CN111320173A - Preparation method of modified activated carbon material for capacitor - Google Patents
Preparation method of modified activated carbon material for capacitor Download PDFInfo
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- CN111320173A CN111320173A CN202010152628.9A CN202010152628A CN111320173A CN 111320173 A CN111320173 A CN 111320173A CN 202010152628 A CN202010152628 A CN 202010152628A CN 111320173 A CN111320173 A CN 111320173A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 42
- 239000003990 capacitor Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- 239000000047 product Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000001994 activation Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 230000004913 activation Effects 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003213 activating effect Effects 0.000 claims abstract description 18
- 239000012065 filter cake Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical class [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 6
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 6
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Chemical group 0.000 abstract description 3
- 229910052760 oxygen Chemical group 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011363 dried mixture Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- 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
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- 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
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- 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
- C01B32/354—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Environmental & Geological Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a modified activated carbon material for a capacitor, which comprises the following steps: (1) grinding, drying and crushing a carbon source; (2) activating the raw materials by a phosphoric acid solution to obtain a primary activated product; (3) mixing the precursor powder with the primary activation product, and activating with potassium hydroxide to obtain a secondary activation product; (4) and adding the secondary activated product into a saturated lead nitrate solution, performing ultrasonic dispersion, stirring, performing vacuum filtration to obtain a filter cake, and performing heat treatment to obtain the material. The preparation method of the activated carbon is simple, the raw material source is wide, the activated carbon is suitable for large-scale production, a secondary activation process is adopted in the preparation process, precursor powder with high content of heteroatoms such as nitrogen and oxygen is added into the activated carbon, the specific surface area is further increased, micropores are enriched on the surface, the specific capacitance of the material is improved, and the use performance of the material is enhanced.
Description
Technical Field
The invention belongs to the technical field of activated carbon materials, and particularly relates to a preparation method of a modified activated carbon material for a capacitor.
Background
Activated carbon, also referred to as activated carbon, refers to an amorphous carbonaceous material having a high porosity and a large specific surface area (i.e., surface area per unit mass). It is generally manufactured by pyrolysis of different carbonaceous substances, followed by activation by physical or chemical processes, and it can exist in many different forms, such as granules, powders, fibrous materials, cloths, etc. Activated carbon has been widely used in industrial fields, for example, as an electrode material for supercapacitors, as an adsorbent for water and gas purification, and as an inorganic metal catalyst or catalyst support due to its good porosity, high specific surface area, and good thermal and chemical stability. Along with the social development and the improvement of the living standard of people, the demand of the activated carbon tends to rise year by year, and particularly along with the increasing environmental protection requirement in recent years, the demand of the activated carbon at home and abroad is larger and larger, and the demand is increased year by year.
The super capacitor is a novel energy storage device between an electrolytic capacitor and a battery, has the characteristics of long cycle life, large-current charge and discharge and the like, and is a research hotspot in the field of new energy. Activated carbon is widely applied to various fields of industrial production as an adsorbent, a catalyst or a catalyst carrier, and the like, and particularly good conductivity and chemical stability of the activated carbon are always the first materials for manufacturing electrodes of supercapacitors and power batteries. However, the introduction of activated carbon into the above materials also brings other problems, such as that the hydrogen evolution overpotential of activated carbon is lower than that of lead in lead-acid batteries, and hydrogen evolution reaction is accelerated in the later stage of battery charging, so that the electrolyte loses water, and meanwhile, the activated carbon with high specific surface area in the electrode may undergo side reaction, so that products such as carbon dioxide and carbon monoxide are generated, and a large amount of water in the electrolyte is consumed, so that the performance of the materials is reduced. In addition, with the continuous development of the process, the requirements on the physical and chemical properties of the activated carbon are higher and higher, and the industrial production of the high-quality activated carbon is also challenged.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a preparation method of a modified activated carbon material for a capacitor.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a modified activated carbon material for a capacitor comprises the following steps:
(1) dedusting a carbon source by dedusting equipment, and then crushing the carbon source into 40-60 mesh granularity in a crusher for later use as a raw material;
(2) immersing the raw materials in a phosphoric acid solution with the mass concentration of 50%, filtering after 12-18 hours, and then sending the carbide into a tubular furnace for heating and activating to obtain a primary activated product;
(3) pretreating precursor powder, and mixing the pretreated precursor powder with a primary activation product according to the mass ratio of 1: (4-8), washing with clear water until the pH value is 4-7, drying, and mixing with potassium hydroxide according to the alkali-carbon ratio (1-3): 1, mixing, adding a small amount of water, stirring uniformly, and then sending into a tubular furnace for heating and activating to obtain a secondary activated product;
(4) and cooling the secondary activated product, washing with clear water until the pH value is 7-8, drying, adding into a saturated lead nitrate solution, performing ultrasonic dispersion, stirring and vacuum filtration to obtain a filter cake, sending the filter cake into a high-temperature furnace for heat treatment, and cooling to obtain the activated carbon material.
