CN108946695B - Method for preparing porous carbon material for supercapacitor by using tar waste - Google Patents

Method for preparing porous carbon material for supercapacitor by using tar waste Download PDF

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CN108946695B
CN108946695B CN201810833640.9A CN201810833640A CN108946695B CN 108946695 B CN108946695 B CN 108946695B CN 201810833640 A CN201810833640 A CN 201810833640A CN 108946695 B CN108946695 B CN 108946695B
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carbon material
porous carbon
tar waste
waste
tar
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CN108946695A (en
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蒲巧生
王乃玉
冯小童
张建东
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Lanzhou University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a method for preparing a porous carbon material for a supercapacitor by using factory tar waste, which comprises the steps of treating the chemical factory tar waste as a carbon source and potassium carbonate as an activating agent at 650-850 ℃ under the protection of argon, and naturally cooling to room temperature; and grinding and crushing the product, washing the product with dilute hydrochloric acid solution and ultrapure water in sequence, filtering and drying the product to obtain the catalyst. The invention adopts the factory tar waste as the carbon source, not only can recycle the waste and reduce the resource waste, but also utilizes a plurality of components contained in the material, can dope heteroatoms while activating, and prepares the carbon material with the hierarchical pore structure with nested distribution of macropores and micropores.

Description

Method for preparing porous carbon material for supercapacitor by using tar waste
Technical Field
The invention relates to a preparation technology of a porous carbon material, in particular to a method for preparing the porous carbon material by using tar waste, which is mainly used as a super capacitor electrode material and belongs to the technical field of composite carbon materials and super capacitors.
Background
China is a country with large energy consumption, and although the country has rich energy resource sum, the per-capita energy resource holding amount is lower and even less than half of the average level of the world. Therefore, it is very slow to develop new energy to replace the fossil energy which is now consumed in large quantities. A supercapacitor is a new type of energy storage device, which has a higher power density and a longer cycle life than a conventional battery, and also has a higher energy density than a conventional dielectric capacitor. The porous carbon material has the physical and chemical characteristics of high heat resistance, strong acid and alkali resistance, conductivity, high chemical stability and the like, and occupies an important position in the field of electrochemical energy storage.
At present, nitrogen-doped porous carbon materials for supercapacitors are prepared by mainly using high-nitrogen-containing substances such as ionic liquids, organic polymers, metal organic framework compounds and the like as raw materials, and nitrogen atoms can be introduced during preparation of the carbon materials. The methods can be used for preparing uniform nitrogen-doped porous carbon materials, but the cost of the required raw materials is high, the preparation technology at the early stage is complex, and the large-scale production of factories is not facilitated.
Tar waste is the waste produced by some decoking processes and contains a large amount of carbon-containing organic polymers and various volatile substances inside. The waste is used as main waste in factory production, and the common treatment mode is direct incineration and destruction. This not only results in the waste of limited resources, but also causes secondary pollution by smoke and gases generated by combustion entering the air, and even causes greenhouse effect. However, tar, as an abundant carbon precursor, and containing abundant heteroatoms therein, is considered as a promising candidate in the production of functional carbon materials.
Disclosure of Invention
The invention aims to provide a method for preparing a porous carbon material by using tar waste aiming at the defects of high cost of raw materials, complex technology and the like required by the conventional preparation of the porous carbon material.
Preparation of porous carbon material
The invention takes tar waste generated by acid precipitation and decoking of pendimethalin wastewater as a carbon source and potassium carbonate as an activating agent, adopts a conventional heating device tubular furnace to prepare the porous carbon material for the supercapacitor, and comprises the following specific steps:
(1) pretreatment of reactants: drying the chemical plant tar waste in a 60-100 ℃ blast drying oven for 20-24 hours to change the tar waste from a sticky state into a hard solid; grinding the dried tar waste and potassium carbonate in a mortar according to the mass ratio of 1: 2-1: 4 to powder, and uniformly mixing to obtain a pretreated reactant;
(2) preparation of porous carbon material: using argon as protective gas, and carrying out constant temperature treatment on the pretreated reactant at 650-850 ℃ (preferably 750 ℃) for 60-120 min; naturally cooling to room temperature; and grinding and crushing the obtained product in a mortar, washing the crushed product with dilute hydrochloric acid solution and ultrapure water in sequence, filtering and drying to obtain the porous carbon material for the supercapacitor.
