CN111977651A - Preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon - Google Patents
Preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 137
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 title claims abstract description 94
- 229910000027 potassium carbonate Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 38
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims abstract description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000003476 subbituminous coal Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 229920005610 lignin Polymers 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 6
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 6
- 241001330002 Bambuseae Species 0.000 claims description 6
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 6
- 244000060011 Cocos nucifera Species 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000011425 bamboo Substances 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000003077 lignite Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- 238000007602 hot air drying Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 2
- 239000011148 porous material Substances 0.000 abstract description 26
- 239000003990 capacitor Substances 0.000 abstract description 19
- 238000005087 graphitization Methods 0.000 abstract description 19
- 239000007772 electrode material Substances 0.000 abstract description 13
- 238000012983 electrochemical energy storage Methods 0.000 abstract 1
- 239000003245 coal Substances 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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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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- 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
- C01B32/20—Graphite
- C01B32/205—Preparation
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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
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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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- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention aims to provide a preparation method of potassium carbonate chemically activated low-order carbon source-based porous carbon, which has developed pores, better graphitization degree, simple preparation process and obvious graphitization structure and can be applied to the field of electrochemical energy storage such as double electric layer super capacitor electrode materials. The invention relates to a preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon, which comprises the steps of processing a low-order carbon source into powder and drying the powder; dissolving 2-5 parts by weight of potassium carbonate in water to obtain a potassium carbonate solution, adding 1 part by weight of the powdery low-order carbon source obtained in the step A into the potassium carbonate solution, and placing the potassium carbonate solution mixed with the powdery low-order carbon source in a stirrer to be uniformly stirred to obtain a mixture. And C, placing the mixture obtained in the step B into an atmosphere furnace, filling nitrogen or argon into the atmosphere furnace, heating the atmosphere furnace at the speed of 3-20 ℃/min, and heating the atmosphere furnace to 900-1300 ℃.
Description
Technical Field
The invention relates to a preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon.
Background
Compared with the conventional chemical battery, the super capacitor has the advantages of long service life, high power density, high charge-discharge rate, wide working temperature limit and the like, and is widely applied to the application fields of solar energy, wind power generation, new energy automobiles, smart power grids and the like. The electrode material is a key component of the super capacitor, and mainly comprises a carbon-based material, a transition metal oxide and a high molecular polymer.
According to the calculation formulas C, E and E of the specific capacitance, power and energy of the super capacitor, A/d and 1/2CV2And P ═ U2and/R (C is specific capacitance and is related to the conductivity of the material, A is specific surface area, d is interlayer distance, and U is working voltage of the electrolyte), it can be shown that the specific capacitance of the super capacitor depends on the porosity and conductivity of the electrode material. The electrode material with higher specific surface area and better conductivity can promote the surface adsorption of electrolyte ions and the transmission of electrons in the electrode, thereby being beneficial to improving the specific capacitance, the power density and the energy density of the super capacitor. The carbon-based electrode material has the advantages of good physical and chemical properties, stable structure, high conductivity, environmental friendliness and the like, and is widely applied to double electric layer supercapacitors, particularly carbon nanomaterials such as graphene, carbon nanotubes and mesoporous carbon. The specific surface of the carbon nano materials can reach 2000-3000m3Has a high graphitization degree and can improve the conductivity, so the carbon material is often used as an electrode material of a super capacitor. However, the carbon nano materials have high preparation cost and complex process, and the application range of the super capacitor is seriously influenced.
The porous carbon material prepared by taking coal or biomass as a raw material provides a thought for a low-cost carbon-based super capacitor due to large reserves and low raw material cost. However, the coal or biomass-based porous carbon material prepared by the conventional processes of physical activation or high-temperature carbonization and the like has undeveloped pore structure (the specific surface area is generally lower than 1000 m)3And/g) mainly comprises amorphous carbon, and the requirements of high-performance double-electric-layer electrode materials on porosity and graphitization degree are difficult to meet.
