CN115020121A - Lignite residue based porous carbon material and preparation method and application thereof - Google Patents
Lignite residue based porous carbon material and preparation method and application thereof Download PDFInfo
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- 239000003077 lignite Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001291 vacuum drying Methods 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 17
- 238000010000 carbonizing Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
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- 238000003756 stirring Methods 0.000 claims abstract description 11
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
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- 238000005554 pickling Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 239000010431 corundum Substances 0.000 claims description 14
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000009656 pre-carbonization Methods 0.000 claims description 6
- 238000001994 activation Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
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- 239000003990 capacitor Substances 0.000 abstract description 10
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 239000011148 porous material Substances 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000002802 bituminous coal Substances 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a lignite residue based porous carbon material, which is prepared by adding lignite powder and ethanol into a high-pressure kettle and charging N 2 Heating under stirring for reaction, filtering, removing ethanol from the filtrate to obtain soluble component A, and adding acetone/CS with equal volume to the filter cake 2 Ultrasonic extracting, filtering, and further treating with acetone/CS 2 Extracting for 5 times, evaporating all the extract liquor to remove the solvent to obtain a soluble component B, combining the soluble components A and B to obtain a lignite hot-melt matter, and drying a filter cake in vacuum to obtain lignite hot-melt residue; deashing with HF, vacuum drying, N 2 Heating, pre-carbonizing and cooling; grinding the sample, ZnO and KOH, N 2 And heating, carbonizing, activating, cooling, grinding, pickling, washing with deionized water, and vacuum drying to obtain the porous carbon material. The invention adopts a hot melting method to removeSoluble micromolecular organic matters in the lignite are removed, and the deashed hot-melt residue is used as a precursor to prepare the porous carbon material with high porosity and high specific surface, and the porous carbon material is applied to the super capacitor.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation, and particularly relates to a lignite residue based porous carbon material, and a preparation method and application thereof.
Background
The development of energy storage equipment is being promoted by continuous development and utilization of various energy sources, the available energy sources tend to be diversified, the demand of renewable energy sources for energy storage is continuously increased, and the problem of environmental pollution caused by the traditional energy storage equipment is gradually highlighted. Reducing environmental pollution while dealing with energy storage issues is one of the major issues that currently require targeted research. The super capacitor has the characteristics of good pore structure, rapid charge and discharge, high power density, cycle stability and the like, and has a promising development prospect in energy storage.
The reserves of the lignite which is proved in China exceed 1300 hundred million tons, and account for about 13 percent of the total reserves of the coal in China. Compared with bituminous coal and anthracite, lignite is directly used as fuel due to the characteristics of high moisture and oxygen content, high ash yield, low heat value, poor stability and the like, and the natural insufficiency is caused, and the waste gas generated after combustion threatens the environment and the human health. The macromolecule aromatic ring structure in the organic matter of the lignite can be used as a precursor for preparing a carbon material, the prepared carbon material can be used as an electrode material, energy storage can be realized by accumulating electrostatic charges in an electric double layer of an electrolyte/electrode interface, and the porous structure in the lignite can provide a quick channel and an effective ion adsorption site for ion transportation in electrolyte, so that quick energy storage is realized.
