CN110577222B - Activated carbon and preparation method and application thereof - Google Patents
Activated carbon and preparation method and application thereof Download PDFInfo
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- CN110577222B CN110577222B CN201910997508.6A CN201910997508A CN110577222B CN 110577222 B CN110577222 B CN 110577222B CN 201910997508 A CN201910997508 A CN 201910997508A CN 110577222 B CN110577222 B CN 110577222B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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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
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
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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 provides activated carbon and a preparation method and application thereof, belonging to the technical field of activated carbon preparation. The invention takes the bean hulls as raw materials, adds phosphoric acid solution for hydrothermal reaction, controls the temperature of the hydrothermal reaction to ensure that the obtained coke has certain pore structures, and the activating agent can enter the pore structures when the activating agent is activated later, so that the activation is more complete, and the activated carbon with large specific surface area is obtained. The data of the embodiment show that the specific surface area of the activated carbon prepared by the preparation method provided by the invention is 1319-2570 m2·g‑1Preparing the electrode slice of the super capacitor for electrochemical performance test at 100 mA.g‑1Has a specific capacitance of 207 to 301 F.g at a current density of‑1。
Description
Technical Field
The invention relates to the technical field of activated carbon preparation, in particular to activated carbon and a preparation method and application thereof.
Background
Electrochemical capacitors (also called supercapacitors) have received extensive attention due to their characteristics of rapid charge and discharge, high power density, long cycle life, and environmental friendliness. The electrode material is a key factor in determining the performance of the electrochemical capacitor. The activated carbon material has the characteristics of high specific surface area, low price, good conductivity and the like, so that the activated carbon material becomes a preferred material for preparing an electrochemical capacitor electrode. The electrochemical performance of the electrochemical capacitor is greatly influenced by the specific surface area of the activated carbon, and the activated carbon with large specific surface area can obtain large specific capacitance and good electrochemical performance.
The existing preparation methods of the activated carbon include a physical activation method and a chemical activation method. The active carbon prepared by a physical activation method and a chemical activation method in the prior art has the problems of low specific surface area and poor electrochemical performance.
Disclosure of Invention
In view of the above, the present invention aims to provide an activated carbon, and a preparation method and an application thereof. The activated carbon provided by the invention has large specific surface area and good electrochemical performance when being used as an electrode material of a super capacitor.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of activated carbon, which comprises the following steps:
mixing legume hulls with H3PO4Mixing the solutions, and then carrying out hydrothermal reaction at the temperature of 170-180 ℃ to obtain coke;
mixing the coke with an activating agent for activation to obtain an activated product, wherein the activating agent is KOH or NaOH;
and washing the activated product with hydrochloric acid and water in sequence to obtain the activated carbon.
Preferably, said H3PO4The mass fraction of the solution is 5-20%, and the legume shells and the H are3PO4The dosage ratio of the solution is 1.5-2 g:50 mL.
Preferably, the hydrothermal reaction time is 11-12 h.
Preferably, the legume shells are washed with ethanol and water sequentially prior to use.
Preferably, the mass ratio of the activating agent to the coke is 2: 1-4: 1.
Preferably, the activation temperature is 600-800 ℃, and the activation time is 2 h.
Preferably, the rate of temperature rise to the temperature of activation is 10 ℃/min.
Preferably, after the activation is finished, the method further comprises the step of naturally cooling to room temperature.
The invention also provides the activated carbon prepared by the preparation method of the technical scheme, and the specific surface area of the activated carbon is 1319-2570 m2·g-1。
The invention also improves the application of the activated carbon in the technical scheme as an electrode material in the field of super capacitors.
The invention provides a preparation method of activated carbon, which comprises the following steps: mixing legume hulls with H3PO4Mixing the solutions, and then carrying out hydrothermal reaction at the temperature of 170-180 ℃ to obtain coke; activating the cokeMixing the agents for activation to obtain an activated product, wherein the activating agent is KOH or NaOH; and washing the activated product with hydrochloric acid and water in sequence to obtain the activated carbon. According to the method, the bean hulls are taken as raw materials, a phosphoric acid solution is added for hydrothermal reaction, the temperature of the hydrothermal reaction is controlled, the obtained coke has a certain pore structure, and when the activated coke is activated with an activating agent later, the activating agent can enter the pore structures, so that the activation is more complete, the activated carbon with a large specific surface area is obtained, and meanwhile, the specific capacitance of the activated carbon is jointly improved by combining pore size distribution and surface functional groups. The data of the embodiment show that the specific surface area of the activated carbon prepared by the preparation method provided by the invention is 1319-2570 m2·g-1Preparing the electrode slice of the super capacitor for electrochemical performance test at 100 mA.g-1Has a specific capacitance of 207 to 301 F.g at a current density of-1。
Detailed Description
The invention provides a preparation method of activated carbon, which comprises the following steps:
mixing legume hulls with H3PO4Mixing the solutions, and then carrying out hydrothermal reaction at the temperature of 170-180 ℃ to obtain coke;
mixing the coke with an activating agent for activation to obtain an activated product, wherein the activating agent is KOH or NaOH;
and washing the activated product with hydrochloric acid and water in sequence to obtain the activated carbon.
