CN111943192A - Preparation method of carbon material for supercapacitor, carbon material and application of carbon material - Google Patents
Preparation method of carbon material for supercapacitor, carbon material and application of carbon material Download PDFInfo
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- CN111943192A CN111943192A CN202010854228.2A CN202010854228A CN111943192A CN 111943192 A CN111943192 A CN 111943192A CN 202010854228 A CN202010854228 A CN 202010854228A CN 111943192 A CN111943192 A CN 111943192A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000003245 coal Substances 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000002893 slag Substances 0.000 claims abstract description 38
- 238000002309 gasification Methods 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 34
- 238000001994 activation Methods 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 230000003213 activating effect Effects 0.000 claims abstract description 24
- 238000000967 suction filtration Methods 0.000 claims abstract description 23
- 230000004913 activation Effects 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 238000011282 treatment Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 32
- 239000003990 capacitor Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000012190 activator Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- FEMRXDWBWXQOGV-UHFFFAOYSA-N potassium amide Chemical compound [NH2-].[K+] FEMRXDWBWXQOGV-UHFFFAOYSA-N 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 16
- 230000007935 neutral effect Effects 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 5
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 5
- 239000003830 anthracite Substances 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 238000007781 pre-processing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000003081 coactivator Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- -1 hydrogen Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method 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
- C01B32/318—Preparation characterised by the starting materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—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
- 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
- C01B32/354—After-treatment
- C01B32/382—Making shaped products, e.g. fibres, spheres, membranes or foam
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
-
- 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)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Environmental & Geological Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation method of a carbon material for a supercapacitor, the carbon material and application thereof, wherein the preparation method of the carbon material for the supercapacitor comprises the following steps: step 102, pretreating a certain amount of raw coal and gasification slag enriched carbon, uniformly mixing the pretreated raw coal and gasification slag enriched carbon with a certain amount of activating assistant, and performing high-temperature activation treatment; and step 104, mixing the first product obtained after the high-temperature activation treatment with a certain amount of acid-alcohol mixed solution, heating and stirring, and performing suction filtration, washing and drying after the reaction is finished for later use. The preparation method has the advantages of cheap and easily-obtained raw materials, simple and controllable process, mild operation conditions and capability of realizing industrial production, and the carbon material prepared by the preparation method has the characteristics of high specific surface area, high specific capacitance, small internal resistance and the like.
Description
Technical Field
The invention relates to the field of supercapacitors, in particular to a preparation method of a carbon material for a supercapacitor, the carbon material and application thereof.
Background
The super-capacitor activated carbon can be widely applied to novel energy storage devices such as super capacitors and lead-carbon batteries, and further can be butted with new energy automobiles, wind power generation, high-speed rails, communication base stations, aerospace, military industry and other fields. The core material of the super capacitor is a carbon material, and at present, the carbon material is mainly prepared by an alkali activation method and used for the super capacitor, but the defects of low ash content, low specific surface area, small number of micropores, low specific capacitance, large internal resistance and the like exist, so that the performance of the super capacitor is improved. The reason is mainly that most of alkali is melted and adhered to the reactor due to direct mixing and activation of the carbon-containing precursor and the alkali, so that insufficient activation and low capacitance are caused; in addition, the ash and deoxidation functional groups are reduced without subsequent washing, so that the internal resistance is increased and obviously attenuated.
Therefore, it is highly desirable to develop a porous carbon material having a high specific surface area, a high specific capacitance, and a low internal resistance.
Disclosure of Invention
The invention aims to provide a preparation method of a porous carbon material with high specific surface area, high specific capacitance and small internal resistance, which has the advantages of cheap and easily-obtained raw materials, simple and controllable process, mild operating conditions and capability of realizing industrial production.
In order to achieve the above purpose, the invention provides a preparation method of a carbon material for a supercapacitor, which comprises the following steps: step 102, pretreating a certain amount of raw coal and gasification slag enriched carbon, uniformly mixing the pretreated raw coal and gasification slag enriched carbon with a certain amount of activating assistant, and performing high-temperature activation treatment; and step 104, mixing the first product obtained after the high-temperature activation treatment with a certain amount of acid-alcohol mixed solution, heating and stirring, and performing suction filtration, washing and drying after the reaction is finished for later use.
Preferably, the preparation method further comprises: and 106, carrying out high-temperature reaction on the second product obtained in the step 104 and a certain amount of mixed gas of nitrogen and hydrogen.
Preferably, in step 102, the preprocessing includes: mixing a certain amount of raw coal, gasification slag enriched carbon and a certain amount of strong acid solution, heating and stirring, after the reaction is finished, carrying out suction filtration, washing and drying to obtain a preoxidation precursor.
Preferably, in step 102, in the pretreatment process, the mass ratio of the raw coal, the gasification slag enriched carbon and the strong acid solution is (4-12): 1-3): 3-9.
Preferably, in step 102, the preprocessing includes: mixing raw coal, gasification slag enriched carbon and strong acid solution in a mass ratio of (4-12) to (1-3) to (3-9), heating to 60-90 ℃, stirring at a constant temperature for 4-8h, introducing reaction liquid into a funnel for suction filtration after the reaction is finished, repeatedly washing with deionized water until the filtrate becomes neutral, and drying in a vacuum drying box at the temperature of 110 ℃ and 150 ℃ for 10-24h to obtain the pre-oxidized precursor.
Preferably, the raw coal is one or more of anthracite, coking coal and fat coal; the gasification slag enriched carbon is one or two of palm shell gasification slag or bituminous coal gasification slag; the strong acid is one of concentrated nitric acid, concentrated sulfuric acid and perchloric acid, and preferably concentrated nitric acid.
