CN110734064B - Preparation method of super-capacity carbon - Google Patents
Preparation method of super-capacity carbon Download PDFInfo
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- CN110734064B CN110734064B CN201810799390.1A CN201810799390A CN110734064B CN 110734064 B CN110734064 B CN 110734064B CN 201810799390 A CN201810799390 A CN 201810799390A CN 110734064 B CN110734064 B CN 110734064B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 22
- 230000004913 activation Effects 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003575 carbonaceous material Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 23
- 239000003990 capacitor Substances 0.000 description 12
- 238000001514 detection method Methods 0.000 description 4
- 241000143432 Daldinia concentrica Species 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000003415 peat Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 101100092381 Arabidopsis thaliana RRT3 gene Proteins 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102100024400 Diphthine methyltransferase Human genes 0.000 description 1
- 101001053233 Homo sapiens Diphthine methyltransferase Proteins 0.000 description 1
- 101150058817 RRT1 gene Proteins 0.000 description 1
- 101100008874 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) DAS2 gene Proteins 0.000 description 1
- 239000002174 Styrene-butadiene Substances 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
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
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- 230000005055 memory storage Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of electrode material preparation, and particularly relates to a preparation method of super-capacity carbon. The method comprises the following steps: carrying out the following treatment on non-qualified super-capacity carbon or non-qualified super-capacity carbon pre-activation raw materials, namely 1) carrying out pre-activation in the atmosphere of carbon dioxide; 2) cooling the product obtained in the step 1), mixing the product with an alkaline compound, and activating the product. By using the preparation method, the non-qualified super-capacity carbon or the non-qualified super-capacity carbon preactivation raw material can be further converted into the qualified super-capacity carbon with higher specific surface area, spherical profile, median particle size and compressive strength with good yield and lower cost. The method has simple operation steps, can improve the performance of the target product, achieves the aim of changing waste into valuable, and has practical application value.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a preparation method of super-capacity carbon.
Background
The super capacitor is a novel electricity storage device between a secondary battery and a common capacitor, has double functions of the common capacitor and a battery, has power density far higher than that of the common battery (10-100 times), and has energy density far higher than that of the traditional physical capacitor. Compared with the common capacitor and the battery, the super capacitor has the advantages of small volume, large capacity, high charging speed, long cycle life, high discharge power, wide working temperature range (-25 ℃ -85 ℃), good reliability, low cost and the like, and has very wide application prospects in the fields of energy, communication, electronic power, national defense and the like, for example: portable instrument equipment, data memory storage system, electric automobile power supply, emergent reserve power etc..
Activated carbon has a wide range of non-specific adsorption properties and is therefore the most widely used adsorbent. In general, activated carbon may be derived from coconut shells, charcoal and wood, peat, stone coal, pitch, resins, and the like. In recent years, a supercapacitor activated carbon (also referred to as "super capacity carbon") which is a novel highly adsorptive activated carbon and is mainly used for supercapacitors (also referred to as electric double layer capacitors and electrochemical capacitors) has been developed. The super-capacity carbon applied to the super capacitor needs to have higher specific surface area and capacity and excellent electrochemical performance.
However, in the process of preparing spherical activated carbon, carbon materials which are not suitable for being used as spherical activated carbon and ultra-tolerant carbon due to parameters such as breakage, strength, morphology or BET may be generated by the preparation process or the post-treatment mode, and if such products are directly discarded or used as common activated carbon, the production cost is increased and resources are wasted.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of super-capacity carbon, which comprises the following steps: the non-super-capacity carbon material is processed as follows,
1) pre-activating in an atmosphere of carbon dioxide;
2) cooling the product obtained in the step 1), mixing the product with an alkaline compound, and activating the product.
According to the preparation method of the present invention, the non-super capacity carbon material may be prepared from coconut shell, charcoal and wood, peat, stone coal, pitch and/or resin.
According to the preparation method of the invention, the non-super-capacity carbon material can comprise a carbon material which does not meet the requirements of the electrode material of the supercapacitor, such as a carbon material with at least one parameter of specific surface area (BET), morphology and the like which does not meet the conditions for preparing the electrode material of the supercapacitor. For example, the non-super-capacity carbon material is selected from non-qualified super-capacity carbon materials obtained in the post-treatment process after activation. For example, a specific surface area of not more than 800m2Activated carbon granules, powder, or agglomerates per gram.
