CN112479207A - Method for recycling activated carbon, double-electric-layer capacitor comprising activated carbon recycled by method and preparation method of double-electric-layer capacitor - Google Patents
Method for recycling activated carbon, double-electric-layer capacitor comprising activated carbon recycled by method and preparation method of double-electric-layer capacitor Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000003990 capacitor Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000004064 recycling Methods 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 52
- 239000007787 solid Substances 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 238000003763 carbonization Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 230000006641 stabilisation Effects 0.000 claims abstract description 20
- 238000011105 stabilization Methods 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 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 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 24
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 24
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 230000004913 activation Effects 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 239000003292 glue Substances 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 13
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 claims description 12
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 5
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 description 16
- 238000001816 cooling Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C01B32/318—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
- C01B32/354—After-treatment
- C01B32/36—Reactivation or regeneration
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for recovering activated carbon, an electric double layer capacitor comprising the activated carbon recovered by the method and a preparation method thereof, and belongs to the field of capacitor preparation. The invention carries out stabilization treatment by placing the mask containing active carbon in an oxidation stabilization furnace, then carries out carbonization treatment in a high-temperature carbonization furnace with the temperature of 700-2Or O3Is activated in the oxidizing atmosphere, is circularly rinsed, is purified in a vacuum carbonization furnace at 800-1000 ℃, and is crushed and separated by airflowAnd recycling the activated carbon after the stage treatment. The method for obtaining the low-cost active carbon for the electric double layer capacitor by using the active carbon mask is realized, the stable and uniform mixing of the active carbon slurry is realized by gradually reducing the solid content of the slurry, the cylindrical electric double layer capacitor with high energy density and high power is formed, the whole preparation process is simple and scalable, and the large-scale harmless treatment of the disposable mask is facilitated.
Description
Technical Field
The invention relates to a method for recovering activated carbon, an electric double layer capacitor comprising the activated carbon recovered by the method and a preparation method thereof, and belongs to the field of capacitor preparation.
Background
As a novel energy storage device, the double-electric-layer capacitor is a core power core in the fields of rail transit, wind power generation, intelligent four-meter and military industry and the like due to the characteristics of high power density (second-level charging can be realized), long service life (the service life can be more than 10 years), good temperature characteristic (basically no difference in electrochemical characteristics of products at minus 40 ℃ and 65 ℃), green and environment friendliness. As a core energy storage material of an electric double layer capacitor, activated carbon has a major interest in cost control in the electric double layer capacitor industry (the cost of activated carbon accounts for about 30-40% of the cost of an electric double layer capacitor) in addition to the energy storage and release function of the device. Currently, there are few reports of activated carbon that can satisfy the scale use of electric double layer capacitors due to the limitation of raw materials, manufacturing processes, and other factors, and the market price is 15 ten thousand/t or more, and the high capacity activated carbon for electric double layer capacitors mainly based on the petroleum coke series of korean PCT corporation and the high rate activated carbon for electric double layer capacitors mainly based on the coconut shell series of japan kory corporation are represented.
Chinese patent CN101844765B discloses a preparation method of activated carbon for a carbon electrode of a super capacitor, which comprises the steps of mixing one of coal pitch-based, mesophase pitch-based, petroleum coke-based and needle coke-based amphiphilic carbon materials with sodium hydroxide, adding deionized water, stirring, drying and grinding to obtain mixed powder, activating the mixed powder, and finally cooling, cleaning, drying and grinding to obtain the activated carbon for the super capacitor. However, the preparation process still has the defects of high production cost, inapplicability to industrial production and the like. As such, it is difficult to realize a reduction in product price of the activated carbon for electric double layer capacitors and the energy storage element thereof.
Disclosure of Invention
In view of the above-mentioned problems of the conventional activated carbon, the present invention provides a method for recovering activated carbon, an electric double layer capacitor including the activated carbon recovered by the method, and a method for manufacturing the electric double layer capacitor, in which activated carbon for an electric double layer capacitor is obtained at low cost using a disposable mask, and an electric double layer capacitor having high energy density and high power is obtained using the activated carbon.
