the system is increased, which is also not beneficial to the stability of the liquid drops.
The application also provides the application of the micro-spherical phenolic resin, which is applied to carbon materials; more preferably in the activated carbon material.
Preferably, the specific surface area of the activated carbon is 1800-2500 m 2 The content of mesopores (2-50 nm) is 25-30%, and the content of macropores (more than 50 nm) is less than 5%.
The application also provides a preparation method of the carbon material, which comprises the following steps: and carbonizing the micro-spherical phenolic resin to obtain 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, when the micro-spherical phenolic resin is carbonized, the secondary particles are automatically dissociated into the primary particles, and the micro-spherical phenolic resin carbon material is prepared.
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 are excessive to cause the reduction of conductivity, the carbonization temperature is too high to cause the excessive consumption of energy sources, and the production cost of the product is increased.
According to the invention, the carbonization can be carried out in succession in 1 or 2 or more temperature zones. And, preferably, the temperatures of the temperature regions are different from each other. Alternatively, carbonization may be carried out at a temperature that is increased in gradient.
According to the invention, the phenolic resin microspheres are carbonized and classified to obtain the carbon microspheres with small particle size and narrow dispersion average particle size of 0.1-20 microns. The carbon microspheres are not adhered to each other and still keep close to a spherical shape.
The invention also provides a preparation method of the activated carbon material, which comprises the following steps: and activating the carbon material to obtain the activated carbon material.
Specifically, the carbon material is directly or after being taken out, put into an activation furnace again, and activated carbon in a microsphere shape is prepared by using an activation method commonly used in the prior art.
According to the present invention, the activation is performed in an atmosphere of steam, carbon dioxide, or the like, and a conventional chemical activation method may be used. Preferably by activation in an atmosphere of carbon dioxide,
according to the invention, the activation temperature is 700-1200 ℃.
According to the invention, the activated carbon prepared after activation can be classified to obtain the 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 application also provides application of the carbon material and the activated carbon, and the carbon material and the activated carbon are applied to lithium ion or sodium ion secondary batteries, preferably active substances of negative electrode materials of the lithium ion secondary batteries and super capacitor electrodes.
Advantageous effects
(1) The application provides a method for efficiently preparing a large amount of microspherical phenolic resin, wherein the phenolic resin microspheres are secondary particles and at least comprise one primary particle of the phenolic resin microsphere with the average particle size of 0.1-20 microns. After the phenolic resin microspheres are carbonized and activated, secondary particles are dissociated into primary particles with the particle size of less than 20 microns. The microspherical phenolic resin is particularly suitable for preparing microspherical carbon materials or microspherical activated carbon materials as a raw material.
(2) The electrode material prepared from the microspherical carbon material by using the microspherical phenolic resin as the precursor raw material can greatly improve the unit volume filling density of the electrode, the particles are more easily in close contact with each other, and the electrical conduction characteristic is improved. In addition, in the process of transporting and using the electrode material, nano-scale dust is not easy to generate among particles, so that the electrical characteristics of the electrode are not reduced.
(3) The microspherical phenolic resin has the characteristics of small particle size and narrow distribution, does not need mechanical crushing which is low in efficiency and time-consuming in a production process, does not need processes such as suction filtration and water washing which are time-consuming and generate a large amount of waste water, and is particularly suitable for large-scale industrial production.
Drawings
FIG. 1 is a schematic view of the structure of the microspherical phenolic resin of 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 technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Part of the data used in this application is derived from the following method:
the average particle diameter of the particles was measured by taking a photograph of the microspherical phenol resin using a JSM-6390 electron microscope manufactured by Japan Electron, randomly selecting 50 microspheres in the photograph, measuring the diameter in the X direction, and averaging.
The mean particle size of the droplets after atomization was determined using a Spraytec tester manufactured by Malvern Instruments Ltd.
Example 1
A preparation method of micro-spherical phenolic resin comprises the following specific steps:
the first step is as follows: a1 liter pressurizable reactor equipped with a thermometer and stirrer was charged with 300 g of water, 200 g of phenol (2.12 mol), 60 g of 18% medium molecular weight fully alkalized polyvinyl alcohol (derived from POVAL 28-98 produced by KURAAY), stirred and heated to 40 ℃ until phenol was completely dissolved, 260 g (3.21 mol) of 37% formaldehyde was charged, uniformly stirred at 120 rpm and heated to 50 ℃, 30 g of basic catalyst triethylamine was charged into the reactor, heated to 90 ℃ and reacted for 4 hours.