The method adopts strong acid solution to carry out preoxidation treatment on the raw coal and the gasification slag enriched carbon, has double effects of predeliming and oxidizing, can effectively reduce the influence of subsequent metal impurities, can form surface reaction to generate a large number of active points and promote the pore-forming capability in the activation process, and simultaneously, the oxygen-containing acidic functional group can react with ammonia generated by decomposing the amino potassium of the auxiliary activator in the activation process to generate an alkaline nitrogen-containing functional group so as to improve the electrochemical performance of the carbon material.
Preferably, in step 102, the preprocessing further includes: and carrying out high-temperature carbonization on the preoxidized precursor to obtain a carbonized precursor.
Preferably, the high temperature carbonization comprises: and (3) the pre-oxidized precursor is carbonized for 2-5h in a high-temperature tube furnace from room temperature to 550-800 ℃, and naturally cooled to room temperature to obtain the carbonized precursor. High temperature carbonization helps to form a primary carbon skeleton and pores, and is beneficial to further fully react with an activating assistant to form a more developed pore structure.
Preferably, in step 102, the mass ratio of the carbonization precursor to the co-activator is 1: 2-7.
Preferably, in step 102, after a certain amount of raw coal and gasification slag enriched carbon are pretreated and then uniformly mixed with a certain amount of activating assistant, and before high-temperature activation treatment, the method further comprises the following steps: and grinding the mixture of the pretreated raw coal, the gasification slag enriched carbon and the activating aid which are uniformly mixed into fine powder, and performing extrusion forming to obtain the columnar precursor. The fine powder is preferably 200-300 mesh fine powder.
Preferably, the extrusion molding comprises: standing the fine powder on a flat die rolling machine for 3-6h under the pressure of 15-20MPa, and then extruding the fine powder into a cylinder shape with the diameter of 1-4mm in stages under the pressure of 25-40MPa to obtain the columnar precursor. The materials can be uniformly and compactly mixed by stage extrusion, and simultaneously, millimeter-scale columnar formation is favorable for overcoming the defects that the coactivator and the carbon-containing precursor are separated at high temperature and fused and adhered to the furnace wall due to simple physical mixing, so that the reaction participation probability of the effective coactivator is improved, the reaction is sufficient, and the specific surface area of the product is improved.
Preferably, in step 102, after a certain amount of raw coal and gasification slag enriched carbon are pretreated and then uniformly mixed with a certain amount of activating assistant, and before high-temperature activation treatment, the method further comprises the following steps: and crushing the columnar precursor into particles. The particulate material is preferably 100-150 mesh. The columnar precursor is crushed into particles of 100 meshes and 150 meshes, so that the inconvenient operation in the fine powder pickling process is overcome, the carbon is more fully contacted with the acid-alcohol mixed solution in the pickling process, the efficiency of the reaction with the subsequent acid-alcohol mixed solution is improved, and the ash content is reduced to the maximum extent.
Preferably, in step 102, the co-activator is one of sodium hydroxide, potassium carbonate and potassium amide, preferably potassium amide.
Preferably, in step 102, the high temperature activation process includes: and heating the particles in a high-temperature tube furnace from room temperature to 850-1050 ℃, activating at a constant temperature for 4-6h, and naturally cooling to room temperature to obtain the first product. In the high-temperature activation treatment process, the co-activator of the amino potassium can generate potassium hydroxide and ammonia by virtue of high temperature, wherein the potassium hydroxide can be used as an alkaline activator to react with a carbon-containing precursor, so that the specific surface area and the developed degree of micropores in the product are improved; and ammonia can react with carbon to generate basic nitrogen-containing functional groups, and the potential synergistic effect of C atoms and N atoms provides sufficient space and active sites for charge storage, so that the ion diffusion of the product is fast, and the charge transfer capacity is enhanced.
Preferably, in step 104, the mass ratio of the first product to the acid-alcohol mixed solution is (2-7): 5-15.
Preferably, step 104 comprises: heating the first product and the acid-alcohol mixed solution in the mass ratio of (2-7) to (5-15) to 60-90 ℃, stirring at constant temperature for 10-15h, introducing the reaction solution into a funnel for suction filtration after the reaction is finished, repeatedly washing with deionized water until the filtrate becomes neutral, and drying in a vacuum drying oven at 250 ℃ for 10-24h to obtain the second product.
Preferably, the acid-alcohol mixed solution comprises hydrochloric acid and ethanol, wherein the volume ratio of the hydrochloric acid to the ethanol is preferably (5-15): (2-6). The wetting quality of acid liquor and carbon can be improved by replacing single acid washing with acid-alcohol mixed liquor, metal impurities contained in the over-high ash can be removed more fully, chemical reaction in the charging and discharging process of the super capacitor is avoided, leakage current is reduced, and charging and discharging efficiency is improved.
Preferably, in step 106, the volume ratio of the nitrogen to the hydrogen in the mixed gas of the nitrogen and the hydrogen is (1-4): 0.25-1.
Preferably, step 106 comprises: heating 100-200g of the second product in a tube furnace from room temperature to 750-900 ℃, introducing 60-100L/h of mixed gas of nitrogen and hydrogen with the volume ratio of (1-4) - (0.25-1), keeping the temperature for 3-5h, and naturally cooling to room temperature to obtain the product. A large amount of oxygen or carboxyl groups are simultaneously bonded on the surface layer of a first product formed after high-temperature activation, and meanwhile, a small amount of oxygen or hydroxyl or carboxyl groups are usually bonded on the surface of the activated carbon by an acid solution used in the acid washing process, so that a stable saturated bond is formed in the graphite structure, particularly on the surface of the activated carbon micropores, and the conductivity of the activated carbon is reduced. Reduction of H in mixed gas by nitrogen and hydrogen2Can pass through a large amount of oxygen or OH or carboxyl groups bonded to the microporous surface layer formed by the activation process and a small amount of oxygen introduced secondarily by the acid washing processOr hydroxyl group, carboxyl group and the like react to remove the passivating group on the carbon surface, activate the surface structure characteristic of the carbon material and further improve the conductivity of the carbon material.
