CN108455555B - High-volume specific-capacity coal-based supercapacitor electrode material and preparation method thereof - Google Patents
High-volume specific-capacity coal-based supercapacitor electrode material and preparation method thereof Download PDFInfo
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- CN108455555B CN108455555B CN201810049967.7A CN201810049967A CN108455555B CN 108455555 B CN108455555 B CN 108455555B CN 201810049967 A CN201810049967 A CN 201810049967A CN 108455555 B CN108455555 B CN 108455555B
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- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- 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
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- 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 relates to the technical field of electrode materials of super capacitors, in particular to a coal-based super capacitor electrode material with high volume specific capacity and a preparation method thereof, wherein the coal-based super capacitor electrode material with high volume specific capacity is obtained according to the following steps: crushing coal to obtain coal powder, and oxidizing the coal powder and an oxidant to obtain oxidized coal; mixing oxidized coal and potassium hydroxide to obtain a mixture; compacting the obtained mixture, and carrying out carbonization treatment on the compacted mixture to obtain a carbonized sample; and washing and drying the carbonized sample to obtain the capacitor electrode material. According to the invention, coal with wide sources is used as a raw material, and the porous carbon material with high apparent density, high specific surface area and high volume specific capacity is prepared by a simple and universal compaction activation method.
Description
Technical Field
The invention relates to the technical field of electrode materials of super capacitors, in particular to a coal-based super capacitor electrode material with high volume specific capacity and a preparation method thereof.
Background
Supercapacitors are favored by researchers because of their advantages of high energy density, excellent cycle performance, low cost, and environmental friendliness. The electrode material is the core of the super capacitor, and the research and development of the high-performance electrode material are the research in the related fieldEmphasis is placed on. At present, the electrode material of the most applied super capacitor belongs to a porous carbon material. The carbon material prepared by the common method has large specific surface area and high specific capacity, but the apparent density is small, so that the specific capacity is not high. Energy storage devices are required to release energy in a relatively limited space as much as possible in consumer electronic products and electric vehicles, so that it is very important to prepare a capacitor material with both high-quality specific capacity and high-volume specific capacity. The calculation formula of the specific volume capacity of the material is Cv=CmX ρ wherein CmThe material is the mass specific capacity, and rho is the apparent density of the material. Therefore, increasing the apparent density ρ of the electrode material and reducing the porosity of the material are effective means for increasing the specific capacity of the electrode material. However, decreasing porosity results in a decrease in the specific surface area and porosity of the material, and a decrease in the number of active energy storage sites and ion transport channels. This not only gives C of the materialmThe volume specific capacity is still not high due to the large reduction, and the rapid charge and discharge capacity of the material is also sacrificed. Therefore, the improvement of the volume specific capacity of the electrode material needs to be started from the comprehensive physical properties of the material, the contradiction relation between the porosity and the apparent density is balanced, the micro-morphology and the pore structure distribution of the material are reasonably designed, and the prepared electrode material has high-quality specific capacity CmAnd an electrode material having a high apparent density ρ. This remains a research hotspot and challenge in this field.
Disclosure of Invention
The invention provides a coal-based supercapacitor electrode material with high volume specific capacity and a preparation method thereof, overcomes the defects of the prior art, and can effectively solve the problem that the volume specific capacity of the electrode material of the conventional supercapacitor is not high.
One of the technical schemes of the invention is realized by the following measures: a high-volume specific capacity coal-based supercapacitor electrode material is obtained according to the following steps: the first step, crushing and screening coal to obtain coal powder, and carrying out oxidation reaction on the coal powder and an oxidant to obtain oxidized coal; step two, uniformly mixing required amount of oxidized coal and potassium hydroxide according to the mass ratio of 1: 0-4 to obtain a mixture; thirdly, compacting the obtained mixture, taking nitrogen as protective gas, carrying out carbonization treatment on the compacted mixture, carrying out temperature programming at the speed of 5 ℃/min, and heating to 500-1200 ℃ from room temperature to obtain a carbonized sample; and fourthly, washing the carbonized sample by deionized water until the washing liquid is neutral, and drying the washed carbonized sample to obtain the high-volume specific-capacity coal-based supercapacitor electrode material.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the oxidant is a mixed solution of concentrated sulfuric acid and concentrated nitric acid, wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed solution is 3: 1.
The pressure of the mixture obtained is 0.1MPa to 40 MPa.
The sieving process described above used a 200 mesh sieving apparatus.