And secondly, switching the reactor to a pressurized state, setting the internal pressure to be 2 times of atmospheric pressure, gradually raising the temperature in the reactor to 115 ℃, continuing to react for 2 hours at 115 ℃, and cooling to prepare 850 g of microspherical phenolic resin dispersion, namely microspherical phenolic resin suspension containing primary particles. A small amount of the dispersion was taken, and the average particle diameter of the primary particles was calculated to be 13.2 μm after photographing with JSM-6390.
And thirdly, cooling the suspension to 40 ℃, and carrying out atomization drying by using a Japanese small spray drying device SD-1010. The droplets had an average particle size of 200 microns on atomization. The drying temperature was set at 280 ℃ and about 300 g of secondary particles having an average particle size of 120 μm were recovered by drying to prepare a microspherical phenol resin.
Carbonizing:
the prepared microspherical secondary particle phenolic resin is heated for 5 hours at 160 ℃, heated for 5 hours at 200 ℃ for deep thermocuring treatment, put into a carbonization furnace, heated for 2 hours at 300 ℃, heated for 3 hours at 500 ℃ and heated for 2 hours at 900 ℃ under the protection of nitrogen for carbonization treatment.
Activation:
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 with the average grain diameter of 11 microns is prepared.
The specific surface area of the prepared activated carbon is 1800m 2 The content of mesopores (2-50 nm) is 25 percent, and the content of macropores (more than 50 nm) is 3 percent.
Example 2
The first step is as follows: A1L pressurizable reactor equipped with a thermometer and stirrer was charged with 300 g of water, 200 g of phenol (2.12 mol), 180 g of 18% medium molecular weight fully alkalized polyvinyl alcohol (derived from POVAL 28-98 produced by KURARAAY), stirred and heated to 40 ℃ until phenol was completely dissolved, 260 g of formaldehyde (3.21 mol) at 37% concentration was charged, stirred uniformly at 120 rpm and heated to 50 ℃, 10 g of basic catalyst triethylamine was charged into the reactor, heated to 90 ℃ and reacted for 4 hours.
And secondly, switching the reactor to a pressurized state, setting the internal pressure to be 2 times of atmospheric pressure, gradually raising the temperature in the reactor to 115 ℃, continuing to react for 2 hours at 115 ℃, and cooling to prepare 850 g of microspherical phenolic resin dispersion, namely microspherical phenolic resin suspension containing primary particles. A small amount of the dispersion was photographed with JSM-6390 to calculate the average particle diameter of the primary particles to be 5.2. Mu.m.
Thirdly, the suspension is cooled to 40 ℃ and then atomized and dried by a Japanese mini spray dryer SD-1010. The droplets had an average particle size of 230 microns on atomization. The drying temperature was set at 280 ℃ and about 320 g of secondary particles having an average particle size of 140 μm were recovered by drying to prepare a microspherical phenolic resin.
Carbonizing:
the obtained microspherical secondary particle phenolic resin is heated for 5 hours at 160 ℃, heated for 5 hours at 200 ℃ for deep thermocuring treatment, put into a carbonization furnace, heated for 2 hours at 300 ℃, heated for 3 hours at 500 ℃ and heated for 2 hours at 900 ℃ under the protection of nitrogen for carbonization treatment.
And (3) activation:
after the carbonization process is finished, carbon dioxide activation is continuously carried out at 900 ℃, and after the activation process lasts for 5 hours, a microspherical activated carbon material with the average grain diameter of 4 microns is prepared.
Specific surface area of activated carbon 1950m 2 The content of mesopores (2-50 nm) is 28 percent and the content of macropores (more than 50 nm) is 1 percent.
Comparative example 1
The first step is as follows: A1L pressurizable reactor equipped with a thermometer and stirrer was charged with 300 g of water, 200 g of phenol (2.12 mol), 60 g of 18% medium molecular weight fully alkalized polyvinyl alcohol (derived from POVAL 28-98 produced by KURARAAY), stirred and heated to 40 ℃ until phenol was completely dissolved, 260 g of formaldehyde (3.21 mol) at 37% concentration was charged, stirred uniformly at 120 rpm and heated to 50 ℃, 30 g of basic catalyst triethylamine was charged into the reactor, heated to 90 ℃ and reacted for 4 hours.