The invention also provides a carbon material for the supercapacitor, and the carbon material is prepared by adopting the preparation method of the carbon material for the supercapacitor.
The invention also provides a carbon electrode of the supercapacitor, which is prepared from the carbon material for the supercapacitor.
The invention also provides a super capacitor, which comprises the super capacitor carbon electrode.
The invention has the beneficial effects that:
the preparation method of the carbon material for the supercapacitor provided by the invention has the advantages of cheap and easily-obtained raw materials, simple and controllable process and mild operation conditions, and specifically takes raw coal and gasified slag enriched carbon as a main body and an activating assistant as an object, and sequentially carries out pre-oxidation, carbonization, mixing, grinding, rolling, crushing, high-temperature activation and other treatments to obtain the porous carbon material; and finally, washing by using mixed liquid and reducing by using mixed gas to form the carbon material for the super capacitor. The method selects strong acid for pre-deliming and pre-oxidation to promote the formation of a large number of active points, activate pore-forming capability and alkaline nitrogen-containing functional groups; the auxiliary activating agent is preferably amino potassium, has double effects of an alkaline activating agent and a doped nitrogen element, provides sufficient space and active sites for charge storage, and enhances the charge transfer capacity; dry extrusion is carried out by stages to form a millimeter-grade columnar precursor, so that the reaction participation probability and the reaction degree of the co-activator are effectively improved; the acid-alcohol washing of the granular carbon can improve the wettability of acid liquor and the carbon, effectively overcome the inconvenience operation in the fine powder acid washing process, replace single acid washing, more fully remove metal impurities contained in overhigh ash content and reduce the ash content to the maximum extent; h in nitrogen and hydrogen mixed gas2Can effectively reduce and remove the passivation groups on the surface of the carbon material, activate the surface structure characteristics of the activated carbon and improve the conductivity of the carbon material. The carbon material for the supercapacitor prepared by the preparation method of the carbon material for the supercapacitor provided by the invention has the advantages of high specific surface area, capacity of more than 170F/g,The rising rate of the internal resistance is less than 10 percent.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"first," "second," and the like are used to distinguish similar objects, regardless of order or sequence.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
In the present invention, "step 102", "step 104", etc. are used merely as step numbers for explaining details of each step, and do not limit the sequence of the steps.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
In one embodiment of the present invention, a method for preparing a carbon material for a supercapacitor is provided, which comprises the following steps:
step 102, pretreating a certain amount of raw coal and gasification slag enriched carbon, uniformly mixing the pretreated raw coal and gasification slag enriched carbon with a certain amount of activating assistant, and performing high-temperature activation treatment;
step 104, mixing the first product obtained after high-temperature activation treatment with a certain amount of acid-alcohol mixed solution, heating and stirring, and performing suction filtration, washing and drying after the reaction is finished for later use;
and 106, carrying out high-temperature reaction on the second product obtained in the step 104 and a certain amount of mixed gas of nitrogen and hydrogen.
As a preferred embodiment, in step 102, the pre-processing includes: mixing a certain amount of raw coal, gasification slag enriched carbon and a certain amount of strong acid solution, heating and stirring, after the reaction is finished, carrying out suction filtration, washing and drying to obtain a preoxidation precursor.
Specifically, raw coal, gasification slag enriched carbon and strong acid solution in a mass ratio of (4-12) to (1-3) to (3-9) are mixed and heated to 60-90 ℃, stirred at a constant temperature for 4-8h, reaction liquid is introduced into a funnel for suction filtration after the reaction is finished, and is repeatedly washed by deionized water until filtrate becomes neutral, and dried in a vacuum drying box at 110 ℃ and 150 ℃ for 10-24h to obtain a pre-oxidized precursor.
Preferably, the raw coal is one or more of anthracite, coking coal and fat coal; the gasification slag enriched carbon is one or two of palm shell gasification slag or bituminous coal gasification slag; the strong acid is one of concentrated nitric acid, concentrated sulfuric acid and perchloric acid, and preferably concentrated nitric acid.
The method adopts strong acid solution to carry out preoxidation treatment on the raw coal and the gasification slag enriched carbon, has double effects of predeliming and oxidizing, can effectively reduce the influence of subsequent metal impurities, can form surface reaction to generate a large number of active points and promote the pore-forming capability in the activation process, and simultaneously, the oxygen-containing acidic functional group can react with ammonia generated by decomposing the amino potassium of the auxiliary activator in the activation process to generate an alkaline nitrogen-containing functional group so as to improve the electrochemical performance of the carbon material.
As a preferred embodiment, in step 102, the preprocessing further includes: and (3) carrying out high-temperature carbonization on the preoxidized precursor to obtain a carbonized precursor.
Specifically, the pre-oxidized precursor is carbonized for 2-5h in a high-temperature tube furnace from room temperature to 550-800 ℃, and naturally cooled to room temperature to obtain the carbonized precursor. High temperature carbonization helps to form a primary carbon skeleton and pores, and is beneficial to further fully react with an activating assistant to form a more developed pore structure.
As a preferred embodiment, in step 102, after a certain amount of raw coal and gasification slag enriched char are pretreated and then uniformly mixed with a certain amount of activating agent, and before high temperature activation treatment, the method further comprises the following steps: grinding the mixture of the pretreated raw coal, the gasification slag enriched carbon and the co-activator into fine powder, and performing extrusion forming to obtain a columnar precursor; and crushing the columnar precursor into particles.