Preferably, the carbon source is waste plant straws, husks or polyimide film leftover materials.
Further, the temperature during the activation in the step 2 is controlled to be 400-500 ℃, and the time is controlled to be 60-90 minutes.
Further, the preparation method of the precursor powder in the step 3 is as follows: mixing formaldehyde and glycoluril, adding sodium hydroxide to regulate pH to 9-10, heating to 45-55 deg.C, reacting for 1-2 hr, distilling the product under reduced pressure, collecting the solution, pouring into ethanol, stirring to precipitate solid, filtering, and oven drying to obtain precursor powder.
Further, the specific process of the precursor powder pretreatment in step 3 is as follows: treating the precursor powder at 190 ℃ for 12h at 170 ℃ and then heating to 260 ℃ at 220 ℃ and keeping the temperature for 48h, and then grinding.
Further, the temperature is raised to 850 ℃ and 950 ℃ at the speed of 5-10 ℃/min during the activation in the step 3, and the activation is carried out for 1-2 hours at constant temperature.
Further, the specific process of the heat treatment in the step 4 is as follows: heating the filter cake at the temperature of 190-210 ℃ for 50-70 minutes, then continuously heating to the temperature of 450-550 ℃, keeping the temperature for 2 hours, and finally naturally cooling.
The invention also provides an activated carbon material prepared by the preparation method of the modified activated carbon material for the capacitor.
The invention has the advantages that:
the preparation method of the activated carbon is simple, the raw material source is wide, the activated carbon is suitable for large-scale production, a secondary activation process is adopted in the preparation process, phosphoric acid is used as an activating agent for the first time, the phosphoric acid has strong dehydration property, and the lignin can be well depolymerized under the hydration action of water molecules in a phosphoric acid solution and a carbide in the dipping process, so that phosphate ions can more easily enter cellulose and lignin to form pores, and favorable conditions are provided for subsequent activation and pore forming; and potassium hydroxide is taken as an activating agent for the second time, the potassium hydroxide can more easily enter the carbon material through the previous pore channel to realize further activation, and gas generated by oxidation reaction of the activating agent and carbon is separated out to form a pore structure, so that pores with uniform size are formed on the surface of the biochar.
On the basis, precursor powder containing higher content of heteroatoms such as nitrogen and oxygen is added into the activated carbon, and certain content of nitrogen and oxygen and higher content of carbon can be kept after heat treatment, so that the speed of wetting the electrode surface by electrolyte when the activated carbon is used as a capacitor material can be increased, the conductivity of the activated carbon can also be increased, and the specific capacitance of the material is increased.
Meanwhile, lead nitrate is added into the activated carbon material for reaction at last during preparation, so that sufficient lead and lead oxide are loaded, and the hydrogen evolution current of the negative electrode is better inhibited by utilizing the Faraday and non-Faraday functions of the activated carbon material in an electrolyte system, so that the problem that the potential of Faraday charge-discharge reaction and the potential of carbon non-Faraday charge-discharge reaction are inconsistent, which are brought by the traditional activated carbon material, is solved, and the performance of the activated carbon material as a capacitor material is further enhanced.
Detailed Description
The technical scheme of the invention is further explained by combining the specific examples as follows:
example 1
A preparation method of a modified activated carbon material for a capacitor comprises the following steps:
(1) after dust is removed by dust removing equipment, the rice straws are sent to a crusher to be crushed into 40-mesh particles, and the particles are used as raw materials for standby;
(2) immersing the raw materials in a phosphoric acid solution with the mass concentration of 50%, filtering after 12 hours, and then sending the carbide into a tubular furnace for heating and activating, wherein the temperature during activation is controlled to be 400 ℃, and the time is 60 minutes, so as to obtain a primary activated product;
(3) mixing formaldehyde and glycoluril, adding sodium hydroxide to regulate the pH value to 9, heating to 45 ℃, reacting for 2 hours, distilling the obtained product under reduced pressure, collecting the solution, pouring the solution into ethanol, stirring until solid is separated out, performing suction filtration and drying to obtain precursor powder, treating the precursor powder at 170 ℃ for 12 hours, heating to 220 ℃, preserving heat for 48 hours, grinding the precursor powder, and mixing the ground precursor powder with a primary activation product according to the mass ratio of 1: 4, washing the mixture with clear water to a pH value of 4, drying the mixture, and mixing the dried mixture with potassium hydroxide according to an alkali-carbon ratio of 1: 1, mixing, adding a small amount of water, stirring uniformly, then sending into a tubular furnace for heating and activating, heating to 850 ℃ at the speed of 5 ℃/min during activation, and activating for 2 hours at constant temperature to obtain a secondary activated product;
(4) and cooling the secondary activated product, washing with clear water until the pH value is 7, drying, adding into a saturated lead nitrate solution, performing ultrasonic dispersion, stirring and vacuum filtration to obtain a filter cake, feeding the filter cake into a high-temperature furnace, heating the filter cake at 190 ℃ for 50 minutes, continuously heating to 450 ℃, keeping for 2 hours, naturally cooling, and cooling to obtain the activated carbon material.