According to the preparation method of the present invention, the preactivation of step 1) is performed in a mixed atmosphere containing carbon dioxide and an inert gas.
According to the preparation method of the invention, the temperature of the preactivation is 30-1050 ℃, for example 40-1000 ℃, such as 55-950 ℃, such as 60-800 ℃; the time for the pre-activation step may be from 1 to 24 hours, for example from 5 to 15 hours, such as from 6 to 12 hours.
Preferably, the pre-activation step may be carried out while raising the temperature within the above-mentioned temperature range. The rate of temperature rise may be no more than 10 deg.C/min, for example no more than 5 deg.C/min, such as no more than 3 deg.C/min.
Preferably, the preactivation can be carried out sequentially in 2 or more temperature zones, for example in 2 to 10 temperature zones. And preferably, the temperatures of the temperature regions are different from each other. Alternatively, the preactivation may be carried out at a gradient of increasing temperature.
Preferably, the preactivation may have the same or different ramp rates and the same or different incubation times in different temperature zones.
Preferably, when the preactivation is carried out sequentially in 2 or more temperature zones, first carbonization is carried out in a first temperature zone, and then carbonization is carried out sequentially in a next temperature zone, for example, a second temperature zone; for example, the temperature of the first temperature region may be 30 to 600 ℃, for example 40 to 600 ℃; the temperature of the second temperature region may be higher than the first temperature region, for example 600 to 950 ℃, such as 700 to 950 ℃.
Preferably, when the preactivation is sequentially performed in 2 or more temperature zones, carbon dioxide, or a mixed gas of carbon dioxide and an inert gas, may be introduced as follows: a1) when the pre-activation is carried out in a plurality of temperature areas, the mixed gas of carbon dioxide and inert gas is introduced at the same time; or a2) introducing nitrogen only in the first temperature range and introducing a mixed gas of carbon dioxide and an inert gas simultaneously in the other temperature ranges when preactivation is carried out in a plurality of temperature ranges, or a3) introducing carbon dioxide during cooling, for example, during cooling to 50 to 200 ℃ after heating in a plurality of temperature ranges in an inert gas atmosphere.
Preferably, the inert gas is selected from at least one of nitrogen, helium, argon;
preferably, the volume ratio (flow rate ratio) of the inert gas to carbon dioxide is 2:1 or more, for example, 2 to 10: 1.
According to the invention, the basic compound used in step 2) can be chosen from organic or inorganic bases chosen from hydroxides, carbonates or bicarbonates of alkali or alkaline earth metals, such as LiOH, NaOH, KOH, Ca (OH)2、Na2CO3、NaHCO3、K2CO3One, two or more.
Alternatively, the basic compound isCan be an oxide of an alkali metal or an oxide of an alkaline earth metal, e.g. CaO, K2O、Li2O or mixtures thereof.
According to the invention, the mass ratio of the product obtained in the step 1) in the step 2) to the alkaline compound is 1 (1-5), and preferably 1 (3-4).
Preferably, the temperature of the activation step is 700-1300 ℃, preferably 800-1200 ℃, for example 850-950 ℃; the time for the activation step is 1 to 10 hours, for example 3 to 8 hours.
Preferably, the atmosphere of the activation step is selected from an atmosphere containing no oxygen.
Preferably, the temperature increase process of the present invention may be continuous or intermittent.
The invention also provides the super-capacity carbon prepared by the method.
The invention also provides application of the super-capacitance carbon as an electrode material of a super capacitor.
The invention also provides an electrode comprising the super-capacity carbon.
The invention also provides a super capacitor which comprises the super-capacitance carbon.
Advantageous effects
The inventors have surprisingly found that certain non-super-capacity carbon materials can be prepared in good yield and at low cost using the preparation method of the present invention to convert into suitable super-capacity carbon materials. The method has simple operation steps, can improve the performance of the target product, achieves the aim of changing waste into valuable, and has practical application value.
