CN111573670A - Preparation method and application of cellulose-based porous carbon - Google Patents
Preparation method and application of cellulose-based porous carbon Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 58
- 239000001913 cellulose Substances 0.000 title claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 51
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000227 grinding Methods 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052786 argon Inorganic materials 0.000 claims abstract description 18
- 239000001307 helium Substances 0.000 claims abstract description 18
- 229910052734 helium Inorganic materials 0.000 claims abstract description 18
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000004913 activation Effects 0.000 claims abstract description 16
- 239000013077 target material Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 40
- 239000000706 filtrate Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 24
- 238000007605 air drying Methods 0.000 claims description 21
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 239000011363 dried mixture Substances 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 7
- 235000018417 cysteine Nutrition 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000009656 pre-carbonization Methods 0.000 abstract description 13
- 239000003990 capacitor Substances 0.000 abstract description 10
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
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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
-
- 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
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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
- H01G11/22—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, 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
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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
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- Power Engineering (AREA)
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- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to the technical field of carbon material preparation, and relates to a preparation method and application of cellulose-based porous carbon, wherein the preparation method comprises the following steps: (1) grinding cellulose powder and a nitrogen source, and then carrying out pre-carbonization treatment under the protection of argon or helium to obtain a pre-carbonized product; (2) uniformly mixing the obtained pre-carbonized product with potassium hydroxide in deionized water, drying, and performing high-temperature activation treatment under the protection of argon or helium to obtain an activated product; (3) and (3) carrying out acid washing and water washing on the obtained activated product, and then drying to obtain the target material cellulose-based porous carbon. The preparation method has the advantages of simple operation process, low equipment cost and easily obtained raw materials, and has a series of advantages of high specific capacitance, good rate capability, long cycle life and the like when used as the electrode material of the super capacitor.
Description
Technical Field
The invention relates to a preparation method and application of cellulose-based porous carbon, and belongs to the technical field of carbon material preparation.
Background
The super capacitor is a novel energy storage device which stores electric charge inside an active material to complete electric energy storage mainly based on a physical adsorption or surface/near surface oxidation reduction mode. The high-power-density permanent magnet synchronous motor has the characteristics of long service life, high power density, good stability and the like, and is widely applied to various fields of vehicle starting power supplies, military equipment and the like. Porous carbon is a widely used electrode material for super capacitors. The commonly used carbon sources mainly include coal, biomass, organic polymers and the like, and among numerous carbon sources, biomass becomes one of ideal carbon sources due to the advantages of wide sources, renewability and the like.
Cellulose is one of macromolecular polysaccharide biomasses consisting of glucose, has good chemical stability due to the existence of a large number of hydrogen bonds between molecules and the cellulose, and is a polysaccharide which is distributed most widely and contains the most amount in nature and accounts for more than 50% of the carbon content in the plant world. In view of the above characteristics, cellulose, as a precursor of the porous carbon material, is also widely used in the field of supercapacitors. However, the thermal stability of the cellulose is poor due to the oxygen-rich characteristic of the cellulose, and carbon atoms in the cellulose are easy to be CO in the high-temperature carbonization process2The gasification of micromolecule forms leads to low yield of the product carbon, which is only about 10 percent. Finally, the utilization efficiency of biomass is low, the environmental pollution is serious, and industrialization is difficult to realize. Therefore, from the standpoint of atom economy, environmental pollution, and the like, increasing the yield of the cellulose-based carbon material has become a hotspot and difficulty in the research of biomass-based carbon materials for supercapacitors.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method and application of cellulose-based porous carbon. The preparation method has the advantages of simple process, safe operation, simple and easily obtained raw materials, low cost, high yield of the prepared cellulose-based porous carbon material, large mass specific capacitance and good rate capability when being used for the super capacitor, and can promote the application of the high-performance super capacitor.