Specifically, the carbonized precursor and the activating assistant agent with the mass ratio of 1:2-7 are uniformly mixed at the stirring speed of 500r/min and then ground into fine powder with the particle size of 200-300 meshes in a ball mill; standing the fine powder on a flat die rolling machine for 3-6h under the pressure of 15-20MPa, and extruding the fine powder into a cylindrical shape with the diameter of 1-4mm in stages under the pressure of 25-40MPa to obtain a cylindrical precursor; the columnar precursor is broken into particles with 100-150 meshes. According to the invention, the dry method and normal temperature staged extrusion molding are adopted, so that the uniform and dense mixing of materials can be ensured, and the millimeter-scale columnar molding is favorable for overcoming the defect that the coactivator and the carbon-containing precursor are separated at high temperature due to simple physical mixing, are melted and adhered to the furnace wall, so that the reaction participation probability of the effective coactivator is improved, the reaction is sufficient, and the specific surface area of the product is improved; the columnar precursor is crushed into particles of 100 meshes and 150 meshes, so that the inconvenient operation of the fine powder pickling process can be overcome, the carbon is more fully contacted with the acid-alcohol mixed solution in the pickling process, the efficiency of the reaction with the subsequent acid-alcohol mixed solution is improved, and the ash content is reduced to the maximum extent.
Preferably, in step 102, the co-activator is one of sodium hydroxide, potassium carbonate and potassium amide, preferably potassium amide.
As a preferred embodiment, in step 102, the high temperature activation process includes: and heating the particles in a high-temperature tube furnace from room temperature to 850-1050 ℃, activating at a constant temperature for 4-6h, and naturally cooling to room temperature to obtain the first product. In the high-temperature activation treatment process, the co-activator of the amino potassium can generate potassium hydroxide and ammonia by virtue of high temperature, wherein the potassium hydroxide can be used as an alkaline activator to react with a carbon-containing precursor, so that the specific surface area and the developed degree of micropores in the product are improved; and ammonia can react with carbon to generate basic nitrogen-containing functional groups, and the potential synergistic effect of C atoms and N atoms provides sufficient space and active sites for charge storage, so that the ion diffusion of the product is fast, and the charge transfer capacity is enhanced.
As a preferred embodiment, step 104 includes: heating the first product and the acid-alcohol mixed solution in the mass ratio of (2-7) to (5-15) to 60-90 ℃, stirring at constant temperature for 10-15h, introducing the reaction solution into a funnel for suction filtration after the reaction is finished, repeatedly washing with deionized water until the filtrate becomes neutral, and drying in a vacuum drying oven at 250 ℃ for 10-24h to obtain the second product.
Preferably, the acid-alcohol mixed solution comprises hydrochloric acid and ethanol, wherein the volume ratio of the hydrochloric acid to the ethanol is preferably (5-15): (2-6). The wetting quality of acid liquor and carbon can be improved by replacing single acid washing with acid-alcohol mixed liquor, metal impurities contained in the over-high ash can be removed more fully, chemical reaction in the charging and discharging process of the super capacitor is avoided, leakage current is reduced, and charging and discharging efficiency is improved.
As a preferred embodiment, step 106 includes: heating 100-200g of the second product in a tube furnace from room temperature to 750-900 ℃, introducing 60-100L/h of mixed gas of nitrogen and hydrogen with the volume ratio of (1-4) - (0.25-1), keeping the temperature for 3-5h, and naturally cooling to room temperature to obtain the product. A large amount of oxygen or carboxyl groups are simultaneously bonded on the surface layer of a first product formed after high-temperature activation, and meanwhile, a small amount of oxygen or hydroxyl or carboxyl groups are usually bonded on the surface of the activated carbon by an acid solution used in the acid washing process, so that a stable saturated bond is formed in the graphite structure, particularly on the surface of the activated carbon micropores, and the conductivity of the activated carbon is reduced. H2 in the nitrogen and hydrogen reduction mixed gas can react with a large amount of oxygen or OH or carboxyl groups bonded on the surface layer of the micropores formed in the activation process and a small amount of oxygen or hydroxyl, carboxyl groups and the like introduced secondarily in the acid washing process to remove the passivating groups on the carbon surface, activate the surface structure characteristic of the carbon material and further improve the conductivity of the carbon material.
In another embodiment of the invention, a carbon material for a supercapacitor is provided, and the carbon material is prepared by the preparation method of the carbon material for the supercapacitor.
In a third embodiment of the invention, a carbon electrode of a super capacitor is provided, and the carbon electrode is prepared from the carbon material for the super capacitor. The preparation method of the carbon electrode adopts the conventional preparation method in the prior art, and is not described in detail herein.
In a fourth embodiment of the invention, a supercapacitor comprises the carbon electrode of the supercapacitor.