The purpose of the invention is realized by the following technical scheme:
a method for recovering activated carbon, characterized in that the method comprises the following steps: firstly, placing the mask containing active carbon in an oxidation stabilization furnace for stabilization, then carrying out carbonization treatment in a high-temperature carbonization furnace at 700-850 ℃, and then carrying out carbonization treatment in CO2Or O3The activated carbon is subjected to activation treatment in an oxidizing atmosphere, then is subjected to circulating rinsing, is subjected to purification treatment in a vacuum carbonization furnace at the temperature of 800-1000 ℃, and is finally recycled after airflow crushing and classification treatment to obtain the activated carbon.
The mask production capacity of China as a world mask production large country occupies more than 50% of the world, and active carbon is placed in a large part of masks to adsorb organic gas, stink, toxic dust and the like, but the masks are often used as disposable articles and are not effectively recycled, so that great waste is caused. Particularly, activated carbon which adsorbs various toxic gases or toxic solutions can cause serious influence on water sources, air and the surrounding environment if the activated carbon is treated randomly or improperly. The invention obtains the active carbon suitable for the double electric layer capacitor by carrying out oxidation stabilization, high-temperature carbonization, high-temperature activation and vacuum purification on the mask, has simple process, can be industrially produced, and can carry out harmless treatment on the mask in a large scale at one time.
The cotton cloth in the mask is easy to form fluid under the high-temperature condition, oxidation stabilization refers to that the cotton cloth is fixed by oxidation and does not form fluid, then carbon is formed under the high-temperature condition, the process is called high-temperature carbonization, then high-temperature activation is carried out to form new active carbon, and then impurities are removed by vacuum purification. Lack of oxidation stabilization treatment can cause unstable quality of finished products, lack of high-temperature carbonization treatment can cause low product yield, lack of activation treatment can not form new active carbon, and lack of purification treatment can cause insufficient product purity.
In the above method for recovering activated carbon, the gas in the stabilization treatment is air or O2One or two of the above, the gas flow rate is 0.5-2L/min, the temperature is 200-350 ℃, the heating rate is 0.5-2 ℃/min, and the time is 12-24 h. After stabilization treatment, the molecular structure in the mask is changed, and molecular crosslinking is performed to fix organic carbon, so that no fluid is formed during high-temperature carbonization.
In the method for recovering the activated carbon, the gas in the carbonization treatment is nitrogen or argon, the gas flow rate is 1-5L/min, the temperature rise rate is 1-5 ℃/min, and the time is 6-12 h.
In the above method for recovering activated carbon, the gas flow rate in the activation treatment is 0.5-3L/min, the temperature is 750-. Oxidation-stabilized carbon formation in CO2Or O3The pore-forming is activated stably under an atmosphere at a fixed flow rate temperature.
In the above method for recovering activated carbon, the cyclic rinsing includes alkaline washing, acid washing, and water washing.
In the method for recovering the activated carbon, the temperature in the purification treatment is 800-1000 ℃, the vacuum degree is less than or equal to 100Pa, and the time is 6-24 h.
In the above method for recovering activated carbon, the specific surface area of the recovered activated carbon is 1450-1700m2/g，D50The grain diameter is 5-8 μm, the surface functional group content is 0.1-0.4meq/g, and the ash content is less than or equal to 0.4%. The specific surface area, the particle size, the surface functional group content and the ash content of the activated carbon influence the specific energy, the specific power and the life safety of the electric double layer capacitor.
An electric double layer capacitor, the active material of the capacitor comprises conductive carbon black and the active carbon recovered by the recovery method.
A method of manufacturing an electric double layer capacitor, the method comprising the steps of:
(1) weighing the following raw materials: weighing 85-90 parts of activated carbon recovered by the recovery method, 5-8 parts of conductive carbon black, 2-4 parts of styrene butadiene rubber and 1-3 parts of sodium carboxymethylcellulose;
(2) preparing sodium carboxymethylcellulose into glue solution with solid content of 1-3 wt% by using deionized water;
(3) mixing active carbon and conductive carbon black, and then adding carboxymethyl cellulose sodium glue solution into the mixture of the active carbon and the conductive carbon black for three times to form slurry;
(4) adding deionized water, and mixing to obtain slurry with solid content of 30-35%;
(5) adding styrene butadiene rubber and mixing to form slurry for the double electric layer capacitor;
(6) and coating, rolling, cutting, winding, assembling, drying, injecting, aging and detecting the slurry for the double electric layer capacitor to obtain the double electric layer capacitor.