The invention combines the legume shell with H3PO4And mixing the solutions, and then carrying out hydrothermal reaction at the temperature of 170-180 ℃ to obtain coke. In the present invention, said H3PO4The mass fraction of the solution is preferably 5-20%, more preferably 10-15%, and the legume shells and H are3PO4The dosage ratio of the solution is preferably 1.5-2 g:50 mL.
In the invention, the time of the hydrothermal reaction is preferably 11-12 h. In the present invention, the hydrothermal reaction is preferably carried out in a stainless steel kettle with a polytetrafluoroethylene lining.
In the present invention, the pod shells are preferably washed with ethanol and water in this order before use. After washing, it is preferable to further include a step of drying. The specific manner of washing and drying is not particularly limited in the present invention, and may be any manner known to those skilled in the art.
After the hydrothermal reaction is finished, the obtained hydrothermal product is preferably washed by ethanol and deionized water in sequence and then dried to obtain coke.
After the coke is obtained, the coke is mixed with an activating agent for activation to obtain an activated product, wherein the activating agent is KOH or NaOH. In the invention, the mass ratio of the activating agent to the coke is preferably 2: 1-4: 1, and more preferably 3: 1.
In the invention, the activation temperature is preferably 600-800 ℃, and the activation time is preferably 2 h.
In the present invention, the rate of temperature rise to the temperature for activation is preferably 10 ℃/min.
In the present invention, after the activation is completed, it is preferable to further include a step of naturally cooling to room temperature.
After an activated product is obtained, the activated product is washed by hydrochloric acid and water in sequence to obtain the activated carbon.
In the present invention, the concentration of the hydrochloric acid is preferably 2M.
The manner of washing the hydrochloric acid and water in the present invention is not particularly limited, and may be any manner known to those skilled in the art.
After the washing is completed, the present invention preferably puts the obtained solid in a vacuum drying oven at 105 ℃ overnight to obtain the activated carbon.
The invention also provides the activated carbon prepared by the preparation method of the technical scheme, and the specific surface area of the activated carbon is 1319-2570 m2·g-1。
The invention also improves the application of the activated carbon in the technical scheme as an electrode material in the field of super capacitors.
In a particular embodiment of the invention, said application is preferably: the activated carbon, the acetylene black and the PTFE are weighed according to the mass ratio of 85:10:5, are placed in an agate grinding machine for grinding, and then a sample is pressed on foamed nickel (current collector) by using a table type tabletting machine (6MPa) to prepare a disc-shaped electrode with the diameter of 13 mm.
In order to further illustrate the present invention, the activated carbon provided by the present invention, its preparation method and application are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
2g of pod shells and 50mL of 5 wt.% H3PO4Mixing the solution and performing ultrasonic treatment for 30min, placing the solution in a hydrothermal kettle for reaction for 12h at 180 ℃, cleaning the obtained solid product with ethanol and deionized water, and drying to obtain coke.
Mixing and grinding coke and KOH with the mass ratio of KOH to coke being 3:1, keeping the mixture at the activation temperature of 700 ℃ for 2h, and cleaning to obtain the material with the specific surface area of 2193m2·g-1Activated carbon with high specific surface area.
The obtained activated carbon is prepared into the electrode plate of the super capacitor, the preparation process comprises the steps of weighing the activated carbon, the acetylene black and the PTFE according to the mass ratio of 85:10:5, grinding the materials in agate grinding, pressing a sample on foamed nickel (current collector) by using a table type tablet press (6MPa) to prepare a wafer-shaped electrode with the diameter of 13mm, testing the electrochemical performance, and testing the electrochemical performance at 100 mA-g.g-1Has a specific capacitance of 270 F.g at a current density of-1。
Example 2
Same as example 1, except that H3PO4The mass fraction of the solution was 10%.
The specific surface area of the activated carbon prepared in the example is 2523m2·g-1Specific capacitance of 301F g-1。
Example 3
Same as example 1, except that H3PO4The mass fraction of the solution was 15%.
The specific surface area of the activated carbon prepared in the example is 2314m2·g-1Specific capacitance of 292F g-1。
Example 4
Same as example 1, except that H3PO4The mass fraction of the solution was 20%.
The specific surface area of the activated carbon prepared in this example was 2026m2·g-1Specific capacitance of 227F g-1。
Example 5
The only difference was that the activation temperature was 600 ℃ as in example 2.
The specific surface area of the activated carbon prepared in this example was 1319m2·g-1Specific capacitance of 207F g-1。
Example 6
The only difference was that the activation temperature was 800 ℃ as in example 2.
The specific surface area of the activated carbon prepared in this example was 2230m2·g-1Specific capacitance of 195F g-1。
Comparing the data of examples 2 and 6, it can be seen that the specific surface area of the obtained activated carbon is smaller at the activation temperature of 600 ℃ than 800 ℃, but the specific capacitance is larger because the specific capacitance is not only influenced by the specific surface area, but also influenced by the pore size distribution and the surface functional groups of the activated carbon, the oxygen or nitrogen element content in the raw material at 600 ℃ is higher, which is beneficial to improving the specific capacitance (certain pseudocapacitance exists), and the activation at 800 ℃ removes many functional groups in the raw material, resulting in lower specific capacitance.