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment provides a preparation method of a carbon material for a supercapacitor, which comprises the following steps:
(1) mixing 800g of anthracite, 200g of palm shell gasification slag and 600g of perchloric acid, heating to 90 ℃, stirring at a constant temperature for 4 hours, introducing a reaction solution into a funnel after the reaction is finished, carrying out suction filtration, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven for 10 hours at 150 ℃ to obtain a pre-oxidized precursor;
(2) the preoxidation precursor obtained in the step (1) is heated to 550 ℃ from room temperature in a high-temperature tube furnace and carbonized for 5 hours, and the temperature is naturally reduced to room temperature to obtain a carbonized precursor;
(3) uniformly mixing 400g of the carbonized precursor obtained in the step (2) and 800g of sodium hydroxide at a stirring speed of 500r/min, and then grinding the mixture in a ball mill to obtain 200-mesh fine powder;
(4) standing the fine powder obtained in the step (3) on a flat die rolling machine for 3 hours under the pressure of 15MPa, and then extruding the fine powder into a 1mm cylinder under the pressure of 40MPa to obtain a columnar precursor;
(5) crushing the columnar precursor obtained in the step (4) into particles of 100 meshes;
(6) heating the particles obtained in the step (5) from room temperature to 850 ℃ in a high-temperature tube furnace, activating at the constant temperature for 6h, and naturally cooling to room temperature to obtain a first product;
(7) heating 300g of the porous carbon material (namely the first product) obtained in the step (6) and 750g of a mixed solution of hydrochloric acid and ethanol with the volume ratio of 5:2 to 60 ℃, stirring at a constant temperature for 15 hours, introducing the reaction solution into a funnel for suction filtration after the reaction is finished, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven at 250 ℃ for 10 hours to obtain a second product;
(8) and (3) heating 100g of the washed carbon material (namely the second product) obtained in the step (7) from room temperature to 900 ℃ in a tube furnace, introducing 60L of mixed gas of nitrogen and hydrogen with the volume ratio of 1:0.25, keeping the temperature for 3h, and naturally cooling to room temperature to obtain the carbon material for the supercapacitor.
The embodiment also provides a carbon material for the supercapacitor, which is prepared by the preparation method of the carbon material for the supercapacitor. The specific surface area of the carbon material reaches 2652m2The capacitance reaches 175.5F/g.
The embodiment also provides a carbon electrode of the super capacitor, which is prepared from the carbon material for the super capacitor. The preparation method of the carbon electrode adopts the conventional preparation method in the prior art, and is not described in detail herein.
The embodiment provides a supercapacitor comprising the supercapacitor carbon electrode.
Example 2
The embodiment provides a preparation method of a carbon material for a supercapacitor, which comprises the following steps:
(1) mixing 1000g of coking coal, 400g of flue gas gasification slag and 800g of concentrated sulfuric acid, heating to 75 ℃, stirring at a constant temperature for 6 hours, introducing a reaction solution into a funnel after the reaction is finished, carrying out suction filtration, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven for 12 hours at 110 ℃ to obtain a pre-oxidation precursor;
(2) the preoxidation precursor obtained in the step (1) is carbonized for 3.5 hours in a high-temperature tube furnace from room temperature to 750 ℃, and the temperature is naturally reduced to room temperature to obtain a carbonized precursor;
(3) uniformly mixing 500g of the carbonized precursor obtained in the step (2) and 1500g of potassium carbonate at a stirring speed of 500r/min, and then grinding the mixture into fine powder of 250 meshes in a ball mill;
(4) standing the fine powder obtained in the step (3) on a flat die rolling machine for 4 hours under the pressure of 17MPa, and then extruding the fine powder into a 3mm cylinder under the pressure of 35MPa to obtain a cylindrical precursor;
(5) crushing the columnar precursor obtained in the step (4) into particles of 120 meshes;
(6) heating the particles obtained in the step (5) from room temperature to 950 ℃ in a high-temperature tube furnace, activating the particles at the constant temperature for 5 hours, and naturally cooling the particles to room temperature to obtain a first product;
(7) heating 450g of the porous carbon material (namely the first product) obtained in the step (6) and 1050g of a mixed solution of hydrochloric acid and ethanol with the volume ratio of 7:3 to 75 ℃, stirring at constant temperature for 13 hours, introducing the reaction solution into a funnel for suction filtration after the reaction is finished, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven at 200 ℃ for 12 hours to obtain a second product;
(8) and (3) heating 150g of the washed carbon material (namely the second product) obtained in the step (7) to 900 ℃ from room temperature in a tube furnace, introducing 80L of mixed gas of nitrogen and hydrogen with the volume ratio of 2:0.5, keeping the temperature for 4h, and naturally cooling to room temperature to obtain the carbon material for the supercapacitor.
The embodiment also provides a carbon material for the supercapacitor, which is prepared by the preparation method of the carbon material for the supercapacitor. The specific surface area of the carbon material reaches 2587m2The capacitance reaches 174.6F/g.
The embodiment also provides a carbon electrode of the super capacitor, which is prepared from the carbon material for the super capacitor. The preparation method of the carbon electrode adopts the conventional preparation method in the prior art, and is not described in detail herein.
The embodiment provides a supercapacitor comprising the supercapacitor carbon electrode.
Example 3
The embodiment provides a preparation method of a carbon material for a supercapacitor, which comprises the following steps:
(1) mixing 1200g of fat coal, 360g of palm shell gasification slag and 600g of concentrated nitric acid, heating to 60 ℃, stirring at a constant temperature for 8 hours, introducing a reaction solution into a funnel after the reaction is finished, carrying out suction filtration, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven for 16 hours at 110 ℃ to obtain a pre-oxidized precursor;
(2) the preoxidation precursor obtained in the step (1) is carbonized for 2 hours in a high-temperature tube furnace from room temperature to 800 ℃, and the temperature is naturally reduced to room temperature to obtain a carbonized precursor;
(3) uniformly mixing 600g of the carbonized precursor obtained in the step (2) and 4200g of amino potassium at the stirring speed of 500r/min, and then grinding the mixture into fine powder of 300 meshes in a ball mill;
(4) standing the fine powder obtained in the step (3) on a flat die rolling machine for 6 hours under the pressure of 15MPa, and then extruding the fine powder into a 2mm cylinder under the pressure of 25MPa to obtain a cylindrical precursor;
(5) crushing the columnar precursor obtained in the step (4) into particles of 150 meshes;
(6) heating the particles obtained in the step (5) from room temperature to 1050 ℃ in a high-temperature tube furnace, activating at the constant temperature for 4h, and naturally cooling to room temperature to obtain a first product;
(7) heating 500g of the porous carbon material (namely the first product) obtained in the step (6) and 1100g of a mixed solution of hydrochloric acid and ethanol with the volume ratio of 13:6 to 90 ℃, stirring at constant temperature for 10 hours, introducing the reaction solution into a funnel for suction filtration after the reaction is finished, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven at 150 ℃ for 16 hours to obtain a second product;
(8) and (3) heating 200g of the washed carbon material (namely the second product) obtained in the step (7) from room temperature to 750 ℃ in a tube furnace, introducing 100L of mixed gas of nitrogen and hydrogen with the volume ratio of 4:1, keeping the temperature for 5h, and naturally cooling to room temperature to obtain the carbon material for the supercapacitor.