The invention aims to solve the problem that the conventional coal or biomass-based porous carbon material is low in porosity and graphitization degree. The preparation method of the potassium carbonate chemically activated low-order carbon source-based porous carbon is characterized in that a low-order carbon source which is widely available in the nature, rich in reserves and low in cost is used as a raw material, a high-temperature oxidizing molten salt is used for etching a carbon structure of the low-order carbon source, the growth of a graphite lamellar structure is promoted, and the capacity of regulating and controlling a pore structure and a graphitization degree is coordinated.
Disclosure of Invention
The invention aims to provide a preparation method of potassium carbonate chemically activated low-grade carbon source-based porous carbon, which can be used for preparing porous carbon with developed pores and higher graphitization degree, wherein the developed pore structure and the higher graphitization degree are beneficial to the surface adsorption of electrolyte ions and the transmission of electrons in electrodes, the specific capacitance, power density, energy density and cycling stability of a super capacitor can be improved, and the product has good application potential in the field of electrode materials of double electric layer super capacitors.
The preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon comprises the following steps:
A. processing a low-order carbon source into powder, and drying, wherein the low-order carbon source comprises lignite, subbituminous coal, rice hulls, bamboo powder, coconut shells, wood powder, leaves, lignin and cellulose;
B. dissolving 2-5 parts by weight of potassium carbonate in water to obtain a potassium carbonate solution, adding 1 part by weight of the powdery low-order carbon source obtained in the step A into the potassium carbonate solution, placing the potassium carbonate solution mixed with the powdery low-order carbon source in a stirrer for uniformly stirring, and drying the mixed solution to obtain a mixture;
C. placing the mixture obtained in the step B into an atmosphere furnace, filling nitrogen or argon into the atmosphere furnace, heating the atmosphere furnace at the speed of 3-20 ℃/min, heating the atmosphere furnace to 900-1300 ℃, then preserving heat for 0.5-6 h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain an activated product;
D. c, carrying out acid washing treatment on the activated product obtained in the step C, and then carrying out water washing treatment to obtain a washed activated product;
E. and D, drying the cleaned activated product obtained in the step D to obtain the potassium carbonate chemically activated low-order carbon source based porous carbon.
Preferably, in the step B, 2.5 to 4.5 parts by weight of potassium carbonate is dissolved in water to obtain a potassium carbonate solution, 1 part by weight of the powdery low-grade carbon source obtained in the step A is added to the potassium carbonate solution, the stirrer stirs the potassium carbonate solution mixed with the powdery low-grade carbon source at a rotating speed of 100r/min to 500r/min, and the temperature for drying the mixed solution is 80 ℃ to 200 ℃.
Preferably, the content of nitrogen or argon in the atmosphere furnace gas in the step C is more than 90%, the purity of the nitrogen or argon filled in the atmosphere furnace is more than 99.999%, a small amount of hydrogen can be further filled in the atmosphere furnace, and the content of hydrogen is less than 10%.
Preferably, the particle sizes of the lignite, the subbituminous coal, the rice hull, the bamboo powder, the coconut shell, the wood powder, the leaves, the lignin and the cellulose in the step A are 80-200 meshes; the low-grade carbon source is dried at the temperature of 80-200 ℃ for 5-24 h.
Preferably, the step D is acid washing by hydrochloric acid or nitric acid, and the concentration of hydrochloric acid washing solution or nitric acid washing solution is 0.2-3 mol/L; and the step E, drying the cleaned activated product by utilizing hot air drying or vacuum drying, wherein the drying temperature is 80-200 ℃, and the drying time is 5-24 h.
Preferably, in the step A, the low-order carbon source is processed into powder by a ball mill, the rotating speed of the ball mill is 50 r/min-500 r/min, the ball milling time is 5 h-4 h, and the ball milling tank is made of agate, corundum or stainless steel.
Compared with the prior art, the preparation method of the potassium carbonate chemically activated low-order carbon source based porous carbon has the following beneficial effects:
the preparation method of the low-order carbon source based porous carbon chemically activated by potassium carbonate is provided to solve the problem that the porosity and graphitization degree of the conventional coal or biomass based porous carbon material are underdeveloped. The method takes a low-order carbon source which is widely available in the nature, rich in reserves and low in cost as a raw material, utilizes high-temperature oxidizing molten salt to etch the carbon structure of the low-order carbon source, promotes the growth capability of a graphite lamellar structure, and realizes the coordinated development of a porous carbon pore structure and graphitization degree of the low-order carbon source based on the low-order carbon source.