In the preparation process, organic small molecular compounds are separated from lignite by a hot melting method, and a plurality of organic compound monomers can be obtained after subsequent fine separation, and can be used as high value-added chemicals. The main components of the lignite hot-melting residue are rich in condensed aromatic ring structures and macromolecules of organic oxygen, and the lignite hot-melting residue is an excellent precursor for preparing a supercapacitor electrode material. The existence of oxygen atoms enables the residue to contain more polar functional groups, the surface insulation characteristic of the carbon material is solved, the wettability of the material is improved, electrolyte ions can reach the inside of pores more easily, charges are effectively stored, and the rapid charge and discharge performance of the electrode material is realized. The carbon material precursor is naturally rich in oxygen elements, so that the carbon material precursor is beneficial to being uniformly doped into the material, and is not only remained on the surface through physical mixing. Chinese invention patent application CN 111710530A discloses a preparation method of low-order coal-based porous carbon and application of the low-order coal-based porous carbon in a super capacitor. The method directly takes low-rank coal as a raw material, prepares the coal-based porous carbon material with high porosity by mixing K-based compounds with high proportion and performing high-temperature activation, and applies the coal-based porous carbon material to the super capacitor. Chinese invention patent application CN 112017870A discloses a coal-based porous carbon, a preparation method and application thereof and a lithium ion capacitor. The coal-based porous carbon is obtained by directly mixing coal powder with an activating agent and calcining at high temperature and is applied to a lithium ion capacitor. The porous carbon material prepared by directly using coal as a raw material cannot fully utilize a macromolecular network structure in the coal, and the yield of the carbon material is low. Soluble small organic compounds and ash in the coal can affect the preparation of porous carbon. The porous carbon material is prepared by using the lignite hot-melting residues as the precursor, so that the macromolecular structure in the lignite can be fully utilized, and the energy storage performance of the supercapacitor is improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the problems in the existing coal-based porous carbon material preparation technology, remove soluble small-molecule organic compounds in lignite by a hot-dissolving method, and prepare a porous carbon material with high porosity and high specific surface by taking deashed hot-dissolving residues as a precursor, and apply the porous carbon material to a super capacitor.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a lignite residue based porous carbon material comprises the following steps:
1) adding brown coal powder and ethanol into autoclave, charging 1 MPa N 2 Heating under stirring for reaction, taking out reaction mixture after reaction, filtering, removing ethanol from filtrate with rotary evaporation evaporator to obtain soluble component A, filtering with acetone/CS of equal volume 2 Ultrasonic extracting, filtering, and further adding acetone/CS with the same volume 2 Extracting for 5 times, evaporating all extractive solutions to remove acetone/CS 2 Then obtaining a soluble component B, combining the soluble components A and B to obtain a lignite hot-melt matter, and carrying out vacuum drying on a filter cake to obtain lignite hot-melt residue;
2) deashing the hot melt residue obtained in the step 1) by using HF, drying in vacuum, putting into a corundum porcelain boat, and adding into a furnace 2 Heating to a certain temperature in the atmosphere for pre-carbonization, cooling, and taking out a sample;
3) adding the sample, ZnO and KOH after the pre-carbonization in the step 2) into an agate grinding tank, grinding in a ball mill at the rotating speed of 800 rpm/min, putting into a corundum porcelain boat, and grinding in N 2 Heating to a certain temperature in the atmosphere to perform carbonization and activation, cooling and grinding; and (3) pickling with hydrochloric acid to be neutral, washing with deionized water, and drying in vacuum to obtain the porous carbon material.
Further, in the step 1), the usage ratio of the lignite powder to the ethanol is 1 g: (10-50) mL; the temperature of the reaction was 300 deg.C o And C, the reaction time is 2-4 h.
Further, in the step 2), the using ratio of the hot melting residue to HF is 1 g: (5-30) mL; the volume fraction of the HF is 40 percent, and the temperature of the pre-carbonization is 400- o And C, pre-carbonizing for 1-6 h.
Further, in step 3), the mass ratio of the pre-carbonized sample, ZnO and KOH is 1: (0-2): (0-4), wherein the grinding is to be ground to 60-200 meshes; the temperature of the carbonization activation is 600-1000- o C, carbonizing and activating for 2-6 h; the concentration of the hydrochloric acid is 3M, the vacuum drying temperature is 80-120 ℃, and the vacuum drying time is 4-24 h.
Further, in the step 1) and the step 2), the temperature of vacuum drying is 80 ℃, and the time of vacuum drying is 12 hours; in the step 2) and the step 3), the heating rate is 2-20 o C/min。
The invention also provides the lignite residue based porous carbon material prepared by the preparation method.