And a second step of cooling the suspension to 40 ℃ and carrying out atomization drying by using a Japanese mini spray dryer SD-1010. The droplets had an average particle size of 200 microns on atomization. The drying temperature was set at 280 ℃ and about 300 g of secondary particles having an average particle size of 120 μm were recovered by drying to prepare a microspherical phenol resin.
Carbonizing:
the obtained micro-spherical secondary particle phenolic resin is heated for 5 hours at 160 ℃, heated for 5 hours at 200 ℃, subjected to deep heat curing treatment, put into a carbonization furnace, heated for 2 hours at 300 ℃, heated for 3 hours at 500 ℃ and heated for 2 hours at 900 ℃ under the protection of nitrogen, and subjected to carbonization treatment.
Activation:
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.
The specific surface area of the prepared activated carbon is 1820m 2 The volume ratio of the mesoporous (2-50 nm) to the macroporous (more than 50 nm) is 5 percent per gram.
Comparative example 2
A preparation method of micro-spherical phenolic resin comprises the following specific steps:
the first step is as follows: A1L pressurizable reactor equipped with a thermometer and stirrer was charged with 300 g of water, 200 g of phenol (2.12 mol), 60 g of 18% medium molecular weight fully alkalized polyvinyl alcohol (derived from POVAL 28-98 produced by KURARAAY), stirred and heated to 40 ℃ until phenol was completely dissolved, 260 g (3.21 mol) of formaldehyde with a concentration of 37% was charged, uniformly stirred at 120 rpm and heated to 50 ℃, 10 g of basic catalyst triethylamine was charged into the reactor, heated to 90 ℃ and reacted for 4 hours, and then cooled to room temperature.
And secondly, switching the reactor to a pressurized state, setting the internal pressure to be 2 times of atmospheric pressure, gradually raising the temperature in the reactor to 115 ℃, continuing to react for 2 hours at 115 ℃, and cooling to prepare 850 g of microspherical phenolic resin suspension liquid, wherein the average particle size of the suspension liquid is 15 microns.
And thirdly, adding 1500 g of warm water into the microspherical phenolic resin for diluting in a large amount, performing suction filtration, washing with water to remove the surfactant in the reaction system, performing the same washing process for three times, and drying to obtain 150 g of microspherical phenolic resin with the average particle size of 15 microns. The process produced 3000 grams of wastewater and required a reaction time of 72 hours.
Carbonizing:
the micro-spherical phenolic resin prepared above is heated at 160 ℃ for 5 hours and 200 ℃ for 5 hours for deep heat curing treatment, the whole is crosslinked and can not be separated into blocks, and the blocks are put into a carbonization furnace and carbonized at 300 ℃ for 2 hours, 500 ℃ for 3 hours and 900 ℃ for 2 hours under the protection of nitrogen.
And (3) activation:
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 microsphere active carbon with the average grain diameter of 11 micrometers is prepared.
The prepared activated carbon comprises the following components: specific surface area 1760m 2 The volume ratio of the mesoporous (2-50 nm) to the macroporous (more than 50 nm) is 24 percent per gram.
TABLE 1 particle size of particles in examples 1-2 and comparative examples 1-2
By analyzing the data of table 1, the primary particles synthesized in comparative example 1 were not completely cured at high temperature, and thus, after high-temperature carbonization and activated carbon processes, the particles were softened and adhered to each other, and thus, a spherical carbon material could not be obtained. The microspherical phenolic resin synthesized in comparative example 2 can still be used for preparing spherical activated carbon after being washed by a large amount of water, but the whole process is time-consuming and generates a large amount of waste water, thus generating great burden on the manufacturing cost and the environment.
The carbon microspheres and the activated carbon microspheres prepared by using the microspherical phenolic resin prepared by the method as a precursor still keep complete spherical shapes. The production process does not need the processes of 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 within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A microspherical phenolic resin, characterized in that the microspherical phenolic resin is a secondary particle, the secondary particle of the phenolic resin has a particle size of more than 20 μm, the secondary particle is composed of a plurality of primary particles, and after carbonization and/or activation, the phenolic resin is cracked into primary particles with the particle size of less than 20 μm.
2. The microspherical phenolic resin of claim 1, wherein the secondary phenolic resin particles have a particle size of 20 to 2000 μm.
Preferably, at least one primary particle is included in the phenolic resin.
Preferably, the particle size of the dissociated primary particles of the carbonized micro-spherical phenolic resin is 0.1-20 μm.