In order to achieve the purpose of the invention and solve the problems existing in the prior art, the invention adopts the technical scheme that: a preparation method of cellulose-based porous carbon comprises the following steps:
and 2, mixing the pre-carbonized product prepared in the step 1 with potassium hydroxide according to the weight ratio of 1: mixing the raw materials in a mass ratio of 1-5, adding the mixture into 10-150 mL of deionized water, uniformly stirring and mixing, placing the mixture in a blast drying oven at a temperature of 60-140 ℃ for drying for 3-24 hours, placing the dried mixture in a tubular furnace under the protection of argon or helium for high-temperature activation treatment, raising the temperature from room temperature to 600-1000 ℃ at a heating rate of 1-10 ℃/min, keeping the temperature for 30-240 min, and naturally cooling to room temperature to obtain an activated product;
and 3, adding the activated product obtained in the step 2 into 50-1000 mL of 2mol/L hydrochloric acid solution, performing magnetic stirring for 5-24 h, performing suction filtration, washing with deionized water until the filtrate is neutral, and drying in a forced air drying oven at 60-120 ℃ for 8-24 h to obtain the target material cellulose-based porous carbon.
The cellulose-based porous carbon prepared by the preparation method is applied to the electrode material of the super capacitor.
The invention has the beneficial effects that: a preparation method and application of cellulose-based porous carbon are disclosed, wherein the preparation method comprises the following steps: (1) grinding cellulose powder and a nitrogen source according to a certain mass ratio, and then carrying out pre-carbonization treatment under the protection of argon or helium to obtain a pre-carbonized product; (2) uniformly mixing the obtained pre-carbonized product and potassium hydroxide in deionized water according to a certain mass ratio, drying, and performing high-temperature activation treatment under the protection of argon or helium to obtain an activated product; (3) and (3) carrying out acid washing and water washing on the obtained activated product, and then drying to obtain the target material cellulose-based porous carbon. Compared with the prior art, the invention has the following advantages: firstly, fully grinding cellulose and a nitrogen source (one selected from cysteine or melamine) to uniformly mix the cellulose and the nitrogen source, and performing pre-carbonization and high-temperature activation treatment to obtain the cellulose-based porous carbon. The activation of the potassium hydroxide can greatly improve the specific surface area, and the use of the nitrogen source not only introduces nitrogen atoms, but also improves the number of mesopores in the target material, thereby being beneficial to enhancing the transmission and diffusion of electrolyte ions on the surface and in the electrode material. The target material is used as a super capacitor electrode material, and shows a series of excellent electrochemical properties such as high specific capacity, good rate characteristic and long cycle life. Secondly, the preparation method has the advantages of simple operation process, low equipment cost and easy industrialization. In addition, the method can effectively improve the yield of the cellulose-based activated carbon, and realizes the high-efficiency high-added-value utilization of cellulose.
Drawings
Fig. 1 is a scanning electron micrograph of the cellulose-based porous carbon prepared in example 1.
Fig. 2 is a cyclic voltammogram of the cellulose-based porous carbon for a supercapacitor prepared in example 5.
Fig. 3 is a constant current charge and discharge graph of a cellulose-based porous carbon-assembled symmetrical supercapacitor prepared in example 8.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Weighing 1g of industrial cellulose and 1.5g of melamine, and placing the mixture in a grinding tank for grinding for 15 min; then, taking out the ground mixture, placing the mixture in a tube furnace under the protection of argon gas for pre-carbonization treatment, raising the temperature from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 240min, and naturally cooling to room temperature to obtain 0.45g of a pre-carbonized product; 0.3g of the pre-carbonized product and 0.9g of potassium hydroxide are weighed, added into 10mL of deionized water, uniformly stirred and mixed, and then dried in a forced air drying oven at 80 ℃ for 12 hours. Placing the dried mixture in a tubular furnace under the protection of helium gas for high-temperature activation treatment, raising the temperature from room temperature to 800 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 30min, and naturally cooling to room temperature to obtain an activated product; and adding the obtained activated product into 50mL of hydrochloric acid solution with the concentration of 2mol/L, performing suction filtration after magnetic stirring for 12 hours, washing the filtrate by using deionized water until the filtrate is neutral, and drying the filtrate in a forced air drying oven at 80 ℃ for 12 hours to obtain the target material cellulose-based porous carbon. Fig. 1 is a scanning electron micrograph of cellulose-based porous carbon for a supercapacitor, and it can be seen from fig. 1 that the cellulose-based porous carbon has a block structure of a micrometer scale.