Structural characterization of porous carbon materials
FIG. 1 is a nitrogen adsorption and desorption isotherm diagram of a porous carbon material prepared by the present invention. As can be seen from FIG. 1, the porous carbon material prepared by the invention is a hierarchical porous structure carbon material with nested distribution of macropores and micropores, and the structure has the advantages that the material has high specific surface area and can accelerate mass transfer speed.
FIG. 2 is a graph showing the pore size distribution of the porous carbon material prepared by the present invention. As shown in FIG. 2, the pore diameter of the porous carbon material prepared by the invention is mainly distributed in the range of 0.1-2 nm, and the distribution of the microporous sections is more.
Table 1 shows the pore structure parameters of the porous carbon material for a supercapacitor according to the present invention. As can be seen from Table 1, the BET specific surface area of the porous carbon material prepared by the invention can reach 2105m2The pore volume is predominantly provided by micropores.
Figure DEST_PATH_IMAGE002
FIG. 3 shows a porous carbon material PC prepared by the present invention4-750Transmission electron micrograph (c). From fig. 3, it can be obtained that the macropores are uniformly distributed on the carbon material.
Electrochemical testing of porous carbon materials
The porous carbon material is used as an active substance, 5% of polytetrafluoroethylene dispersion liquid diluted by the porous carbon material is used as a bonding agent, the porous carbon material is dispersed in ethanol and uniformly coated on foamed nickel to be used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, 6 mol/L KOH solution is used as electrolyte, and a three-electrode system is adopted to carry out a series of electrochemical performance tests on the material.
FIG. 4 shows specific capacitance values of the porous carbon materials prepared in examples 1, 2, 3, 4, 5 and 6 of the present invention at a current density of 0.5A/g. The results in FIG. 4 show that the porous carbon material prepared by the invention has good capacitance performance, and in 6 mol/LKOH solution, when the current density is 0.5A/g, the specific capacitance value can reach 321.5F/g, and higher capacitance is shown.
In summary, compared with the prior art, the invention has the following technical effects:
1. the tar waste of the factory is used as a carbon source, so that the waste can be recycled, and the resource waste is reduced; the material is activated by utilizing various components, and heteroatom doping can be realized at the same time, so that the carbon material with the macroporous and microporous nested distribution hierarchical pore structure is prepared, and the structure has the advantages that the material has a high specific surface area, the solution transmission speed is high, and the material has a certain application prospect in the field of electrochemical energy storage;
2. the hierarchical pore structure carbon material prepared by the method shows good capacitance performance and higher capacitance, has good cycle life, and has excellent development prospect in the aspect of super capacitors;
3. the method directly takes the factory tar waste as the carbon source, utilizes the chemical activation method to prepare the porous carbon material, does not use a template agent, has simple process and low cost, and is beneficial to environmental protection.
Drawings
FIG. 1 is a nitrogen adsorption and desorption isotherm diagram of a porous carbon material prepared by the present invention.
FIG. 2 shows the pore size distribution of the porous carbon material prepared by the present invention.
FIG. 3 shows a porous carbon material PC prepared by the present invention4-750Transmission electron micrograph (D).
FIG. 4 shows specific capacitance values of the porous carbon materials prepared in examples 1, 2, 3, 4, 5 and 6 of the present invention at a current density of 0.5A/g.
Detailed Description
The preparation, properties and the like of the porous carbon material of the present invention are further illustrated by the following specific examples.
Example 1
(1) Pretreatment of reactants: putting the tar waste of the factory into a forced air drying oven at 100 ℃ for drying for 24 hours to change the tar waste from a sticky state into a hard solid; 1g of dried tar waste was weighed and put into a mortar to be ground into powder, to obtain a pretreated reactant.
(2) Preparation of porous carbon material: putting the pretreated reactant obtained in the step (1) into a corundum porcelain boat, putting the corundum porcelain boat into a tubular furnace, introducing argon as protective gas to exhaust air in the tubular furnace, keeping the tubular furnace at room temperature for not less than 30 min,then the tubular furnace is heated to the final temperature of 750 ℃ at the heating rate of 5 ℃/min, and is naturally cooled to the room temperature after being kept at the temperature for 120 min; putting the obtained product into a mortar for grinding and crushing, putting the ground product into a round-bottom flask, adding enough 1 mol/L HCl, fully stirring by using a magnetic stirrer, performing suction filtration, and washing the filtrate to be neutral by using ultrapure water; finally, putting the obtained filtrate into a vacuum drying oven for drying to obtain the porous carbon material for the supercapacitor, wherein the porous carbon material is marked as PC0-750。