Drawings
FIG. 1 is a scanning electron micrograph of the product of preparation example 1.
FIG. 2 is a scanning electron micrograph of the product 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. The specific surface areas in the examples were measured by a nitrogen physisorption instrument model Belsorp mini II from microtrac bel corp.
Preparation example 1
1.1 preparation of the Polymer matrix
Adding 20 liters of water into a 50 liter polymerization kettle, heating to 30 ℃, respectively adding 11g of magnesium carbonate, 24g of gelatin and 0.18g of methylene blue under the stirring state, adding an oil phase formed by mixing 3.4kg of methyl styrene, 1.1kg of dipentene and 24g of benzoyl peroxide after uniformly stirring, then adding 1.1kg of paraffin, sealing the polymerization kettle, introducing clean compressed air into the polymerization kettle, and keeping the gas phase pressure in the kettle at 0.04 MPa. Then, stirring is started, liquid beads in the kettle are adjusted to be proper in particle size, the temperature is raised to 88 ℃, the temperature is maintained for 10 hours, the temperature is raised to 95 ℃, the temperature is maintained for 18 hours, 2.56kg of white spherical polymer is obtained through filtration, washing, drying and screening, and the BET of the product is 10.577m through detection2/g。
1.2 carbonization
220g of median particle diameter D50The white spherical polymer having a particle size of 0.8mm was charged into a rotary tube furnace, and subjected to the following heat treatment at a heating rate of 5 ℃/min under a nitrogen atmosphere:
heating to 100 deg.C, and standing for 100 min;
heating to 150 ℃, and staying for 200 minutes;
the following heat treatment was carried out at a heating rate of 6 ℃/min:
heating to 300 ℃, and staying for 100 minutes;
heating to 500 deg.C, and standing for 200 min;
then heated to 650 ℃ and left for 100 minutes. And cooling to obtain 200g of carbonized product.
1.3 Pre-activation and activation
In a rotating tube furnace, the carbonized product obtained in the step 1.2 is heated to 950 ℃ at the speed of 4 ℃/min under the mixed atmosphere of water vapor, carbon dioxide and nitrogen with the flow rate ratio of 1:1:4.5(L/min), stays for 360min, is heated to 1000 ℃ at the speed of 3 ℃/min, and stays for 240 min. After cooling, 1000g of NaOH is added, and under the mixed atmosphere of carbon dioxide and nitrogen with the flow velocity ratio of 1:1:4.5(L/min), the spherical super-capacity carbon is obtained by heating to 700 ℃ at the speed of 3 ℃/min, staying for 240min and cooling. Collecting the cracked carbon spheres. And repeating the steps until the amount of the collected non-qualified carbon balls is enough for the next batch of activation, and collecting 210.2g of cracked and powdery carbon balls. The photograph of the carbon spheres is shown in fig. 1.
Preparation example 2
2.1 preparation of the Polymer matrix
Adding 20 liters of water into a 50 liter polymerization kettle, heating to 30 ℃, respectively adding 11g of magnesium carbonate, 24g of gelatin and 0.18g of methylene blue under the stirring state, adding an oil phase formed by mixing 3.4kg of methyl styrene, 1.1kg of dipentene and 24g of benzoyl peroxide after uniformly stirring, then adding 1.1kg of paraffin, sealing the polymerization kettle, introducing clean compressed air into the polymerization kettle, and keeping the gas phase pressure in the kettle at 0.04 MPa. Then, stirring is started, liquid beads in the kettle are adjusted to be proper in particle size, the temperature is raised to 88 ℃, the temperature is maintained for 10 hours, the temperature is raised to 95 ℃, the temperature is maintained for 18 hours, 2.56kg of white spherical polymer is obtained through filtration, washing, drying and screening, and the BET of the product is 10.577m through detection2/g。
2.2 carbonization
220g of median particle diameter D50The white spherical polymer having a particle size of 0.8mm was charged into a rotary tube furnace, and subjected to the following heat treatment at a heating rate of 5 ℃/min under a nitrogen atmosphere:
heating to 100 deg.C, and standing for 100 min;
heating to 150 ℃, and staying for 200 minutes;
the following heat treatment was carried out at a heating rate of 6 ℃/min:
heating to 300 ℃, and staying for 100 minutes;
heating to 500 deg.C, and standing for 200 min;
then heated to 650 ℃ and left for 100 minutes. And cooling to obtain 200g of carbonized product.