Wherein, carbon black is used as a conductive agent, styrene butadiene rubber is used as a binder, and the final viscosity is adjusted by sodium carboxymethylcellulose.
In the above method for preparing an electric double layer capacitor, the step of adding the sodium carboxymethyl cellulose glue solution in three times is as follows: the solid content of the slurry is 65-75% after the sodium carboxymethyl cellulose is added for the first time; the solid content of the slurry is 50-65% after the sodium carboxymethyl cellulose is added for the second time; the solid content of the slurry is 40-48% after the carboxymethyl cellulose sodium is added for the third time. The invention controls the solid content of the slurry by adding the carboxymethyl cellulose sodium glue solution for three times, so that the electrode density and the capacitor capacity achieve the optimal effect.
Compared with the prior art, the invention has the following advantages: the invention realizes the method for obtaining the low-cost active carbon for the electric double layer capacitor by using the active carbon mask through oxidation stabilization, high-temperature carbonization, high-temperature activation and vacuum purification, realizes the stable and uniform mixing of the active carbon slurry by gradually reducing the solid content of the slurry, forms the cylindrical electric double layer capacitor with high energy density and high power, has simple whole preparation process, can be scaled, and is beneficial to the large-scale harmless treatment of the disposable mask.
Drawings
FIG. 1 is a flowchart of the process for producing activated carbon for an electric double layer capacitor by recovering a mask in example 1.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1:
10kg of mask containing activated carbon is placed in an oxidation stabilization furnace, heated to 300 ℃ at the heating rate of 0.5 ℃/min, and is treated at constant temperature for 12 hours by introducing air with the flow rate of 0.5L/min. Then, under the protection of nitrogen in a high-temperature carbonization furnace, the temperature is raised to 800 ℃ at the temperature rise rate of 2 ℃/min for constant-temperature treatment for 6 h. Naturally cooling to room temperature, transferring into an activation furnace, heating to 850 deg.C at a heating rate of 2 deg.C/min, and introducing CO at a flow rate of 1L/min2The gas was activated for 6h to give 1.5kg of product.
After naturally cooling to room temperature, 1.5kg of the product was added to a 1M KOH solution for alkali washing, filtered and then transferred to a 0.5M HCl solution for acid washing. After filtration, the material was transferred to deionized water for water washing. Repeating the above process for 3 times, and drying at 80 deg.C/12 h.
And placing the dried material in a vacuum purification furnace which is heated to 1000 ℃ at the heating rate of 5 ℃/min under the protection of argon, wherein the vacuum degree is lower than-95 Pa, calcining at constant temperature for 12h, and naturally cooling to room temperature. And transferring the materials into a jet mill, and crushing, classifying and recycling the materials to obtain the activated carbon.
Example 2:
placing 15kg of mask containing activated carbon in an oxidation stabilization furnace, heating to 250 deg.C at a heating rate of 0.2 deg.C/min, introducing air at a flow rate of 1.0L/min, and treating at constant temperature for 20 hr. Then heating up at a heating rate of 3 ℃/min in the nitrogen protection atmosphere of the high-temperature carbonization furnaceThe temperature is increased to 800 ℃ and the constant temperature treatment is carried out for 12 h. Naturally cooling to room temperature, transferring into an activation furnace, heating to 850 deg.C at a heating rate of 2 deg.C/min, and introducing CO at a flow rate of 1L/min2The gas was activated for 12h to give 3.2kg of product.
After naturally cooling to room temperature, 3.2kg of the product was added to a 1.0M KOH solution for alkali washing, filtered and then transferred to a 1.0M HCl solution for acid washing. After filtration, the material was transferred to deionized water for water washing. Repeating the above process for 3 times, and drying at 80 deg.C/12 h.
And placing the dried material in a vacuum purification furnace which is heated to 900 ℃ at the heating rate of 2 ℃/min under the protection of argon, wherein the vacuum degree is lower than-95 Pa, calcining at constant temperature for 24 hours, and naturally cooling to room temperature. And transferring the materials into a jet mill, and crushing, classifying and recycling the materials to obtain the activated carbon.