(3) Electrochemical testing of porous carbon materials: mixing porous carbon material PC0-750Mixing 5% of polytetrafluoroethylene dispersion liquid and carbon black according to a mass ratio of 85:10:5, adding a few drops of ethanol as an adhesive, fully grinding, uniformly coating on foamed nickel as a working electrode, and in 6 mol/LKOH electrolyte, when the current density is 0.5A/g, the specific capacitance value is 41.5F/g.
Example 2
(1) Pretreatment of reactants: putting the tar waste of the factory into a forced air drying oven at 100 ℃ for drying for 24 hours to change the tar waste from a sticky state into a hard solid; weighing 1g of dried tar waste and 2 g of potassium carbonate, putting into a mortar, grinding into powder, and uniformly mixing to obtain a pretreated reactant;
(2) preparation of porous carbon material: in the same manner as in example 1, the porous carbon material obtained was designated PC2-750。
(3) Electrochemical properties of porous carbon material: PC (personal computer)2-750The specific capacitance value of the electrode material in 6 mol/LKOH electrolyte is 215.7F/g when the current density is 0.5A/g.
Example 3
(1) Pretreatment of reactants: putting the tar waste of the factory into a forced air drying oven at 100 ℃ for drying for 24 hours to change the tar waste from a sticky state into a hard solid; weighing 1g of dried tar waste and 3g of potassium carbonate, putting into a mortar, grinding into powder, and uniformly mixing to obtain a pretreated reactant;
(2) preparation of porous carbon material: in the same manner as in example 1, the porous carbon material obtained was designated PC3-750；
(3) Multiple purposeElectrochemical properties of the porous carbon material: PC (personal computer)3-750The specific capacitance value of the electrode material in 6 mol/LKOH electrolyte is 233.0F/g when the current density is 0.5A/g.
Example 4
(1) Pretreatment of reactants: putting the tar waste of the factory into a forced air drying oven at 100 ℃ for drying for 24 hours to change the tar waste from a sticky state into a hard solid; weighing 1g of dried tar waste and 4g of potassium carbonate, putting into a mortar, grinding into powder, and uniformly mixing to obtain a pretreated reactant;
(2) preparation of porous carbon material: in the same manner as in example 1, the porous carbon material obtained was designated PC4-750；
(3) Electrochemical properties of porous carbon material: PC (personal computer)4-750The specific capacitance value of the electrode material in 6 mol/LKOH electrolyte is 321.5F/g when the current density is 0.5A/g.
Example 5
(1) Pretreatment of reactants: putting the tar waste of the factory into a forced air drying oven at 100 ℃ for drying for 24 hours to change the tar waste from a sticky state into a hard solid; weighing 1g of dried tar waste and 4g of potassium carbonate, putting into a mortar, grinding into powder, and uniformly mixing to obtain a pretreated reactant;
(2) preparation of porous carbon material: the final heating temperature in the tube furnace was 650 ℃ and the rest of example 1; the obtained porous carbon material was labeled as PC4-650；
(3) Electrochemical properties of porous carbon material: PC (personal computer)4-650The specific capacitance value of the electrode material in 6 mol/LKOH electrolyte is 281.4F/g when the current density is 0.5A/g.
Example 6
(1) Pretreatment of reactants: putting the tar waste of the factory into a forced air drying oven at 100 ℃ for drying for 24 hours to change the tar waste from a sticky state into a hard solid; weighing 1g of dried tar waste and 4g of potassium carbonate, putting into a mortar, grinding into powder, and uniformly mixing to obtain a pretreated reactant;
(2) preparation of porous carbon material: the heating final temperature of the tubular furnace is 850 ℃, and the rest is the same as the example 1; marking with porous carbon materialIs PC4-850；
(3) Electrochemical properties of porous carbon material: PC (personal computer)4-850The specific capacitance value of the electrode material in 6 mol/LKOH electrolyte is 262.1F/g when the current density is 0.5A/g.

Claims (3)

1. The method for preparing the porous carbon material for the supercapacitor by using the tar waste comprises the following steps:
(1) pretreatment of reactants: the tar waste of the chemical plant is put into a blast drying oven for drying, so that the tar waste is changed into a hard solid from a sticky state; mixing the dried tar waste with potassium carbonate, and grinding the mixture to powder to obtain a pretreated reactant; the chemical plant tar waste is tar waste generated by acid precipitation decoking of pendimethalin wastewater;
(2) preparation of porous carbon material: using argon as protective gas, and carrying out constant-temperature treatment on the pretreated reactant at 650-850 ℃ for 60-120 min; naturally cooling to room temperature; and grinding and crushing the obtained product in a mortar, washing the crushed product with dilute hydrochloric acid solution and ultrapure water in sequence, filtering and drying to obtain the porous carbon material for the supercapacitor.
2. The method of preparing a porous carbon material for a supercapacitor using tar waste according to claim 1, wherein: the drying of the tar waste is carried out for 20-24 hours in a blast drying oven at 60-100 ℃.
3. The method of preparing a porous carbon material for a supercapacitor using tar waste according to claim 1, wherein: the mass ratio of the tar waste to the potassium carbonate is 1: 2-1: 4.
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