Example 2
Weighing 1g of industrial cellulose and 2g of cysteine, placing the weighed materials into a grinding tank for grinding for 15min, taking out the ground mixture, placing the ground mixture into a tube furnace under the protection of helium for pre-carbonization treatment, raising the temperature from room temperature to 500 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 30min, and naturally cooling to room temperature to obtain 0.4g of a pre-carbonized product; weighing 0.3g of pre-carbonized product and 0.3g of potassium hydroxide, adding the pre-carbonized product and the potassium hydroxide into 10mL of deionized water, uniformly stirring and mixing, placing the mixture in a 60 ℃ forced air drying oven for drying for 10 hours, placing the dried mixture in a tubular furnace under the protection of helium gas for high-temperature activation treatment, raising the temperature from room temperature to 800 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 30min, and naturally cooling to the room temperature to obtain an activated product; adding the obtained activated product into 400mL of hydrochloric acid solution with the concentration of 2mol/L, performing suction filtration after magnetically stirring for 8h, washing the filtrate by using deionized water until the filtrate is neutral, and drying the filtrate in a forced air drying oven at 60 ℃ for 12h to obtain the target material cellulose-based porous carbon.
Example 3
Weighing 1g of industrial cellulose and 2g of melamine, placing the weighed industrial cellulose and melamine in a grinding tank for grinding for 15min, taking out the ground mixture, placing the ground mixture in a tube furnace under the protection of helium for pre-carbonization treatment, raising the temperature from room temperature to 700 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 70min, and naturally cooling to room temperature to obtain 0.52g of a pre-carbonized product; 0.3g of the pre-carbonized product and 1.2g of potassium hydroxide are weighed and added into 10mL of deionized water to be uniformly stirred and mixed, and then the mixture is placed in a forced air drying oven at 100 ℃ to be dried for 15 hours. Placing the dried mixture in a tubular furnace under the protection of helium gas for high-temperature activation treatment, heating the temperature from room temperature to 700 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 70min, and naturally cooling to room temperature to obtain an activated product; adding the obtained activated product into 150mL of hydrochloric acid solution with the concentration of 2mol/L, performing suction filtration after magnetic stirring for 24 hours, washing the filtrate by using deionized water until the filtrate is neutral, and drying the filtrate in a forced air drying oven at 100 ℃ for 12 hours to obtain the target material cellulose-based porous carbon.
Example 4
Weighing 1g of industrial cellulose and 1g of cysteine, placing the weighed materials in a grinding tank for grinding for 15min, taking out the ground mixture, placing the ground mixture in a tube furnace under the protection of argon gas for pre-carbonization treatment, raising the temperature from room temperature to 750 ℃ at the heating rate of 7 ℃/min, keeping the temperature for 120min, and naturally cooling to room temperature to obtain 0.25g of a pre-carbonized product; 0.2g of the pre-carbonized product and 0.8g of potassium hydroxide are weighed, added into 10mL of deionized water, uniformly stirred and mixed, and then placed in a forced air drying oven at 70 ℃ for drying for 18 h. Placing the dried mixture in a tubular furnace under the protection of argon gas for high-temperature activation treatment, heating the temperature from room temperature to 1000 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 120min, and naturally cooling to room temperature to obtain an activated product; adding the obtained activated product into 100mL of hydrochloric acid solution with the concentration of 2mol/L, performing suction filtration after magnetic stirring for 24 hours, washing the filtrate by using deionized water until the filtrate is neutral, and drying the filtrate in a forced air drying oven at 70 ℃ for 24 hours to obtain the target material cellulose-based porous carbon.
Example 5
Weighing 3g of industrial cellulose and 3g of melamine, placing the weighed industrial cellulose and the weighed melamine in a grinding tank for grinding for 20min, taking out the ground mixture, placing the ground mixture in a tube furnace under the protection of helium for pre-carbonization treatment, raising the temperature from room temperature to 800 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 70min, and naturally cooling to room temperature to obtain 1.25g of a pre-carbonized product; 1g of the pre-carbonized product and 2g of potassium hydroxide are weighed and added into 100mL of deionized water to be uniformly stirred and mixed, and then the mixture is placed in a forced air drying oven at 80 ℃ to be dried for 13 hours. Placing the dried mixture in a tubular furnace under the protection of helium gas for high-temperature activation treatment, heating the temperature from room temperature to 800 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 100min, and naturally cooling to room temperature to obtain an activated product; adding the obtained activated product into 240mL of hydrochloric acid solution with the concentration of 2mol/L, performing suction filtration after magnetic stirring for 10h, washing the filtrate by using deionized water until the filtrate is neutral, and drying the filtrate in a forced air drying oven at 80 ℃ for 10h to obtain the target material cellulose-based porous carbon.