Example 2
A preparation method of a modified activated carbon material for a capacitor comprises the following steps:
(1) dedusting coconut shells by dedusting equipment, and then crushing the coconut shells into 60-mesh particles by a crusher to serve as a raw material for later use;
(2) immersing the raw materials in a phosphoric acid solution with the mass concentration of 50%, filtering after 18 hours, and then sending the carbide into a tubular furnace for heating and activating, wherein the temperature during activation is controlled at 500 ℃ and the time is 60 minutes, so as to obtain a primary activated product;
(3) mixing formaldehyde and glycoluril, adding sodium hydroxide to regulate the pH value to 10, heating to 55 ℃, reacting for 1 hour, distilling the obtained product under reduced pressure, collecting the solution, pouring the solution into ethanol, stirring until solid is separated out, performing suction filtration and drying to obtain precursor powder, treating the precursor powder at 190 ℃ for 12 hours, heating to 260 ℃, preserving heat for 48 hours, grinding the precursor powder, and mixing with a primary activation product according to the mass ratio of 1: 8, washing the mixture with clear water to a pH value of 7, drying the mixture, and mixing the dried mixture with potassium hydroxide according to an alkali-carbon ratio of 3: 1, mixing, adding a small amount of water, stirring uniformly, then sending into a tubular furnace for heating and activating, heating to 950 ℃ at a speed of 10 ℃/min during activation, and activating for 1 hour at constant temperature to obtain a secondary activated product;
(4) and cooling the secondary activated product, washing with clear water until the pH value is 8, drying, adding into a saturated lead nitrate solution, performing ultrasonic dispersion, stirring and vacuum filtration to obtain a filter cake, feeding the filter cake into a high-temperature furnace, heating the filter cake at 210 ℃ for 70 minutes, continuously heating to 550 ℃, keeping for 2 hours, naturally cooling, and cooling to obtain the activated carbon material.
Example 3
A preparation method of a modified activated carbon material for a capacitor comprises the following steps:
(1) dedusting the polyimide film leftover material by a dedusting device, and then conveying the polyimide film leftover material to a crusher to crush and crush the polyimide film leftover material to 50-mesh granularity, wherein the crushed polyimide film leftover material is used as a raw material for later use;
(2) immersing the raw materials in a phosphoric acid solution with the mass concentration of 50%, filtering after 15 hours, and then sending the carbide into a tubular furnace for heating and activating, wherein the temperature during activation is controlled to be 450 ℃ and the time is 75 minutes, so as to obtain a primary activated product;
(3) mixing formaldehyde and glycoluril, adding sodium hydroxide to regulate the pH value to 9, heating to 50 ℃, reacting for 1.5 hours, distilling the obtained product under reduced pressure, collecting the solution, pouring the solution into ethanol, stirring until solid is separated out, filtering, drying to obtain precursor powder, treating the precursor powder at 180 ℃ for 12 hours, heating to 240 ℃, preserving heat for 48 hours, grinding, and mixing with a primary activated product according to the mass ratio of 1: 6, washing the mixture with clear water until the pH value is 6, drying the mixture, and mixing the dried mixture with potassium hydroxide according to the ratio of alkali to carbon of 2: 1, mixing, adding a small amount of water, stirring uniformly, then sending into a tubular furnace for heating and activating, heating to 900 ℃ at a speed of 9 ℃/min during activation, and activating for 1.5 hours at constant temperature to obtain a secondary activated product;
(4) and cooling the secondary activated product, washing with clear water until the pH value is 7, drying, adding into a saturated lead nitrate solution, performing ultrasonic dispersion, stirring and vacuum filtration to obtain a filter cake, feeding the filter cake into a high-temperature furnace, heating the filter cake at 200 ℃ for 60 minutes, continuously heating to 500 ℃, keeping for 2 hours, naturally cooling, and cooling to obtain the activated carbon material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 (8)
1. A preparation method of a modified activated carbon material for a capacitor is characterized by comprising the following steps:
(1) dedusting a carbon source by dedusting equipment, and then crushing the carbon source into 40-60 mesh granularity in a crusher for later use as a raw material;
(2) immersing the raw materials in a phosphoric acid solution with the mass concentration of 50%, filtering after 12-18 hours, and then sending the carbide into a tubular furnace for heating and activating to obtain a primary activated product;
(3) pretreating precursor powder, and mixing the pretreated precursor powder with a primary activation product according to the mass ratio of 1: (4-8), washing with clear water until the pH value is 4-7, drying, and mixing with potassium hydroxide according to the alkali-carbon ratio (1-3): 1, mixing, adding a small amount of water, stirring uniformly, and then sending into a tubular furnace for heating and activating to obtain a secondary activated product;
(4) and cooling the secondary activated product, washing with clear water until the pH value is 7-8, drying, adding into a saturated lead nitrate solution, performing ultrasonic dispersion, stirring and vacuum filtration to obtain a filter cake, sending the filter cake into a high-temperature furnace for heat treatment, and cooling to obtain the activated carbon material.