The second technical scheme of the invention is realized by the following measures: a preparation method of a high-volume specific-capacity coal-based supercapacitor electrode material comprises the following steps: the first step, crushing and screening coal to obtain coal powder, and carrying out oxidation reaction on the coal powder and an oxidant to obtain oxidized coal; step two, uniformly mixing required amount of oxidized coal and potassium hydroxide according to the mass ratio of 1: 0-4 to obtain a mixture; thirdly, compacting the obtained mixture, taking nitrogen as protective gas, carrying out carbonization treatment on the compacted mixture, carrying out temperature programming at the speed of 5 ℃/min, and heating to 500-1200 ℃ from room temperature to obtain a carbonized sample; and fourthly, washing the carbonized sample by deionized water until the washing liquid is neutral, and drying the washed carbonized sample to obtain the high-volume specific-capacity coal-based supercapacitor electrode material.
The following is further optimization or/and improvement of the second technical scheme of the invention:
the oxidant is a mixed solution of concentrated sulfuric acid and concentrated nitric acid, wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed solution is 3: 1.
The pressure of the mixture obtained is 0.1MPa to 40 MPa.
The sieving process described above used a 200 mesh sieving apparatus.
According to the invention, coal with wide sources is used as a raw material, and the porous carbon material with high apparent density, high specific surface area and high volume specific capacity is prepared by a simple and universal compaction activation method.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the solution in the present invention is an aqueous solution in which the solvent is water, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution, unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to the following examples:
example 1: the high-volume specific capacity coal-based supercapacitor electrode material is characterized by being prepared according to the following steps: the first step, crushing and screening coal to obtain coal powder, and carrying out oxidation reaction on the coal powder and an oxidant to obtain oxidized coal; step two, uniformly mixing required amount of oxidized coal and potassium hydroxide according to the mass ratio of 1: 0-4 to obtain a mixture; thirdly, compacting the obtained mixture, taking nitrogen as protective gas, carrying out carbonization treatment on the compacted mixture, carrying out temperature programming at the speed of 5 ℃/min, and heating to 500-1200 ℃ from room temperature to obtain a carbonized sample; and fourthly, washing the carbonized sample by deionized water until the washing liquid is neutral, and drying the washed carbonized sample to obtain the high-volume specific-capacity coal-based supercapacitor electrode material.
The prior known material volume specific capacity calculation formula is Cv=CmX ρ wherein CmThe material is the mass specific capacity, and rho is the apparent density of the material.
The apparent density of the high-volume specific-capacity coal-based supercapacitor electrode material obtained by the invention is 0.70g/m3To 1.0g/m3(ii) a The specific surface area is 1700g/m2To 1800g/m2(ii) a The total pore volume was 0.6g/m3To 0.9g/m3(ii) a Micropore volume 0.6g/m3To 0.8g/m3(ii) a Under the current density of 1A/g, the specific mass capacity is F/g 200-300F/g; under the current density of 1A/g, the volume-to-volume specific capacity is 150F/cm3To 300F/cm3(ii) a Fast charge and discharge performance: under the current density of 50A/g, the volume specific capacity retention rate can reach more than 50% under the current density of 1A/g.
Example 2: the high-volume specific capacity coal-based supercapacitor electrode material is characterized by being prepared according to the following steps: the first step, crushing and screening coal to obtain coal powder, and carrying out oxidation reaction on the coal powder and an oxidant to obtain oxidized coal; step two, uniformly mixing required amount of oxidized coal and potassium hydroxide according to the mass ratio of 1:0.1 or 3 to obtain a mixture; thirdly, compacting the obtained mixture, taking nitrogen as protective gas, carrying out carbonization treatment on the compacted mixture, carrying out temperature programming at the speed of 5 ℃/min, and raising the temperature from room temperature to 500 ℃ or 1200 ℃ to obtain a carbonized sample; and fourthly, washing the carbonized sample by deionized water until the washing liquid is neutral, and drying the washed carbonized sample to obtain the high-volume specific-capacity coal-based supercapacitor electrode material.
Example 3: as an optimization of the above embodiment, the oxidant is a mixed solution of concentrated sulfuric acid and concentrated nitric acid, wherein a volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed solution is 3: 1.
Example 4: as an optimization of the above examples, the resulting mixture was pressurized to a pressure of 0.1MPa to 40 MPa.
The mixture is compacted using a hydraulic press at a pressure of 0.1 to 40 MPa.
Example 5: as an optimization of the above embodiment, a 200-mesh sieving apparatus was used for the sieving process.
The coal is crushed and screened to obtain fine coal powder with the coal powder of less than 200 meshes.