And (3) uniformly mixing 10mg of the cellulose-based porous carbon with conductive carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, and pressing into uniform sheets by using a tablet press to obtain the electrode slices. And (3) taking the foamed nickel as a current collector, and pressing the electrode plate into the foamed nickel to be used as a working electrode of the super capacitor. 100mL of potassium hydroxide aqueous solution with the concentration of 6mol/L is taken as electrolyte, Hg/HgO is taken as a reference electrode, and a platinum sheet is taken as a counter electrode for carrying out electrochemical performance test. FIG. 2 is a cyclic voltammogram of the electrode material, showing that the electrode material exhibits good squareness at a sweep rate of 20mV/s, indicating that it has good capacitive characteristics.
Example 6
Weighing 3g of industrial cellulose and 1g of melamine, placing the weighed industrial cellulose and 1g of melamine in a grinding tank for grinding for 15min, taking out the ground mixture, placing the ground mixture in a tube furnace under the protection of argon for pre-carbonization treatment, raising the temperature from room temperature to 650 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 100min, and naturally cooling to room temperature to obtain 0.5g of a pre-carbonized product; 0.3g of the pre-carbonized product and 1.5g of potassium hydroxide are weighed and added into 10mL of deionized water to be uniformly stirred and mixed, and then the mixture is placed in a forced air drying oven at the temperature of 140 ℃ to be dried for 20 hours. Placing the dried mixture in a tubular furnace under the protection of argon gas for high-temperature activation treatment, heating the temperature from room temperature to 850 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 90min, and naturally cooling to room temperature to obtain an activated product; adding the obtained activated product into 250mL of hydrochloric acid solution with the concentration of 2mol/L, performing suction filtration after magnetic stirring for 5h, washing the filtrate by using deionized water until the filtrate is neutral, and drying the filtrate in a forced air drying oven at 80 ℃ for 10h to obtain the target material cellulose-based porous carbon.
Example 7
Weighing 4g of industrial cellulose and 2g of cysteine, placing the weighed materials into a grinding tank for grinding for 15min, taking out the ground mixture, placing the ground mixture into a tube furnace under the protection of argon gas for pre-carbonization treatment, raising the temperature from room temperature to 1000 ℃ at the heating rate of 6 ℃/min, keeping the temperature for 180min, and naturally cooling to room temperature to obtain 0.8g of a pre-carbonized product; 0.3g of the pre-carbonized product and 0.6g of potassium hydroxide are weighed, added into 30mL of deionized water, uniformly stirred and mixed, and then dried in a blast drying oven at 120 ℃ for 10 hours. Placing the dried mixture in a tubular furnace under the protection of argon gas for high-temperature activation treatment, heating the temperature from room temperature to 1000 ℃ at the heating rate of 8 ℃/min, keeping the temperature for 180min, and naturally cooling to room temperature to obtain an activated product; adding the obtained activated product into 500mL of hydrochloric acid solution with the concentration of 2mol/L, performing suction filtration after magnetically stirring for 18h, washing the filtrate by using deionized water until the filtrate is neutral, and drying the filtrate in a forced air drying oven at 120 ℃ for 10h to obtain the target material cellulose-based porous carbon.
Example 8
Weighing 3g of industrial cellulose and 4g of melamine, placing the weighed industrial cellulose and melamine in a grinding tank for grinding for 20min, taking out the ground mixture, placing the ground mixture in a tube furnace under the protection of helium for pre-carbonization treatment, raising the temperature from room temperature to 600 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 100min, and naturally cooling to room temperature to obtain 1.4g of a pre-carbonized product; 0.5g of the pre-carbonized product and 1.5g of potassium hydroxide are weighed and added into 50mL of deionized water to be uniformly stirred and mixed, and then the mixture is placed in a forced air drying oven at 100 ℃ to be dried for 18 hours. Placing the dried mixture in a tubular furnace under the protection of helium gas for high-temperature activation treatment, heating the temperature from room temperature to 850 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 240min, and naturally cooling to room temperature to obtain an activated product; adding the obtained activated product into 800mL of hydrochloric acid solution with the concentration of 2mol/L, performing suction filtration after magnetically stirring for 18h, washing the filtrate by using deionized water until the filtrate is neutral, and drying the filtrate in a forced air drying oven at 120 ℃ for 15h to obtain the target material cellulose-based porous carbon.