2. The method of preparing a modified activated carbon material for capacitors as claimed in claim 1, wherein the carbon source is waste plant straw, husk or polyimide film scrap.
3. The method as claimed in claim 1, wherein the temperature of the activation in step 2 is controlled to be 400-500 ℃ and the time is 60-90 minutes.
4. The method for preparing a modified activated carbon material for capacitors as claimed in claim 1, wherein the precursor powder in the step 3 is prepared by the following method: mixing formaldehyde and glycoluril, adding sodium hydroxide to regulate pH to 9-10, heating to 45-55 deg.C, reacting for 1-2 hr, distilling the product under reduced pressure, collecting the solution, pouring into ethanol, stirring to precipitate solid, filtering, and oven drying to obtain precursor powder.
5. The method for preparing a modified activated carbon material for capacitors as claimed in claim 1, wherein the precursor powder pre-treatment in step 3 comprises the following steps: treating the precursor powder at 190 ℃ for 12h at 170 ℃ and then heating to 260 ℃ at 220 ℃ and keeping the temperature for 48h, and then grinding.
6. The method as claimed in claim 1, wherein the temperature is raised to 850-.
7. The method for preparing a modified activated carbon material for capacitors as claimed in claim 1, wherein the heat treatment in step 4 comprises the following steps: heating the filter cake at the temperature of 190-210 ℃ for 50-70 minutes, then continuously heating to the temperature of 450-550 ℃, keeping the temperature for 2 hours, and finally naturally cooling.
8. An activated carbon material, characterized by being produced by the method for producing a modified activated carbon material for capacitors claimed in any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010152628.9A CN111320173B (en) | 2020-03-06 | 2020-03-06 | Preparation method of modified activated carbon material for capacitor |
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| CN112138664A (en) * | 2020-09-10 | 2020-12-29 | 广州大学 | Carbon-based electrocatalyst and preparation method thereof |
| CN112216518A (en) * | 2020-09-15 | 2021-01-12 | 暨南大学 | Flexible zinc ion hybrid capacitor and preparation method and application thereof |
| CN113314353A (en) * | 2021-03-12 | 2021-08-27 | 浙江省林业科学研究院 | Degradable super capacitor based on mao bamboo biological activity carbon electrode |
| CN115636413A (en) * | 2022-09-09 | 2023-01-24 | 江西金糠新材料科技有限公司 | Preparation method of activated carbon |
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| CN1865133A (en) * | 2006-01-24 | 2006-11-22 | 李国君 | Preparation method of active carbon for absorbing gasoline steam |
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| CN112138664A (en) * | 2020-09-10 | 2020-12-29 | 广州大学 | Carbon-based electrocatalyst and preparation method thereof |
| CN112138664B (en) * | 2020-09-10 | 2022-12-20 | 广州大学 | Carbon-based electrocatalyst and preparation method thereof |
| CN112216518A (en) * | 2020-09-15 | 2021-01-12 | 暨南大学 | Flexible zinc ion hybrid capacitor and preparation method and application thereof |
| CN113314353A (en) * | 2021-03-12 | 2021-08-27 | 浙江省林业科学研究院 | Degradable super capacitor based on mao bamboo biological activity carbon electrode |
| CN115636413A (en) * | 2022-09-09 | 2023-01-24 | 江西金糠新材料科技有限公司 | Preparation method of activated carbon |
| CN115636413B (en) * | 2022-09-09 | 2024-04-30 | 江西金糠新材料科技有限公司 | Preparation method of activated carbon |
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