Example 3:
12kg of mask containing activated carbon is placed in an oxidation stabilization furnace, heated to 350 ℃ at the heating rate of 0.2 ℃/min, and is treated for 24 hours at constant temperature by introducing air with the flow rate of 1.5L/min. And then under the protection of nitrogen in a high-temperature carbonization furnace, heating to 750 ℃ at a heating rate of 3 ℃/min for constant-temperature treatment for 12 h. Naturally cooling to room temperature, transferring into an activation furnace, heating to 900 deg.C at a heating rate of 1 deg.C/min, and introducing CO at a flow rate of 0.5L/min2The gas was activated for 12h to give 3.0kg of product.
After naturally cooling to room temperature, 3.0kg of the product was added to 0.5M KOH solution for alkali washing, filtered and then transferred to 1.0M HCl solution for acid washing. After filtration, the material was transferred to deionized water for water washing. Repeating the above process for 3 times, and drying at 80 deg.C/12 h.
And placing the dried material in a vacuum purification furnace which is heated to 800 ℃ at the heating rate of 5 ℃/min under the protection of argon, wherein the vacuum degree is lower than-98 Pa, calcining at constant temperature for 24 hours, and naturally cooling to room temperature. Transferring the materials into a jet mill, crushing the materials, and carrying out classification treatment and recovery to obtain the active carbon
Example 4:
placing 10kg of mask containing active carbon in oxidation stabilization furnace, heating to 300 deg.C at a heating rate of 0.5 deg.C/min, and introducing O at a flow rate of 0.5L/min2And (5) carrying out constant temperature treatment for 12 h. And then under the protection of argon in a high-temperature carbonization furnace, heating to 800 ℃ at the heating rate of 2 ℃/min, and carrying out constant-temperature treatment for 6 h. Naturally cooling to room temperature, transferring into an activation furnace, heating to 850 deg.C at a heating rate of 2 deg.C/min, and introducing O at a flow rate of 1L/min3The gas was activated for 6h to give 1.5kg of product.
After naturally cooling to room temperature, 1.5kg of the product was added to a 1M KOH solution for alkali washing. After filtration, the mixture was washed with acid by transferring it to a 0.5M HCl solution. After filtration, the material was transferred to deionized water for water washing. Repeating the above process for 3 times, and drying at 80 deg.C/12 h.
And placing the dried material in a vacuum purification furnace which is heated to 1000 ℃ at the heating rate of 5 ℃/min under the protection of argon, wherein the vacuum degree is lower than-95 Pa, calcining at constant temperature for 12h, and naturally cooling to room temperature. And transferring the materials into a jet mill, and crushing, classifying and recycling the materials to obtain the activated carbon.
Example 5:
85 parts of activated carbon recovered in example 1, 6 parts of conductive carbon black, 3 parts of styrene butadiene rubber and 2 parts of sodium hydroxymethyl cellulose are weighed.
Sodium carboxymethylcellulose is prepared into glue solution with solid content of 2 wt% by deionized water.
Mixing active carbon and conductive carbon black, and then adding sodium carboxymethylcellulose glue solution into the mixture for three times to form slurry; when the carboxymethyl cellulose sodium is added for the first time, the solid content of the slurry is 70 percent; when the carboxymethyl cellulose sodium is added for the second time, the solid content of the slurry is 60 percent; the slurry solids content was 45% when the sodium carboxymethylcellulose was added for the third time.
Deionized water is added for uniform mixing, so that the solid content of the slurry is 30 percent.
Adding styrene butadiene rubber and mixing to form the slurry for the double electric layer capacitor.
And (3) coating, rolling, cutting, winding, assembling, drying, injecting, aging and detecting the slurry for the double electric layer capacitor to obtain the 2.7V double electric layer capacitor with the diameter of 60mm and the height of 140 mm.
Example 6:
90 parts of the activated carbon recovered in the embodiment 2, 8 parts of conductive carbon black, 4 parts of styrene butadiene rubber and 3 parts of sodium hydroxymethyl cellulose are weighed.
Sodium carboxymethylcellulose is prepared into glue solution with solid content of 3 wt% by deionized water.
Mixing active carbon and conductive carbon black, and then adding sodium carboxymethylcellulose glue solution into the mixture for three times to form slurry; the solid content of the slurry is 75% when the sodium carboxymethyl cellulose is added for the first time; when the carboxymethyl cellulose sodium is added for the second time, the solid content of the slurry is 65 percent; the slurry solids content was 48% when the sodium carboxymethylcellulose was added for the third time.