2.3 Pre-activation and activation
In a rotating tube furnace, the carbonized product obtained in the step 2.2 is heated to 950 ℃ at the speed of 4 ℃/min under the mixed atmosphere of water vapor, carbon dioxide and nitrogen with the flow rate ratio of 1:1:4.5(L/min), stays for 360min, is heated to 1000 ℃ at the speed of 3 ℃/min, and stays for 240 min. Collecting the product with poor sphericity and powder. And (3) repeating the steps 2.1-2.3, and collecting 132g of pre-activated product which is difficult to obtain qualified super-capacity carbon through activation after pre-activation.
Example 1
In a rotary tube furnace, 100g of unqualified carbon balls prepared in the preparation example 1 are heated to 580 ℃ at the speed of 3 ℃/min and stay for 100min under the mixed atmosphere of carbon dioxide and nitrogen with the volume ratio of 1:4, and then are heated to 900 ℃ at the speed of 4 ℃/min and stay for 200 min. Cooling, adding 400g of KOH, mixing, heating to 1000 ℃ at the speed of 4 ℃/min under the mixed atmosphere of carbon dioxide and nitrogen with the volume ratio of 1:4, staying for 240min, and cooling to obtain qualified super-capacity carbon RRT1 with the yield of 69 percent calculated by the non-qualified activated carbon raw material. The specific surface area of the product is 2103m by detection2(ii)/g, bulk density of 0.335g/mL, average pore volume of 1.024cm3(ii) in terms of/g. A photograph of the super capacity carbon product is shown in fig. 2.
Example 2
In a rotary tube furnace, nitrogen is introduced at a speed of 4L/min, 100g of unqualified preactivation product prepared in preparation example 2 is heated to 350 ℃ at a speed of 4 ℃/min, stays for 100min, is heated to 600 ℃ at a speed of 5 ℃/min, and stays for 200 min. Cooling to 150 deg.C, introducing carbon dioxide at a speed of 2L/min, and standing for 50 min. After cooling, 320g of NaOH is added for mixing, and the mixture is heated to 900 ℃ at the speed of 4 ℃/min and stays for 200min under the nitrogen atmosphere to obtain qualified super-capacity carbon RRT2, wherein the yield is 63 percent based on the non-qualified preactivation raw material. The detection proves that the specific surface area of the product is 1692m2(ii)/g, bulk density of 0.312g/mL, average pore volume of 1.044cm3(ii) in terms of/g. The sphericity is good.
Example 3
The specific surface area of the commercial product is 2490m2(ii)/g, and can be used as a super-capacity charcoal,pressed to 120g of a substantially non-spherical product. Introducing nitrogen gas at a speed of 4L/min into a rotary tube furnace, heating to 400 deg.C at a speed of 4 deg.C/min, standing for 100min, heating to 600 deg.C at a speed of 5 deg.C/min, introducing carbon dioxide at a speed of 3L/min, and standing for 150 min. Cooling, adding 300g KOH, mixing, heating to 900 ℃ at the speed of 5 ℃/min and staying for 200min under the nitrogen atmosphere to obtain qualified super-capacity carbon RRT3, wherein the yield is 58% based on non-qualified raw materials. The specific surface area of the product is 1834m2(ii)/g, bulk density of 0.364g/mL, average pore volume of 1.121cm3(ii) in terms of/g. The sphericity is good.
Example 4
The super-capacity carbon prepared in the examples 1 to 3, a binder SBR (styrene butadiene rubber latex) and CMC (sodium carboxymethylcellulose) are mixed and homogenized, evenly coated on an aluminum foil, and then dried, rolled and stamped to assemble a super capacitor (organic system, 2.7V), wherein when the current density is 2A/g, the mass specific capacitance is more than 250F/g.