3. The method for preparing the micro-spherical phenolic resin according to any one of claims 1 to 2, which comprises the following specific steps: the preparation method comprises the steps of carrying out pressurized heating reaction on a phenol monomer and a formaldehyde monomer in the presence of an alkaline catalyst and a surfactant to prepare a microspherical phenolic resin suspension containing primary particles, and carrying out atomization drying on the microspherical phenolic resin suspension containing the primary particles to prepare the microspherical phenolic resin.
4. The method according to claim 3, wherein the molar ratio of the formaldehyde-based monomer to the phenol-based monomer is 1 to 3:1.
5. The process according to claim 3, wherein the pressure of the reaction is greater than one standard atmosphere, preferably 1.5-2.5atm; the reaction temperature is 10-150 ℃.
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.
Preferably, the specific surface area of the activated carbon is 1800-2500 m 2 The content of mesopores (2-50 nm) is 25-30% and the content of macropores (more than 50 nm) is less than 5%.
7. Use of the microspherical phenolic resin according to claim 6, characterized by being applied to a lithium ion or sodium ion secondary battery;
preferably, the active material is used for the negative electrode material of the lithium ion secondary battery and the super capacitor electrode.
8. A process for producing a microspherical phenolic resin carbonaceous material, which comprises carbonizing the microspherical phenolic resin according to any one of claims 1 to 2.
Preferably, the carbonization is carried out in an inert atmosphere, which is nitrogen, argon or carbon monoxide.
Preferably, when the micro-spherical phenolic resin is carbonized, the secondary particles are dissociated into primary particles to prepare the micro-spherical phenolic resin carbon material.
9. A method for producing an activated carbon material, characterized in that the activated carbon material is produced by activating the carbon material produced by the production method according to claim 8.
Preferably, the activation temperature is 700-1200 ℃.
10. The method for preparing the carbon dioxide according to the claim 8, wherein the activated carbon prepared after activation is classified to obtain the 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 close to a sphere shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110644479.2A CN115449041A (en) | 2021-06-09 | 2021-06-09 | Preparation method of micro-spherical phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110644479.2A CN115449041A (en) | 2021-06-09 | 2021-06-09 | Preparation method of micro-spherical phenolic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115449041A true CN115449041A (en) | 2022-12-09 |
Family
ID=84295302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110644479.2A Pending CN115449041A (en) | 2021-06-09 | 2021-06-09 | Preparation method of micro-spherical phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115449041A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070191572A1 (en) * | 2006-02-14 | 2007-08-16 | Tustin Gerald C | Resol beads, methods of making them, and methods of using them |
| CA2752684A1 (en) * | 2009-03-03 | 2010-09-10 | Umicore | Process for preparing alloy composite negative electrode material for lithium ion batteries |
| CN103871756A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院兰州化学物理研究所 | Preparation method of submicron porous carbon bead |
| CN105845936A (en) * | 2016-03-22 | 2016-08-10 | 福建翔丰华新能源材料有限公司 | Preparation method of modified hard carbon negative electrode material for lithium ion battery |
| CN105914371A (en) * | 2016-05-06 | 2016-08-31 | 宁德新能源科技有限公司 | Phenolic resin-based hard carbon microspheres, preparation method thereof, negative electrode material and secondary battery |
| CN106185919A (en) * | 2016-07-16 | 2016-12-07 | 中国科学院山西煤炭化学研究所 | A kind of method preparing functional resin base spheric active carbon |
| CN108671887A (en) * | 2018-05-18 | 2018-10-19 | 无锡德碳科技股份有限公司 | A kind of activated carbon ball and its preparation method and application |
| CN109292774A (en) * | 2018-10-23 | 2019-02-01 | 武汉理工大学 | A kind of preparation method and applications of pomegranate shape porous carbon sphere material |
| CN112547008A (en) * | 2020-11-13 | 2021-03-26 | 广东宜纳新材料科技有限公司 | Carbon microsphere for adsorbing dioxin |
-
2021
- 2021-06-09 CN CN202110644479.2A patent/CN115449041A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070191572A1 (en) * | 2006-02-14 | 2007-08-16 | Tustin Gerald C | Resol beads, methods of making them, and methods of using them |