Example 7
The only difference is that the mass ratio of KOH to coke is 2:1, as in example 2.
The specific surface area of the activated carbon obtained in this example was 1845m2·g-1Specific capacitance of 270F g-1。
Example 8
The only difference is that the mass ratio of KOH to coke is 4:1, as in example 2.
The specific surface area of the activated carbon prepared in the example is 2570m2·g-1Specific capacitance of 296F g-1。
Comparative example
As a reference experiment, deionized water was used in place of H during the mild pretreatment of the pod shells3PO4And (3) solution. Activating KOH and the obtained hydrothermal solid product at the temperature of 700 ℃ for 2h according to the ratio of 3:1, washing and drying to obtain activated carbon (noted as SSC). The electrochemical performance of the electrode of the super capacitor prepared by the activated carbon is tested at 100 mA.g-1Has a specific capacitance of 207F g at a current density of-1And the specific surface area is only 1293m2·g-1。
The comparative examples and the performance of the activated carbon prepared in examples 1 to 4 were tested, and the results are shown in table 1.
TABLE 1 results of performance test of activated carbon prepared in comparative example and examples 1 to 4
In Table 1, a is the specific surface area of the activated carbon; b is the total pore volume of the activated carbon; c, the average pore diameter of the activated carbon; d is the mass specific capacitance of the activated carbon; e, the area specific capacitance of the activated carbon.
The performance of the activated carbon prepared in examples 2, 5 to 8 was tested, and the results are shown in table 1.
TABLE 2 results of performance test of activated carbon prepared in examples 2, 5 to 8
In Table 2, a is the specific surface area of the activated carbon; b is the total pore volume of the activated carbon; c, the average pore diameter of the activated carbon; d is the mass specific capacitance of the activated carbon; e, the area specific capacitance of the activated carbon.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (9)
1. The preparation method of the activated carbon is characterized by comprising the following steps:
mixing legume hulls with H3PO4Mixing the solutions, and then carrying out hydrothermal reaction at the temperature of 170-180 ℃ to obtain coke; said H3PO4The mass fraction of the solution is 10-15%, and the legume shells and the H are3PO4The dosage ratio of the solution is 1.5-2 g:50 mL;
mixing the coke with an activating agent for activation to obtain an activated product, wherein the activating agent is KOH or NaOH;
and washing the activated product with hydrochloric acid and water in sequence to obtain the activated carbon.
2. The preparation method according to claim 1, wherein the hydrothermal reaction time is 11-12 h.
3. The method of claim 1, wherein the legume shells are washed with ethanol and water sequentially prior to use.
4. The preparation method according to claim 1, wherein the mass ratio of the activating agent to the coke is 2:1 to 4: 1.
5. The preparation method according to claim 1, wherein the activation temperature is 600-800 ℃ and the activation time is 2 h.
6. The production method according to claim 1 or 5, wherein a temperature rise rate for raising the temperature to the activation temperature is 10 ℃/min.
7. The method according to claim 1, further comprising a step of naturally cooling to room temperature after the activation.
8. The process according to claim 1 to 7The specific surface area of the obtained activated carbon is 2314-2570 m2·g-1。
9. Use of the activated carbon according to claim 8 as electrode material in the field of supercapacitors.
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| CN102205963A (en) * | 2011-03-16 | 2011-10-05 | 吉林大学 | Method for preparing activated carbon for biomass-based super capacitor |
| SG11201703235YA (en) * | 2014-11-04 | 2017-05-30 | Univ Singapore | Activated carbon, hydrochar and processes for making same |
| CN104724703A (en) * | 2015-03-20 | 2015-06-24 | 福州大学 | Method for preparing adsorptive activated carbon from Musaceae plants |
| CN105480973A (en) * | 2015-12-14 | 2016-04-13 | 河北工业大学 | Method for efficiently preparing cotton based mesoporous activated carbon fiber |
| CN105399872B (en) * | 2015-12-22 | 2018-06-15 | 齐鲁工业大学 | A kind of method and application using Jujun grasses Preparation of Activated Carbon with Lignin |
| CN105948036B (en) * | 2016-04-26 | 2018-04-03 | 湘潭大学 | A kind of preparation method and applications of root of kudzu vine base interconnection layer time aperture structure porous activated carbon material |
| CN106365163B (en) * | 2016-08-23 | 2018-10-09 | 中南大学 | A kind of preparation method of sisal fiber activated carbon and the application of the sisal fiber activated carbon in lithium-ion capacitor |
| CN108516548A (en) * | 2018-03-06 | 2018-09-11 | 合肥工业大学 | A kind of preparation method of high mesoporous rate activated carbon and its activated carbon of acquisition |
| CN109354015A (en) * | 2018-09-27 | 2019-02-19 | 合肥工业大学 | One kind is with sunflower disk production lithium-ion negative pole active carbon, electrode and test method |
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