Deionized water is added for uniform mixing, so that the solid content of the slurry is 35%.
Adding styrene butadiene rubber and mixing to form the slurry for the double electric layer capacitor.
And (3) coating, rolling, cutting, winding, assembling, drying, injecting, aging and detecting the slurry for the double electric layer capacitor to obtain the 2.7V double electric layer capacitor with the diameter of 60mm and the height of 140 mm.
Example 7:
85 parts of the activated carbon recovered in example 3, 5 parts of conductive carbon black, 2 parts of styrene butadiene rubber and 1 part of sodium hydroxymethyl cellulose are weighed.
Sodium carboxymethylcellulose is prepared into glue solution with solid content of 1 wt% by deionized water.
Mixing active carbon and conductive carbon black, and then adding sodium carboxymethylcellulose glue solution into the mixture for three times to form slurry; the solid content of the slurry is 65% when the sodium carboxymethyl cellulose is added for the first time; when the carboxymethyl cellulose sodium is added for the second time, the solid content of the slurry is 50 percent; the third addition of sodium carboxymethylcellulose gave a slurry solids content of 40%.
Deionized water is added for uniform mixing, so that the solid content of the slurry is 30 percent.
Adding styrene butadiene rubber and mixing to form the slurry for the double electric layer capacitor.
And (3) coating, rolling, cutting, winding, assembling, drying, injecting, aging and detecting the slurry for the double electric layer capacitor to obtain the 2.7V double electric layer capacitor with the diameter of 60mm and the height of 140 mm.
Example 8:
85 parts of activated carbon recovered in example 4, 6 parts of conductive carbon black, 3 parts of styrene butadiene rubber and 2 parts of sodium hydroxymethyl cellulose are weighed.
Sodium carboxymethylcellulose is prepared into glue solution with solid content of 2 wt% by deionized water.
Mixing active carbon and conductive carbon black, and then adding sodium carboxymethylcellulose glue solution into the mixture for three times to form slurry; when the carboxymethyl cellulose sodium is added for the first time, the solid content of the slurry is 70 percent; when the carboxymethyl cellulose sodium is added for the second time, the solid content of the slurry is 60 percent; the slurry solids content was 45% when the sodium carboxymethylcellulose was added for the third time.
Deionized water is added for uniform mixing, so that the solid content of the slurry is 30 percent.
Adding styrene butadiene rubber and mixing to form the slurry for the double electric layer capacitor.
And (3) coating, rolling, cutting, winding, assembling, drying, injecting, aging and detecting the slurry for the double electric layer capacitor to obtain the 2.7V double electric layer capacitor with the diameter of 60mm and the height of 140 mm.
Example 9:
the difference from example 5 is only that after the activated carbon and the conductive carbon black are mixed, the carboxymethyl cellulose sodium cement solution is added to the mixture at one time to form a slurry.
Comparative example 1:
the difference from example 1 is that the activated carbon-containing mask was not stabilized.
Comparative example 2:
the only difference from example 1 is that no carbonization treatment was performed after the stabilization treatment.
Comparative example 3:
the only difference from example 1 is that after the carbonization treatment, the activation treatment was not performed.
Comparative example 4;
the only difference from example 1 is that after the activation treatment, no purification treatment was performed.
Table 1: EXAMPLES 1-4, COMPARATIVE EXAMPLES 1-4 Performance test of the activated carbon recovered
Table 2: results of Performance testing of electric double layer capacitors prepared in examples 5 to 9
As can be seen from the performance test of the activated carbon recovered in Table 1, the activated carbon obtained by performing oxidation stabilization, high-temperature carbonization, high-temperature activation and vacuum purification recovery on the activated carbon mask has good physical properties, one of the steps is lacked to influence the performance of the finally obtained activated carbon, and the price of the activated carbon produced by the method is about 20% lower than the market price, so that the production cost of enterprises is greatly reduced.