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 (1)
1. A preparation method of super-capacity carbon is characterized by comprising the following steps: the non-qualified hyper-capacity carbon material is processed as follows,
1) pre-activating in an atmosphere of carbon dioxide;
2) cooling the product obtained in the step 1), mixing the product with an alkaline compound, and activating;
the preactivation of step 1) is carried out in a mixed atmosphere containing carbon dioxide and inert gas; the volume ratio of the inert gas to the carbon dioxide is 2-10: 1;
in the step 1), the temperature of the preactivation is 40-1000 ℃;
the non-qualified super-capacity carbon material is selected from the materials with the specific surface area not higher than 800m2Activated carbon granules, powders, or briquettes per gram; the non-qualified superThe preparation method of the carbon comprises the following steps:
1.1 preparation of the Polymer matrix
Adding 20 liters of water into a 50 liter polymerization kettle, heating to 30 ℃, respectively adding 11g of magnesium carbonate, 24g of gelatin and 0.18g of methylene blue under the stirring state, adding an oil phase formed by mixing 3.4kg of methyl styrene, 1.1kg of dipentene and 24g of benzoyl peroxide after uniformly stirring, then adding 1.1kg of paraffin, sealing the polymerization kettle, introducing clean compressed air into the polymerization kettle, and keeping the gas phase pressure in the kettle at 0.04 MPa; then, starting stirring, adjusting the liquid beads in the kettle to proper particle size, heating to 88 ℃, preserving heat for 10 hours, heating to 95 ℃, preserving heat for 18 hours, filtering, washing, drying and screening to obtain a white spherical polymer;
1.2 carbonization
220g of the above-mentioned white spherical polymer having a median particle diameter D50 of 0.8mm was charged into a rotary tube furnace and subjected to the following heat treatment at a heating rate of 5 ℃/min under a nitrogen atmosphere:
heating to 100 deg.C, and standing for 100 min;
heating to 150 ℃, and staying for 200 minutes;
the following heat treatment was carried out at a heating rate of 6 ℃/min:
heating to 300 ℃, and staying for 100 minutes;
heating to 500 deg.C, and standing for 200 min;
then heating to 650 ℃, staying for 100 minutes, and cooling to obtain 200g of carbonized product;
1.3 Pre-activation and activation
Heating the carbonized product obtained in the step 1.2 to 950 ℃ at the speed of 4 ℃/min in a rotating tube furnace under the mixed atmosphere of water vapor, carbon dioxide and nitrogen at the flow rate ratio of 1:1:4.5(L/min), staying for 360min, then heating to 1000 ℃ at the speed of 3 ℃/min, staying for 240min, cooling, then adding 1000g of NaOH, heating to 700 ℃ at the speed of 3 ℃/min under the mixed atmosphere of carbon dioxide and nitrogen at the flow rate ratio of 1:1:4.5(L/min), staying for 240min, and cooling to obtain spherical super-capacity carbon, namely non-qualified super-capacity carbon;
alternatively, step 1.3 preactivation and activation is: heating the carbonized product obtained in the step 1.2 to 950 ℃ at the speed of 4 ℃/min in a rotating tube furnace under the mixed atmosphere of water vapor, carbon dioxide and nitrogen with the flow rate ratio of 1:1:4.5(L/min), staying for 360min, heating to 1000 ℃ at the speed of 3 ℃/min, and staying for 240min to prepare the non-qualified super-capacity carbon;
in the step 1), the time of the pre-activation step is 1-24 hours;
the alkaline compound used in step 2) is selected from organic or inorganic bases selected from hydroxides, carbonates or bicarbonates of alkali metals or alkaline earth metals, LiOH, NaOH, KOH, Ca (OH)2、Na2CO3、NaHCO3、K2CO3One, two or more;
or the alkaline compound is oxide of alkali metal or oxide of alkaline earth metal, and is CaO or K2O、Li2O or mixtures thereof;
in the step 2), the mass ratio of the product obtained in the step 1) to the alkaline compound is 1 (1-5);
in the step 2), the temperature of the activation step is 700-1300 ℃;
in the step 2), the time of the activation step is 1-10 hours;
in step 2), the atmosphere of the activation step is selected from an atmosphere containing no oxygen.
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