The embodiment also provides a carbon material for the supercapacitor, which is prepared by the preparation method of the carbon material for the supercapacitor. The specific surface area of the carbon material reaches 2708m2The capacitance reaches 177.3F/g.
The embodiment also provides a carbon electrode of the super capacitor, which is prepared from the carbon material for the super capacitor. The preparation method of the carbon electrode adopts the conventional preparation method in the prior art, and is not described in detail herein.
The embodiment provides a supercapacitor comprising the supercapacitor carbon electrode.
Example 4
The embodiment provides a preparation method of a carbon material for a supercapacitor, which comprises the following steps:
(1) mixing 700g of a mixture of anthracite and coking coal with a mass ratio of 3:1, 100g of palm shell gasification slag and 600g of perchloric acid, heating to 80 ℃, stirring at a constant temperature for 6 hours, introducing a reaction solution into a funnel after the reaction is finished, carrying out suction filtration, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven at 110 ℃ for 18 hours to obtain a pre-oxidized precursor;
(2) the preoxidation precursor obtained in the step (1) is carbonized for 4 hours in a high-temperature tube furnace from room temperature to 700 ℃, and the temperature is naturally reduced to room temperature to obtain a carbonized precursor;
(3) uniformly mixing 300g of the carbonized precursor obtained in the step (2) and 1200g of potassium carbonate at a stirring speed of 500r/min, and then grinding the mixture into fine powder of 250 meshes in a ball mill;
(4) standing the fine powder obtained in the step (3) on a flat die rolling machine for 4 hours under the pressure of 18MPa, and then extruding the fine powder into a 4mm cylinder under the pressure of 30MPa to obtain a cylindrical precursor;
(5) crushing the columnar precursor obtained in the step (4) into particles of 120 meshes;
(6) heating the particles obtained in the step (5) from room temperature to 900 ℃ in a high-temperature tube furnace, activating at the constant temperature for 5 hours, and naturally cooling to room temperature to obtain a first product;
(7) heating 200g of the porous carbon material (namely the first product) obtained in the step (6) and 450g of a mixed solution of hydrochloric acid and ethanol with the volume ratio of 11:5 to 60 ℃, stirring at constant temperature for 13h, introducing the reaction solution into a funnel for suction filtration after the reaction is finished, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven at 180 ℃ for 18h to obtain a second product;
(8) and (3) heating 160g of the washed carbon material (namely the second product) obtained in the step (7) from room temperature to 800 ℃ in a tube furnace, introducing 75L of mixed gas of nitrogen and hydrogen with the volume ratio of 3:0.75, keeping the temperature for 4h, and naturally cooling to room temperature to obtain the carbon material for the supercapacitor.
The embodiment also provides a carbon material for the supercapacitor, which is prepared by the preparation method of the carbon material for the supercapacitor. The specific surface area of the carbon material reaches 2492m2The capacitance reaches 171.7F/g.
The embodiment also provides a carbon electrode of the super capacitor, which is prepared from the carbon material for the super capacitor. The preparation method of the carbon electrode adopts the conventional preparation method in the prior art, and is not described in detail herein.
The embodiment provides a supercapacitor comprising the supercapacitor carbon electrode.
Example 5
The embodiment provides a preparation method of a carbon material for a supercapacitor, which comprises the following steps:
(1) mixing 400g of a mixture of anthracite and fat coal in a mass ratio of 2:3 with 100g of smoke gasification slag and 350g of concentrated nitric acid, heating to 75 ℃, stirring at a constant temperature for 5 hours, introducing a reaction solution into a funnel after the reaction is finished, carrying out suction filtration, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven at 130 ℃ for 20 hours to obtain a pre-oxidized precursor;
(2) the preoxidation precursor obtained in the step (1) is carbonized for 3 hours in a high-temperature tube furnace from room temperature to 750 ℃, and the temperature is naturally reduced to room temperature to obtain a carbonized precursor;
(3) uniformly mixing 200g of the carbonized precursor obtained in the step (2) and 1200g of amino potassium at a stirring speed of 500r/min, and then grinding into fine powder of 300 meshes in a ball mill;
(4) standing the fine powder obtained in the step (3) on a flat die rolling machine for 5 hours under the pressure of 15MPa, and then extruding the fine powder into a 3mm cylinder under the pressure of 35MPa to obtain a cylindrical precursor;
(5) crushing the columnar precursor obtained in the step (4) into particles of 150 meshes;
(6) heating the particles obtained in the step (5) from room temperature to 950 ℃ in a high-temperature tube furnace, activating at the constant temperature for 4h, and naturally cooling to room temperature to obtain a first product;
(7) heating 300g of the porous carbon material (namely the first product) obtained in the step (6) and 650g of a mixed solution of hydrochloric acid and ethanol with the volume ratio of 9:4 to 80 ℃, stirring at constant temperature for 12 hours, introducing the reaction solution into a funnel for suction filtration after the reaction is finished, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven at 220 ℃ for 20 hours to obtain a second product;
(8) and (3) heating 180g of the washed carbon material (namely the second product) obtained in the step (7) from room temperature to 850 ℃ in a tubular furnace, introducing 80L of mixed gas of nitrogen and hydrogen with the volume ratio of 3:1, keeping the temperature for 3h, and naturally cooling to room temperature to obtain the carbon material for the supercapacitor.