The invention also provides an application of the lignite residue based porous carbon material in a super capacitor, which comprises the following steps: adding the lignite residue-based porous carbon material, acetylene black and polytetrafluoroethylene into a beaker according to the mass ratio of 8:1:1, dropwise adding 1-2 drops of ethanol, stirring, ultrasonically oscillating for 10 min to uniformly mix, uniformly coating the mixture on 1 cm-0.25 cm of foamed nickel, and uniformly coating the mixture on 80 cm-1 cm-0.25 cm of foamed nickel o And (C) drying in vacuum for 12 h, and testing the electrochemical performance of the porous carbon material prepared from the lignite residues by placing the prepared material electrode as a working electrode, the platinum electrode as a counter electrode, the mercury/mercury oxide electrode as a reference electrode and the three electrodes in an electrolytic cell containing 6M KOH electrolyte.
Has the advantages that:
the invention removes the soluble small molecular organic compounds in the lignite by a hot-melting method, contains a large amount of monocyclic aromatic compounds such as phenol, ketone and the like, and can obtain high value-added chemicals after fine separation. The deashed hot-melt residue is used as a carbon precursor to prepare a porous carbon material with high porosity and high specific surface, and the porous carbon material is applied to a super capacitor and shows good electrochemical performance. Compared with the prior art, the carbon material precursor is cheap and easy to obtain, the structural characteristics of oxygen-containing functional groups in the lignite are fully utilized, and the full and effective utilization of organic matters in the lignite is realized through a two-step method.
Drawings
FIG. 1 is a SEM image of a porous carbon material of the present invention;
FIG. 2 is a nitrogen adsorption and desorption isotherm of the porous carbon material of the present invention;
FIG. 3 shows that the current density of the electrode material prepared from the porous carbon material of the present invention is 0.5, 1, 2, 5, 10, 20 A.g -1 A lower charge-discharge curve;
FIG. 4 shows that the scanning speed of the electrode material prepared from the porous carbon material of the invention is 10, 20, 50, 100, 200 m.V -1 Cyclic voltammetry curve;
FIG. 5 is an AC impedance curve of an electrode material prepared from the porous carbon material of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples. The reagents or instruments used are not indicated by manufacturers, and are regarded as conventional products which can be purchased in the market.
The dosage ratio is 1 g: (10-50) mL of lignite powder and ethanol were added to an autoclave, and 1 MPa N was charged 2 Heating to 300 ℃ under stirring o C, reacting for 2-4 h, taking out the reaction mixture after the reaction is finished, filtering, removing ethanol from the filtrate by using a rotary evaporation evaporator to obtain a soluble component A, and using acetone/CS with the same volume as the filter cake 2 Ultrasonic extracting, filtering, and further adding acetone/CS with the same volume 2 Extracting for 5 times, evaporating all extractive solutions to remove acetone/CS 2 Then obtaining a soluble component B, combining the soluble components A and B to obtain the lignite hot content, and filtering the filter cake at 80 DEG C o And C, vacuum drying for 12 hours to obtain lignite hot melting residues.
Example 1
And (3) deashing the hot melting residue by using 40% of HF, wherein the using ratio of the hot melting residue to the HF is 1 g: (5-30) mL. Vacuum drying the ash-removed residue at 80 deg.C for 12 hr, placing into corundum porcelain boat, and adding into N 2 Atmosphere in tube furnace with 2 o Heating to 400 deg.C/min o And C, pre-carbonizing for 1 h, cooling to room temperature, and taking out a sample. Putting the pre-carbonized sample, ZnO and KOH with the mass ratio of 1:1:1 into an agate grinding tank, and grinding the mixture in a ball mill to 60-200 meshes. Placing the ground sample into a corundum porcelain boat at N 2 In a tube furnace under atmosphere 2 o Heating to 600 deg.C/min o C, carbonizing and activating for 2 hours, cooling to room temperature, taking out the sample, and fully grinding to 60-200 meshes. The sample was acid washed to neutrality with 3M hydrochloric acid and washed with a large amount of deionized water, followed by vacuum drying at 80 ℃ for 4 hours to obtain a porous carbon material. Adding the obtained porous carbon material, acetylene black and polytetrafluoroethylene into a beaker according to the mass ratio of 8:1:1, dropwise adding 1-2 drops of ethanol, fully stirring, ultrasonically shaking for 10 min at room temperature to uniformly mix, uniformly coating on foam nickel of 1 cm multiplied by 0.25 cm, and coating 80 percent of foam nickel o And C, vacuum drying for 12 h to obtain the electrode material. And testing the electrochemical performance of the porous carbon material prepared from the lignite residues by using the prepared material electrode as a working electrode.