From the performance test results of the electric double layer capacitor prepared in table 2, the solid content of the slurry is gradually reduced in the preparation process to realize stable and uniform mixing of the activated carbon slurry, and the electric double layer capacitor with the advantages of high energy density, large capacity, less electric leakage and the like is obtained. The aim of preparing the double electric layer capacitor by using the low-cost recycled activated carbon is fulfilled, and the prepared capacitor has good physical properties compared with the conventional capacitor.
According to the embodiment and the performance test results of the prepared activated carbon and the double-electric-layer capacitor, the prepared activated carbon for the double-electric-layer capacitor has excellent physical and chemical properties by performing simple preparation processes of oxidation stabilization, high-temperature carbonization, high-temperature activation and vacuum purification on the recovery mask, and the stable and uniform mixing of the activated carbon slurry is realized by gradually reducing the solid content of the slurry, so that the cylindrical double-electric-layer capacitor with the energy density of 3-5Wh/kg and the power density of 14-18Kw/kg is formed, the overall manufacturing process is simple and can be scaled, and the large-scale harmless treatment of the disposable mask is facilitated.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (10)
1. A method for recovering activated carbon, characterized in that the method comprises the following steps: firstly, placing the mask containing active carbon in an oxidation stabilization furnace for stabilization, then carrying out carbonization treatment in a high-temperature carbonization furnace at 700-850 ℃, and then carrying out carbonization treatment in CO2Or O3The activated carbon is subjected to activation treatment in an oxidizing atmosphere, then is subjected to circulating rinsing, is subjected to purification treatment in a vacuum carbonization furnace at the temperature of 800-1000 ℃, and is finally recycled after airflow crushing and classification treatment to obtain the activated carbon.
2. The method for recovering activated carbon according to claim 1, wherein the gas in the stabilization treatment is air or O2One or two of the above, the gas flow rate is 0.5-2L/min, the temperature is 200-350 ℃, the heating rate is 0.5-2 ℃/min, and the time is 12-24 h.
3. The method for recycling activated carbon according to claim 1, wherein the gas in the carbonization treatment is nitrogen or argon, the gas flow rate is 1-5L/min, the temperature rise rate is 1-5 ℃/min, and the time is 6-12 h.
4. The method as claimed in claim 1, wherein the gas flow rate during the activation treatment is 0.5-3L/min, the temperature is 750-.
5. The method for recycling activated carbon according to claim 1, wherein the cyclic rinsing comprises alkaline washing, acid washing and water washing.
6. The method as claimed in claim 1, wherein the temperature of the purification treatment is 800-1000 ℃, the vacuum degree is less than or equal to 100Pa, and the time is 6-24 h.
7. The method as claimed in claim 1, wherein the specific surface area of the activated carbon obtained by the recovery is 1450-1700m2/g，D50The grain diameter is 5-8 μm, the surface functional group content is 0.1-0.4meq/g, and the ash content is less than or equal to 0.4%.
8. An electric double layer capacitor, characterized in that the active material of the capacitor comprises conductive carbon black and activated carbon recovered by the recovery method of claim 1.
9. A method for producing an electric double layer capacitor, comprising the steps of:
(1) weighing the following raw materials: weighing 85-90 parts of activated carbon, 5-8 parts of conductive carbon black, 2-4 parts of styrene butadiene rubber and 1-3 parts of sodium hydroxymethyl cellulose, which are recovered by the recovery method in claim 1;
(2) preparing sodium carboxymethylcellulose into glue solution with solid content of 1-3 wt% by using deionized water;
(3) mixing active carbon and conductive carbon black, and then adding sodium carboxymethylcellulose glue solution into the mixture for three times to form slurry;
(4) adding deionized water, and mixing to obtain slurry with solid content of 30-35%;
(5) adding styrene butadiene rubber and mixing to form slurry for the double electric layer capacitor;
(6) and coating, rolling, cutting, winding, assembling, drying, injecting, aging and detecting the slurry for the double electric layer capacitor to obtain the double electric layer capacitor.
10. The method for preparing an electric double layer capacitor according to claim 9, wherein the three times of adding the carboxymethyl cellulose sodium glue solution are as follows: the solid content of the slurry is 65-75% after the sodium carboxymethyl cellulose is added for the first time; the solid content of the slurry is 50-65% after the sodium carboxymethyl cellulose is added for the second time; the solid content of the slurry is 40-48% after the carboxymethyl cellulose sodium is added for the third time.
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