Example 6: the high-volume specific capacity coal-based supercapacitor electrode material is characterized by being prepared according to the following steps: the first step, crushing and screening coal to obtain coal powder, and carrying out oxidation reaction on the coal powder and an oxidant to obtain oxidized coal; step two, uniformly mixing 1.0g of oxidized coal and 1.0g of potassium hydroxide to obtain a mixture; thirdly, compacting the obtained mixture, performing carbonization treatment on the compacted mixture by using nitrogen as a protective gas under the pressure of 0.1-40 MPa of 3MPa, performing temperature programming at the speed of 5 ℃/min, and heating from room temperature to 600 ℃ to obtain a carbonized sample; and fourthly, washing the carbonized sample by deionized water until the washing liquid is neutral, and drying the washed carbonized sample to obtain the high-volume specific-capacity coal-based supercapacitor electrode material.
Example 7: the high-volume specific capacity coal-based supercapacitor electrode material is characterized by being prepared according to the following steps: the first step, crushing and screening coal to obtain coal powder, and carrying out oxidation reaction on the coal powder and an oxidant to obtain oxidized coal; step two, uniformly mixing 1.0g of oxidized coal and 0.6g of potassium hydroxide to obtain a mixture; thirdly, compacting the obtained mixture, performing carbonization treatment on the compacted mixture by using nitrogen as a protective gas under the pressure of 0.1-40 MPa as 8MPa, performing temperature programming at the speed of 5 ℃/min, and heating from room temperature to 600 ℃ to obtain a carbonized sample; and fourthly, washing the carbonized sample by deionized water until the washing liquid is neutral, and drying the washed carbonized sample to obtain the high-volume specific-capacity coal-based supercapacitor electrode material.
Electrochemical performance tests were performed on the high-volume specific-capacity coal-based supercapacitor electrode materials obtained in examples 6 and 7, and the obtained data are shown in table 1.
As can be seen from Table 1, the apparent density, the specific surface area, the volume specific capacity and the rapid charge and discharge performance of the high-volume specific-capacity coal-based supercapacitor electrode material are all superior to those of the conventional electrode material, and the pore structure distribution of the high-volume specific-capacity coal-based supercapacitor electrode material is reasonable.
In conclusion, coal with wide sources is used as a raw material, and a simple and universal compaction activation method is adopted to prepare the porous carbon material with high apparent density, high specific surface area, high volume specific capacity and good rapid charge and discharge performance. The invention solves the problem of low volume specific capacity of the electrode material of the super capacitor, and provides an idea for clean and efficient utilization of coal.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (2)
1. The high-volume specific-capacity coal-based supercapacitor electrode material is characterized by being prepared by the following steps: the method comprises the following steps of firstly, crushing coal, screening to obtain coal powder, and carrying out oxidation reaction on the coal powder and an oxidant to obtain oxidized coal, wherein the oxidant is a mixed solution of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1; secondly, uniformly mixing required amount of oxidized coal and potassium hydroxide according to the mass ratio of 1: 0-4 to obtain a mixture, wherein the numerical range cannot be zero; thirdly, compacting the obtained mixture, taking nitrogen as protective gas, carrying out carbonization treatment on the compacted mixture, carrying out temperature programming at the speed of 5 ℃/min, and heating to 500-1200 ℃ from room temperature to obtain a carbonized sample, wherein the pressure of the mixture is 0.1-40 MPa in real time; and fourthly, washing the carbonized sample by deionized water until the washing liquid is neutral, and drying the washed carbonized sample to obtain the high-volume specific-capacity coal-based supercapacitor electrode material.
2. A preparation method of a coal-based supercapacitor electrode material with high volume specific capacity is characterized by comprising the following steps: the method comprises the following steps of firstly, crushing coal, screening to obtain coal powder, and carrying out oxidation reaction on the coal powder and an oxidant to obtain oxidized coal, wherein the oxidant is a mixed solution of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1; secondly, uniformly mixing required amount of oxidized coal and potassium hydroxide according to the mass ratio of 1: 0-4 to obtain a mixture, wherein the numerical range cannot be zero; thirdly, compacting the obtained mixture, taking nitrogen as protective gas, carrying out carbonization treatment on the compacted mixture, carrying out temperature programming at the speed of 5 ℃/min, and heating to 500-1200 ℃ from room temperature to obtain a carbonized sample, wherein the pressure of the mixture is 0.1-40 MPa in real time; and fourthly, washing the carbonized sample by deionized water until the washing liquid is neutral, and drying the washed carbonized sample to obtain the high-volume specific-capacity coal-based supercapacitor electrode material.
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| CN109301246B (en) * | 2018-09-28 | 2021-07-02 | 东北大学秦皇岛分校 | Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode |
| CN115650205A (en) * | 2022-11-16 | 2023-01-31 | 安徽清能碳再生科技有限公司 | Pretreatment method for sodium ion battery negative electrode material |
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