| CA2752684A1 (en) * | 2009-03-03 | 2010-09-10 | Umicore | Process for preparing alloy composite negative electrode material for lithium ion batteries |
| CN103871756A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院兰州化学物理研究所 | Preparation method of submicron porous carbon bead |
| CN105845936A (en) * | 2016-03-22 | 2016-08-10 | 福建翔丰华新能源材料有限公司 | Preparation method of modified hard carbon negative electrode material for lithium ion battery |
| CN105914371A (en) * | 2016-05-06 | 2016-08-31 | 宁德新能源科技有限公司 | Phenolic resin-based hard carbon microspheres, preparation method thereof, negative electrode material and secondary battery |
| CN106185919A (en) * | 2016-07-16 | 2016-12-07 | 中国科学院山西煤炭化学研究所 | A kind of method preparing functional resin base spheric active carbon |
| CN108671887A (en) * | 2018-05-18 | 2018-10-19 | 无锡德碳科技股份有限公司 | A kind of activated carbon ball and its preparation method and application |
| CN109292774A (en) * | 2018-10-23 | 2019-02-01 | 武汉理工大学 | A kind of preparation method and applications of pomegranate shape porous carbon sphere material |
| CN112547008A (en) * | 2020-11-13 | 2021-03-26 | 广东宜纳新材料科技有限公司 | Carbon microsphere for adsorbing dioxin |
Non-Patent Citations (3)
| Title |
|---|
| WANG, LL 等: "Phenolic formaldehyde resin/graphene composites as lithium-ion batteries anode", 《MATERIALS LETTERS》, vol. 170, pages 217 - 220, XP029451884, DOI: 10.1016/j.matlet.2016.01.062 * |
| 周岱;雷倩;陈晓红;宋怀河;: "水热法制备纳米酚醛树脂微球的研究", 北京化工大学学报(自然科学版), no. 04, 20 July 2016 (2016-07-20), pages 53 - 58 * |
| 邓仙梅 等: "SiO2掺杂硬炭作锂离子电池负极材料的研究", 《现代化工》, vol. 40, no. 11, pages 82 - 86 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI411576B (en) | A non-thermofusible granular phenol resin and a method for producing the same, and a thermosetting resin composition, a filler for semiconductor and a bonding agent for a semiconductor (2) | |
| JP5947585B2 (en) | Method for producing spherical phenol resin granulated product, method for producing carbon material, and method for producing activated carbon material | |
| JP4949971B2 (en) | Carbon electrode material, carbon electrode material mixture, carbon electrode material manufacturing method, electric double layer capacitor, lithium ion battery, and lithium ion capacitor | |
| CN101659410B (en) | Non-thermofusible phenol resin powder and method for producing the same | |
| CN105289433A (en) | Method for large-scale preparation of transition metal oxide porous microsphere | |
| CN114368739B (en) | Hard carbon material, preparation method thereof, electrode, battery and application | |
| CN109592663B (en) | Microsphere assembled porous carbon material and preparation method and application thereof | |
| CN106824117A (en) | The preparation method of the one order mesoporous adsorbent of species cage type | |
| JP2001146410A (en) | Active carbon and method for producing the same | |
| CN115449041A (en) | Preparation method of micro-spherical phenolic resin | |
| CN112864368A (en) | Preparation method of composite coated modified lithium manganese iron phosphate cathode material | |
| CN107285312B (en) | Flake active carbon material and preparation method and application thereof | |
| CN110171827B (en) | Nitrogen-doped spherical porous carbon, preparation method and application thereof | |
| CN115449042A (en) | Micro-spherical phenolic resin and preparation method and application thereof | |
| CN110215896A (en) | A kind of lithium absorption resin of porous silicon ball support and preparation method thereof | |
| CN114634229B (en) | Adsorption electrode material with porous microsphere morphology and preparation method and application thereof | |
| CN112786878A (en) | Graphite negative electrode material, preparation method thereof and battery | |
| CN111875816B (en) | Phenolic resin microsphere with concave-convex structure and preparation method thereof | |
| CN115275149A (en) | Preparation method of silicon-carbon negative electrode material of lithium ion battery | |
| CN111994895B (en) | Phenolic resin carbon microsphere and preparation method and application thereof | |
| CN105836728A (en) | Preparation method for asphalt hard carbon negative electrode material for lithium ion battery | |
| TW202134175A (en) | Method for producing poly (vinyl chloride) based carbon powders | |
| CN110606898B (en) | Method for reducing fusion of cross-linked starch granules | |
| CN117923467A (en) | Carbon aerogel microsphere and preparation method and application thereof | |
| CN113772654A (en) | Preparation method of nano carbon composite resin microspheres |
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 |