Example 2
And (3) deashing the hot melting residue by using 40% of HF, wherein the using ratio of the hot melting residue to the HF is 1 g: (5-30) mL. Vacuum drying the ash-removed residue at 80 deg.C for 12 hr, placing into corundum porcelain boat, and adding into N 2 In a tube furnace under atmosphere 5 o Heating to 500 deg.C/min o And C, pre-carbonizing for 4 hours, cooling to room temperature, and taking out a sample. Adding the pre-carbonized sample, ZnO and KOH with the mass ratio of 1:1:3 into an agate grinding tank, and grinding to 60-200 meshes in a ball mill at the rotating speed of 800 rpm/min. Putting the ground sample into a corundum porcelain boat, and putting the corundum porcelain boat into the corundum porcelain boat under the condition of N 2 In a tube furnace under atmosphere 5 o Heating to 700 deg.C/min o C, carbonizing and activating for 4 hours, cooling to room temperature, taking out the sample, and fully grinding to 60-200 meshes. The sample was acid washed to neutrality with 3M hydrochloric acid and washed with a large amount of deionized water, followed by vacuum drying at 80 ℃ for 4 hours to obtain a porous carbon material. Adding the obtained porous carbon material, acetylene black and polytetrafluoroethylene into a beaker according to the mass ratio of 8:1:1, dropwise adding 1-2 drops of ethanol, fully stirring, ultrasonically shaking for 10 min at room temperature to uniformly mix, uniformly coating on foam nickel of 1 cm multiplied by 0.25 cm, and coating 80 percent of foam nickel o And C, vacuum drying for 12 h to obtain the electrode material. And testing the electrochemical performance of the porous carbon material prepared from the lignite residues by using the prepared material electrode as a working electrode.
Example 3
And (3) deashing the hot melting residue by using 40% of HF, wherein the using ratio of the hot melting residue to the HF is 1 g: (5-30) mL. Vacuum drying the ash-removed residue at 80 deg.C for 12 hr, placing into corundum porcelain boat, and adding into N 2 In a tube furnace under atmosphere at 10 o Heating to 600 deg.C/min o And C, pre-carbonizing for 6 hours, cooling to room temperature, and taking out a sample. Adding the pre-carbonized sample, ZnO and KOH with the mass ratio of 1:1:2 into an agate grinding tank, and grinding to 60-200 meshes in a ball mill at the rotating speed of 800 rpm/min. Placing the ground sample into a corundum porcelain boat at N 2 In a tube furnace under atmosphere at 10 o Heating to 800 deg.C/min o C, carbonizing and activating for 6 hours, cooling to room temperature, taking out the sample, and fully grinding to 60-200 meshes. The samples were acid washed to neutrality with 3M hydrochloric acid and copious amountsAnd washing with deionized water, and then drying in vacuum at 80 ℃ for 4 h to obtain the porous carbon material. Adding the obtained porous carbon material, acetylene black and polytetrafluoroethylene into a beaker according to the mass ratio of 8:1:1, dropwise adding 1-2 drops of ethanol, fully stirring, ultrasonically shaking for 10 min at room temperature to uniformly mix, uniformly coating on foam nickel of 1 cm multiplied by 0.25 cm, and coating 80 percent of foam nickel o And C, vacuum drying for 12 h to obtain the electrode material. And testing the electrochemical performance of the porous carbon material prepared from the lignite residues by using the prepared material electrode as a working electrode.