And (3) uniformly mixing 10mg of the cellulose-based porous carbon with conductive carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, and pressing into uniform sheets by using a tablet press to obtain the electrode slices. And (3) taking the foamed nickel as a current collector, and pressing the electrode plate into the foamed nickel to be used as a working electrode of the super capacitor. The ionic liquid is used as electrolyte, and two electrode plates with similar mass are assembled into a symmetrical super capacitor. Fig. 3 is a constant current charging and discharging curve of a symmetrical supercapacitor, and the result shows that the constant current charging and discharging curve presents a symmetrical isosceles triangle, which shows that the constant current charging and discharging curve has good capacitance characteristics, and the mass specific capacitance of the electrode material under the discharging current density of 1A/g is 290F/g.
Example 9
Weighing 4g of industrial cellulose and 4.5g of melamine, placing the weighed materials in a grinding tank for grinding for 15min, taking out the ground mixture, placing the ground mixture in a tube furnace under the protection of helium gas for pre-carbonization treatment, raising the temperature from room temperature to 675 ℃ at the heating rate of 7 ℃/min, keeping the temperature for 130min, naturally cooling to room temperature, and obtaining 1.7g of a pre-carbonized product; 0.5g of the pre-carbonized product and 2g of potassium hydroxide are weighed and added into 10mL of deionized water to be uniformly stirred and mixed, and then the mixture is placed in a forced air drying oven at the temperature of 80 ℃ to be dried for 17 hours. Placing the dried mixture in a tubular furnace under the protection of argon gas for high-temperature activation treatment, heating the temperature from room temperature to 1000 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 130min, and naturally cooling to room temperature to obtain an activated product; adding the obtained activated product into 1000mL of hydrochloric acid solution with the concentration of 2mol/L, performing suction filtration after magnetic stirring for 23h, washing the filtrate by using deionized water until the filtrate is neutral, and drying the filtrate in a forced air drying oven at 80 ℃ for 17h to obtain the target material cellulose-based porous carbon.
Example 10
Weighing 8g of industrial cellulose and 9.5g of cysteine, placing the weighed materials in a grinding tank for grinding for 20min, taking out the ground mixture, placing the ground mixture in a tube furnace under the protection of argon gas for pre-carbonization treatment, raising the temperature from room temperature to 1000 ℃ at the heating rate of 9 ℃/min, keeping the temperature for 230min, and naturally cooling to room temperature to obtain 2.1g of a pre-carbonized product; 1g of the pre-carbonized product and 4.5g of potassium hydroxide are weighed, added into 10mL of deionized water, uniformly stirred and mixed, and then placed in a forced air drying oven at 80 ℃ for drying for 13 hours. Placing the dried mixture in a tubular furnace under the protection of argon gas for high-temperature activation treatment, heating the temperature from room temperature to 900 ℃ at the heating rate of 9 ℃/min, keeping the temperature for 150min, and naturally cooling to room temperature to obtain an activated product; adding the obtained activated product into 600mL of hydrochloric acid solution with the concentration of 2mol/L, performing suction filtration after magnetic stirring for 19h, washing the filtrate by using deionized water until the filtrate is neutral, and drying the filtrate in a forced air drying oven at 80 ℃ for 13h to obtain the target material cellulose-based porous carbon.