The embodiment also provides a carbon material for the super capacitor, and the carbon material adopts the super capacitorThe carbon material for the container is prepared by the preparation method. The specific surface area of the carbon material reaches 2633m2The capacitance reaches 175.2F/g.
The embodiment also provides a carbon electrode of the super capacitor, which is prepared from the carbon material for the super capacitor. The preparation method of the carbon electrode adopts the conventional preparation method in the prior art, and is not described in detail herein.
The embodiment provides a supercapacitor comprising the supercapacitor carbon electrode.
Example 6
The embodiment provides a preparation method of a carbon material for a supercapacitor, which comprises the following steps:
(1) mixing 960g of a mixture of coking coal and fat coal in a mass ratio of 3:2 with 240g of palm shell gasification slag and 720g of concentrated sulfuric acid, heating to 90 ℃, stirring at a constant temperature for 4.5 hours, introducing a reaction solution into a funnel for suction filtration after the reaction is finished, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven at 150 ℃ for 24 hours to obtain a pre-oxidation precursor;
(2) the preoxidation precursor obtained in the step (1) is carbonized for 3.5 hours in a high-temperature tube furnace from room temperature to 750 ℃, and the temperature is naturally reduced to room temperature to obtain a carbonized precursor;
(3) uniformly mixing 300g of the carbonized precursor obtained in the step (2) and 1500g of potassium carbonate at a stirring speed of 500r/min, and then grinding the mixture into fine powder of 300 meshes in a ball mill;
(4) standing the fine powder obtained in the step (3) on a flat die rolling machine for 4 hours under the pressure of 15MPa, and then extruding the fine powder into a 4mm cylinder under the pressure of 35MPa to obtain a cylindrical precursor;
(5) crushing the columnar precursor obtained in the step (4) into particles of 150 meshes;
(6) heating the particles obtained in the step (5) from room temperature to 1000 ℃ in a high-temperature tube furnace, activating at the constant temperature for 4h, and naturally cooling to room temperature to obtain a first product;
(7) heating 700g of the porous carbon material (namely the first product) obtained in the step (6) and 1050g of a mixed solution of hydrochloric acid and ethanol in a volume ratio of 15:6 to 90 ℃, stirring at a constant temperature for 15 hours, introducing the reaction solution into a funnel for suction filtration after the reaction is finished, repeatedly washing with deionized water until the filtrate is neutral, and drying in a vacuum drying oven at 250 ℃ for 24 hours to obtain a second product;
(8) and (3) heating 200g of the washed carbon material (namely the second product) obtained in the step (7) from room temperature to 900 ℃ in a tube furnace, introducing 100L of mixed gas of nitrogen and hydrogen with the volume ratio of 2:0.6, keeping the temperature for 3h, and naturally cooling to room temperature to obtain the carbon material for the supercapacitor.
The embodiment also provides a carbon material for the supercapacitor, which is prepared by the preparation method of the carbon material for the supercapacitor. The specific surface area of the carbon material reaches 2559m2The capacitance reaches 173.5F/g.
The embodiment also provides a carbon electrode of the super capacitor, which is prepared from the carbon material for the super capacitor. The preparation method of the carbon electrode adopts the conventional preparation method in the prior art, and is not described in detail herein.
The embodiment provides a supercapacitor comprising the supercapacitor carbon electrode.
Comparative example 1
The method for preparing the carbon material for the supercapacitor of the present comparative example is different from example 1 in that in the present comparative example, the grinding fine powder is not performed in the step (3), and the step (4) and the step (5) are absent, and the high temperature activation is performed on the carbonized precursor and the sodium hydroxide uniformly mixed in the step (3) in the step (6), and the relevant parameters are the same as those in example 1.
The carbon material for the supercapacitor prepared by the preparation method of the carbon material for the supercapacitor of the comparative example has the specific surface area of only 1906m2The capacitance is only 123.2F/g.
Comparative example 2
The method for preparing the carbon material for a supercapacitor of the present comparative example is different from that of example 3 in that the porous carbon material obtained in step (6) is subjected to a high temperature reaction with a mixed gas of nitrogen and hydrogen in step (8) in step (7) as a default, and the relevant parameters are the same as those of example 3.
The supercapacitor prepared by the method for preparing the carbon material for the supercapacitor of the comparative exampleThe specific surface area of the carbon material for the container is 2574m2(iv)/g, capacitance was 169.9F/g.
Comparative example 3
The method for preparing the carbon material for the supercapacitor of the present comparative example is different from that of example 5 in that, in the present comparative example, step (8) is omitted, and the washed carbon material obtained in step (7) is used as the carbon material for the supercapacitor, and the relevant parameters are the same as those of example 5.
The carbon material for the supercapacitor prepared by the preparation method of the carbon material for the supercapacitor of the comparative example has the specific surface area of 2411m2The capacitance is 166.8F/g.
Comparative example 4
Compared with the embodiment 3, the preparation method of the carbon material for the supercapacitor of the comparative example is different from the embodiment 3 in that the step (1) and the step (2) are omitted, the fat coal, the palm shell gasification slag and the potassium amide are mixed in the step (3), and relevant parameters are the same as the embodiment 3.