Example 4
Deashing the hot melting residue by using 40% of HF, wherein the using ratio of the hot melting residue to the HF is 1 g: (5-30) mL. Vacuum drying the ash-removed residue at 80 deg.C for 12 hr, placing into corundum porcelain boat, and adding into N 2 In a tube furnace under atmosphere at 20 deg.C o Heating to 500 deg.C/min o And C, pre-carbonizing for 6 hours, cooling to room temperature, and taking out a sample. Adding the pre-carbonized sample, ZnO and KOH with the mass ratio of 1:1:3 into an agate grinding tank, and grinding to 60-200 meshes in a ball mill at the rotating speed of 800 rpm/min. Placing the ground sample into a corundum porcelain boat at N 2 In a tube furnace under atmosphere at 20 deg.C o Heating to 900 deg.C/min o C, carbonizing and activating for 4 hours, cooling to room temperature, taking out the sample, and fully grinding to 60-200 meshes. The sample was acid washed to neutrality with 3M hydrochloric acid and washed with a large amount of deionized water, followed by vacuum drying at 80 ℃ for 4 hours to obtain a porous carbon material. Adding the obtained porous carbon material, acetylene black and polytetrafluoroethylene into a beaker according to the mass ratio of 8:1:1, dropwise adding 1-2 drops of ethanol, fully stirring, ultrasonically shaking for 10 min at room temperature to uniformly mix, uniformly coating on foam nickel of 1 cm multiplied by 0.25 cm, and coating 80 percent of foam nickel o And C, vacuum drying for 12 h to obtain the electrode material. And testing the electrochemical performance of the porous carbon material prepared from the lignite residues by using the prepared material electrode as a working electrode.
Example 5
Adding the obtained porous carbon material, acetylene black and polytetrafluoroethylene into a beaker according to the mass ratio of 8:1:1, dropwise adding 1-2 drops of ethanol, fully stirring, ultrasonically shaking for 10 min at room temperature to uniformly mix the materials, and uniformly coating the materials on a bubble of 1 cm multiplied by 0.25 cmOn nickel foam, 80 o And C, vacuum drying for 12 h to obtain the electrode material. The electrode plate of the prepared material is clamped on an electrode to be a working electrode, a platinum electrode is a counter electrode, a mercury/mercury oxide electrode is a reference electrode, and the three electrodes are placed in an electrolytic cell with 6M KOH electrolyte. A battery detection system (Neware, BTS 7.6. x) of Shenzhen New Wei energy technology Limited is adopted to carry out constant current charge and discharge test (GCD), the voltage is set to be 0-1V in the test, and the current density is 0.5A/g. Cyclic Voltammetry (CV) was tested using the electrochemical workstation of shanghai chenghua (CHI 660E), with a voltage range set to 0-1V and different scan rates of 200 mV/s. The AC impedance was tested using the electrochemical workstation of Shanghai Chenhua (CHI 660E) with a frequency range of 10 -3 -10 5 Hz, the amplitude of the AC signal used is 10 mV.
Fig. 1 is an SEM image of the porous carbon material of the present invention, and fig. 1 shows that a large amount of pore structures are clearly observed on the surface of a sample, and are uniformly distributed, and pores are connected by channels, which can provide a fast ion channel for a charge and discharge process, thereby increasing a charge transfer rate, and contributing to excellent electrochemical performance of a prepared supercapacitor.
FIG. 2 is a nitrogen adsorption-desorption isotherm of the porous carbon material of the present invention, and FIG. 2 shows that the adsorption curve of the sample is type IV adsorption when the relative pressure is low (P/P) 0 <0.02), the adsorption curve shows a sharp rising trend, indicating that the sample has a large number of micropores: (<2 nm) structure, hysteresis loop (0.02) present in the curve< P/P 0 <0.95) shows that the sample has a certain amount of mesoporous (2-50 nm) structure, and a large number of micropores and mesopores provide a large specific surface area for the material, so that the active adsorption sites of electrolyte ions are improved, and the electricity storage capacity of the supercapacitor is improved.