Claims (2)
1. A preparation method of cellulose-based porous carbon is characterized by comprising the following steps:
step 1, weighing 1-10 g of industrial cellulose powder and 1-15 g of nitrogen source, placing the weighed materials into a grinding tank, grinding for 15-20 min, taking out the ground mixture, placing the mixture into a tube furnace under the protection of argon or helium, pre-carbonizing the mixture, raising the temperature from room temperature to 300-1000 ℃ at a heating rate of 1-10 ℃/min, keeping the temperature for 30-240 min, and naturally cooling the mixture to room temperature to obtain a pre-carbonized product, wherein the nitrogen source is one selected from cysteine or melamine;
and 2, mixing the pre-carbonized product prepared in the step 1 with potassium hydroxide according to the weight ratio of 1: mixing the raw materials in a mass ratio of 1-5, adding the mixture into 10-150 mL of deionized water, uniformly stirring and mixing, placing the mixture in a blast drying oven at a temperature of 60-140 ℃ for drying for 3-24 hours, placing the dried mixture in a tubular furnace under the protection of argon or helium for high-temperature activation treatment, raising the temperature from room temperature to 600-1000 ℃ at a heating rate of 1-10 ℃/min, keeping the temperature for 30-240 min, and naturally cooling to room temperature to obtain an activated product;
and 3, adding the activated product obtained in the step 2 into 50-1000 mL of 2mol/L hydrochloric acid solution, performing magnetic stirring for 5-24 h, performing suction filtration, washing with deionized water until the filtrate is neutral, and drying in a forced air drying oven at 60-120 ℃ for 8-24 h to obtain the target material cellulose-based porous carbon.
2. The application of the cellulose-based porous carbon prepared by the preparation method according to the claim 1 in the aspect of electrode materials of supercapacitors.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112670101A (en) * | 2021-01-04 | 2021-04-16 | 齐鲁工业大学 | Preparation method and application of conventional viscose fiber supercapacitor electrode material |
| CN112735858A (en) * | 2020-12-24 | 2021-04-30 | 上海应用技术大学 | Preparation method of nitrogen and sulfur co-doped layered porous carbon hybrid material for super capacitor |
| CN116216691A (en) * | 2023-02-02 | 2023-06-06 | 湖北万润新能源科技股份有限公司 | Hard carbon and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121678A (en) * | 2012-12-14 | 2013-05-29 | 大连理工大学 | Method for preparing nitrogen-doped activated carbon by utilizing PET (polyethylene terephthalate) waste material |
| US20140177136A1 (en) * | 2012-12-14 | 2014-06-26 | Samsung Electro-Mechanics Co., Ltd. | Activated carbon, method for preparing the same, and electrochemical capacitor including the same |
| EP3249669A1 (en) * | 2016-05-25 | 2017-11-29 | Universiteit van Amsterdam | Supercapacitor and nitrogen-doped porous carbon material |
| CN109534341A (en) * | 2019-01-30 | 2019-03-29 | 中国矿业大学 | A kind of preparation method and applications of N doping pericarp base porous carbon material |
| CN110395731A (en) * | 2019-07-27 | 2019-11-01 | 大连理工大学 | A kind of preparation method and applications of starch base porous carbon with high specific surface area |
-
2020
- 2020-04-04 CN CN202010261688.4A patent/CN111573670A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121678A (en) * | 2012-12-14 | 2013-05-29 | 大连理工大学 | Method for preparing nitrogen-doped activated carbon by utilizing PET (polyethylene terephthalate) waste material |
| US20140177136A1 (en) * | 2012-12-14 | 2014-06-26 | Samsung Electro-Mechanics Co., Ltd. | Activated carbon, method for preparing the same, and electrochemical capacitor including the same |
| EP3249669A1 (en) * | 2016-05-25 | 2017-11-29 | Universiteit van Amsterdam | Supercapacitor and nitrogen-doped porous carbon material |
| CN109534341A (en) * | 2019-01-30 | 2019-03-29 | 中国矿业大学 | A kind of preparation method and applications of N doping pericarp base porous carbon material |
| CN110395731A (en) * | 2019-07-27 | 2019-11-01 | 大连理工大学 | A kind of preparation method and applications of starch base porous carbon with high specific surface area |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112735858A (en) * | 2020-12-24 | 2021-04-30 | 上海应用技术大学 | Preparation method of nitrogen and sulfur co-doped layered porous carbon hybrid material for super capacitor |
| CN112670101A (en) * | 2021-01-04 | 2021-04-16 | 齐鲁工业大学 | Preparation method and application of conventional viscose fiber supercapacitor electrode material |
| CN116216691A (en) * | 2023-02-02 | 2023-06-06 | 湖北万润新能源科技股份有限公司 | Hard carbon and preparation method and application thereof |
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