The carbon material for the supercapacitor prepared by the preparation method of the carbon material for the supercapacitor of the comparative example has the specific surface area of only 1573m2The capacitance is only 108.9F/g.
The specific surface area and pore size distribution of the carbon materials for supercapacitors obtained in examples 1 to 6 and comparative examples 1 to 4 were measured, and the results are shown in table 1.
And (3) measuring the electrochemical performance: the carbon material, the conductive agent and the adhesive for the super capacitor obtained in the examples 1-6 and the comparative examples 1-4 are dissolved in a solvent according to the mass percentage of 85:10:5, mixed, coated on an aluminum foil current collector, and dried in a vacuum oven for standby, wherein a Celgard2400 diaphragm is adopted, 1mol/L TEMA-BF4/PC is adopted as an electrolyte, and a 2025 type button cell is adopted as a shell. The charge and discharge test of the battery is carried out on an electrochemical workstation, and the battery is charged and discharged at a constant current of 0.2A/g under the condition of normal temperature, the charge and discharge voltage is limited to 0.005-3V, and the internal resistance rise rate of the battery is 1200h under the constant voltage of 70 ℃ and 2.7V. The electrochemical results are shown in table 2.
TABLE 1 specific surface area and pore size distribution of carbon materials for supercapacitors obtained in examples 1 to 6 and comparative examples 1 to 4
TABLE 2 attached electrochemical Properties of carbon materials for supercapacitors obtained in examples 1 to 6 and comparative examples 1 to 4
| Specific capacity of mass (F/g) | Internal resistance (omega cm) | Increase in internal resistance (%) | |
| Example 1 | 175.5 | 5.6 | 9.52 |
| Example 2 | 174.6 | 6.1 | 9.87 |
| Example 3 | 177.3 | 5.3 | 9.33 |
| Example 4 | 171.7 | 7.8 | 9.92 |
| Example 5 | 175.2 | 5.8 | 9.58 |
| Example 6 | 173.5 | 7.4 | 9.89 |
| Comparative example 1 | 123.2 | 15.2 | 20.06 |
| Comparative example 2 | 169.9 | 16.9 | 25.15 |
| Comparative example 3 | 166.8 | 17.4 | 24.72 |
| Comparative example 4 | 108.9 | 21.6 | 31.13 |
Supercapacitors obtained by comparing examples 1-6 and comparative examples 1-4The specific surface area, the pore size distribution and the electrochemical performance of the carbon material show that the carbon material for the supercapacitor prepared by the preparation method of the carbon material for the supercapacitor has the advantages of high specific surface area, capacitance of more than 170F/g and internal resistance increase rate of less than 10%. In particular, the specific surface area of the carbon material prepared by adopting the amino potassium as the co-activator, the mixed liquid washing and the mixed gas reduction in the embodiment 3 is the largest (2708 m)2(g), the oxygen content is lowest (0.022mmol/g), the capacitance is highest (177.3F/g), the internal resistance is lowest (5.3 omega-cm), and the rising rate of the internal resistance is lowest (9.33%).
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A preparation method of a carbon material for a supercapacitor is characterized by comprising the following steps:
step 102, pretreating a certain amount of raw coal and gasification slag enriched carbon, uniformly mixing the pretreated raw coal and gasification slag enriched carbon with a certain amount of activating assistant, and performing high-temperature activation treatment;
and step 104, mixing the first product obtained after the high-temperature activation treatment with a certain amount of acid-alcohol mixed solution, heating and stirring, and performing suction filtration, washing and drying after the reaction is finished for later use.
2. The method for preparing a carbon material for a supercapacitor according to claim 1, further comprising:
and 106, carrying out high-temperature reaction on the second product obtained in the step 104 and a certain amount of mixed gas of nitrogen and hydrogen.
3. The method for preparing a carbon material for a supercapacitor according to claim 1 or 2, wherein the pretreatment in step 102 comprises:
mixing a certain amount of raw coal, gasification slag enriched carbon and a certain amount of strong acid solution, heating and stirring, after the reaction is finished, carrying out suction filtration, washing and drying to obtain a preoxidation precursor.
4. The method for preparing a carbon material for a supercapacitor according to claim 3, wherein the pretreatment further comprises, in step 102:
and carrying out high-temperature carbonization on the preoxidized precursor to obtain a carbonized precursor.
5. The method for preparing a carbon material for a supercapacitor according to any one of claims 1 to 4, wherein in the step 102, after a certain amount of raw coal and gasification slag enriched carbon are pretreated and then uniformly mixed with a certain amount of a co-activator, and before high temperature activation treatment, the method further comprises the following steps:
and grinding the mixture of the pretreated raw coal, the gasification slag enriched carbon and the activating aid which are uniformly mixed into fine powder, and performing extrusion forming to obtain the columnar precursor.
6. The method for preparing carbon material for supercapacitor according to claim 5, wherein in step 102, after a certain amount of raw coal and gasification slag enriched carbon are pretreated and then uniformly mixed with a certain amount of activating assistant, and before high temperature activation treatment, the method further comprises the following steps:
and crushing the columnar precursor into particles.
7. The method for preparing a carbon material for a supercapacitor according to any one of claims 1 to 6, wherein in step 102, the co-activator is one of sodium hydroxide, potassium carbonate and amino potassium.
8. A carbon material for a supercapacitor, which is prepared by the method for preparing the carbon material for the supercapacitor according to any one of claims 1 to 7.
9. A carbon electrode of a super capacitor, which is prepared from the carbon material for the super capacitor in claim 8.
10. A supercapacitor comprising the supercapacitor carbon electrode of claim 9.
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| CN114906847A (en) * | 2022-05-16 | 2022-08-16 | 内蒙古科技大学 | Wet activation method for gasification slag carbon residue and application thereof |
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