FIG. 3 shows that the current density of the electrode material prepared from the porous carbon material of the present invention is 0.5, 1, 2, 5, 10, 20 A.g -1 And fig. 3 shows that the sample is in a symmetrical triangular shape under different current densities, which shows that the sample has a rapid charge-discharge reversibility characteristic and embodies an ideal electric double layer capacitance characteristic. When the current density is minimalHas the longest discharge time, and the current density is 0.5 A.g -1 When the specific capacitance value is 300F g in the three-electrode embodiment -1 When the current density increased to 20A g -1 The specific capacitance value is maintained at 242F g -1 ；
FIG. 4 shows the scanning speed of the electrode material prepared from the porous carbon material of the present invention is 10, 20, 50, 100, 200 m.V -1 Fig. 4 shows that the sample presents a closed loop similar to a rectangle at different scanning rates, and the sample does not strongly deform at a higher scanning rate, which indicates that the sample has a fast ion transmission characteristic and presents an ideal double-capacitor behavior;
fig. 5 is an ac impedance curve of an electrode material prepared from the porous carbon material of the present invention, and fig. 5 shows that the sample curve exhibits a smaller intercept with the Z' axis in the high frequency region, which illustrates that the sample has a low equivalent series resistance, and exhibits a straight line almost close to the Z ″ axis in the low frequency region, which illustrates that the sample has a very small valberg diffusion resistance, the electrolyte ions can be rapidly transferred between the electrolyte and the electrode, and the low internal resistance and the high conductivity of the sample benefit from the large number of micropores and mesoporous structures thereof to provide a high-speed and smooth channel for ion transportation, thereby realizing a rapid absorption and desorption process on the surface of the electrode.
The protection content of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art are intended to be included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is to be protected by the following claims.
Claims (8)
1. A preparation method of a lignite residue based porous carbon material is characterized by comprising the following steps: the method comprises the following steps:
1) adding brown coal powder and ethanol into autoclave, charging 1 MPa N 2 Heating under stirring for reaction, taking out reaction mixture after reaction, filtering, removing ethanol from filtrate with rotary evaporation evaporator to obtain soluble component A, filtering with acetone/CS of equal volume 2 Ultrasonic extracting, filtering, and further adding acetone/CS with the same volume 2 The extraction is carried out, and the extraction,extracting repeatedly for 5 times, and evaporating all extractive solutions to remove acetone/CS 2 Then obtaining a soluble component B, combining the soluble components A and B to obtain a lignite hot-melt matter, and carrying out vacuum drying on a filter cake to obtain lignite hot-melt residue;
2) deashing the hot melt residue obtained in the step 1) by using HF, drying in vacuum, putting into a corundum porcelain boat, and adding into a furnace 2 Heating to a certain temperature in the atmosphere for pre-carbonization, cooling, and taking out a sample;
3) adding the sample, ZnO and KOH after the pre-carbonization in the step 2) into an agate grinding tank, grinding in a ball mill at the rotating speed of 800 rpm/min, putting into a corundum porcelain boat, and grinding in N 2 Heating to a certain temperature in the atmosphere to perform carbonization and activation, cooling and grinding; and (3) pickling with hydrochloric acid to be neutral, washing with deionized water, and drying in vacuum to obtain the porous carbon material.
2. The method for preparing a lignite residue based porous carbon material as claimed in claim 1, wherein: in the step 1), the usage ratio of the lignite powder to the ethanol is 1 g: (10-50) mL; the temperature of the reaction was 300 deg.C o And C, the reaction time is 2-4 h.
3. The method for preparing a lignite residue based porous carbon material as claimed in claim 1, wherein: in the step 2), the dosage ratio of the hot melting residue to HF is 1 g: (5-30) mL; the volume fraction of the HF is 40 percent, and the temperature of the pre-carbonization is 400- o And C, pre-carbonizing for 1-6 h.
4. The method for preparing a lignite residue based porous carbon material as claimed in claim 1, wherein: in the step 3), the mass ratio of the pre-carbonized sample to ZnO to KOH is 1: (0-2): (0-4), wherein the grinding is to be ground to 60-200 meshes; the temperature of the carbonization activation is 600-1000- o C, carbonizing and activating for 2-6 h; the concentration of the hydrochloric acid is 3M, the vacuum drying temperature is 80-120 ℃, and the vacuum drying time is 4-24 h.
5. The method for preparing a lignite residue based porous carbon material as claimed in claim 1, wherein: in the steps 1) and 2), the vacuum drying temperature is 80 ℃, and the vacuum drying time is 12 hours; in the step 2) and the step 3), the heating rate is 2-20 o C/min。
6. A lignite residue based porous carbon material produced by the production method according to any one of claims 1 to 5.
7. Use of a lignite residue based porous carbon material as claimed in claim 6 in a supercapacitor.
8. The use of a lignite residue based porous carbon material as claimed in claim 7 in a supercapacitor, wherein: the method comprises the following steps: adding the lignite residue-based porous carbon material, acetylene black and polytetrafluoroethylene into a beaker according to the mass ratio of 8:1:1, dropwise adding 1-2 drops of ethanol, stirring, ultrasonically oscillating for 10 min to uniformly mix, uniformly coating the mixture on 1 cm-0.25 cm of foamed nickel, and uniformly coating the mixture on 80 cm-1 cm-0.25 cm of foamed nickel o And (C) drying in vacuum for 12 hours, and testing the electrochemical performance of the porous carbon material prepared from the lignite residues by placing the prepared material electrode as a working electrode, the platinum electrode as a counter electrode, the mercury/mercury oxide electrode as a reference electrode and the three electrodes into an electrolytic cell containing 6M KOH electrolyte.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB425891A (en) * | 1933-06-24 | 1935-03-25 | Frank Henry Cone | Improvements in or relating to the production of activated carbon and apparatus therefor |
| JP2011001232A (en) * | 2009-06-19 | 2011-01-06 | Kansai Coke & Chem Co Ltd | Method for producing activated carbon, and electric double layer capacitor using activated carbon obtained by the method |
| CN102492451A (en) * | 2011-12-13 | 2012-06-13 | 中国矿业大学 | Extracting and separating method of high-temperature coal tar |
| CN104591184A (en) * | 2015-02-03 | 2015-05-06 | 安徽工业大学 | Preparation method of shell-like mesoporous carbon material for super capacitors |
| CN110586138A (en) * | 2019-09-26 | 2019-12-20 | 中国矿业大学 | High-dispersion vulcanized CoMoSxOyPreparation method and application of @ C bimetallic catalyst |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB425891A (en) * | 1933-06-24 | 1935-03-25 | Frank Henry Cone | Improvements in or relating to the production of activated carbon and apparatus therefor |
| JP2011001232A (en) * | 2009-06-19 | 2011-01-06 | Kansai Coke & Chem Co Ltd | Method for producing activated carbon, and electric double layer capacitor using activated carbon obtained by the method |
| CN102492451A (en) * | 2011-12-13 | 2012-06-13 | 中国矿业大学 | Extracting and separating method of high-temperature coal tar |
| CN104591184A (en) * | 2015-02-03 | 2015-05-06 | 安徽工业大学 | Preparation method of shell-like mesoporous carbon material for super capacitors |
| CN110586138A (en) * | 2019-09-26 | 2019-12-20 | 中国矿业大学 | High-dispersion vulcanized CoMoSxOyPreparation method and application of @ C bimetallic catalyst |
Non-Patent Citations (7)
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