Secondly, uniformly mixing a low-order carbon source and potassium carbonate by a simple process, and performing high-temperature chemical activation and simple cleaning to obtain a porous carbon material with developed pores and good graphitization degree, wherein the preparation process is simple and is easy for large-scale production; in addition, the method can change the pore matching and the carbon structure type of the obtained porous carbon by regulating and controlling the reaction temperature.
Thirdly, the specific surface area of the porous carbon obtained by the invention can reach 1575m2The pore volume can reach 1.11cm3The super capacitor has a remarkable graphitization structure, a developed pore structure and a high graphitization degree, is beneficial to surface adsorption of electrolyte ions and transmission of electrons in an electrode, can improve the specific capacitance, power density, energy density and cycle stability of the super capacitor, and has good application potential in the field of double electric layer super capacitor electrode materials.
The present invention is described in further detail below.
Detailed Description
The invention discloses a preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon, which comprises the following steps:
A. processing a low-order carbon source into powder, and drying, wherein the low-order carbon source comprises lignite, subbituminous coal, rice hulls, bamboo powder, coconut shells, wood powder, leaves, lignin and cellulose;
B. dissolving 2-5 parts by weight of potassium carbonate in water to obtain a potassium carbonate solution, adding 1 part by weight of the powdery low-order carbon source obtained in the step A into the potassium carbonate solution, placing the potassium carbonate solution mixed with the powdery low-order carbon source in a stirrer for uniformly stirring, and drying the mixed solution to obtain a mixture;
C. placing the mixture obtained in the step B into an atmosphere furnace, filling nitrogen or argon into the atmosphere furnace, heating the atmosphere furnace at the speed of 3-20 ℃/min, heating the atmosphere furnace to 900-1300 ℃, then preserving heat for 0.5-6 h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain an activated product;
D. c, carrying out acid washing treatment on the activated product obtained in the step C, and then carrying out water washing treatment to obtain a washed activated product;
E. and D, drying the cleaned activated product obtained in the step D to obtain the potassium carbonate chemically activated low-order carbon source based porous carbon.
Compared with the prior art, the preparation method of the potassium carbonate chemically activated low-order carbon source-based porous carbon has the advantages that:
in the preparation method, a cheap low-order carbon source is used as a raw material, and during the high-temperature chemical activation process of the potassium carbonate, the potassium carbonate etches the carbonaceous structure of the low-order carbon source to form a developed pore structure; on the other hand, a potassium simple substance generated in the high-temperature activation process can be intercalated into a carbon structure, so that the evolution of the amorphous carbon structure to a graphite lamellar structure is catalyzed in the carbon precipitation process in the insertion and removal process, and the synergistic development of the porous carbon pore and the microcrystalline structure with the low-level carbon source is realized.
Secondly, uniformly mixing a low-order carbon source and potassium carbonate by a simple process, and performing high-temperature chemical activation and simple cleaning to obtain a porous carbon material with developed pores and good graphitization degree, wherein the preparation process is simple and is easy for large-scale production; in addition, the method can change the pore matching and the carbon structure type of the obtained porous carbon by regulating and controlling the reaction temperature.
Thirdly, the specific surface area of the porous carbon obtained by the invention is generally 1575m2More than g, the pore volume is usually 1.11cm3About/g, and has obvious graphitized structure. The developed pore structure and the higher graphitization degree are beneficial to the surface adsorption of electrolyte ions and the transmission of electrons in the electrode, the specific capacitance, the power density, the energy density and the cycling stability of the super capacitor can be improved, and the super capacitor has good application potential in the field of double electric layer super capacitor electrode materials. . Therefore, the product of the invention has good application potential in the field of double-electric-layer super capacitor electrode materials.
As a further improvement of the invention, in the step B, 2.5 to 4.5 parts by weight of potassium carbonate is dissolved in water to obtain a potassium carbonate solution, then 1 part by weight of the powdery low-grade carbon source obtained in the step A is added into the potassium carbonate solution, the stirring machine stirs the potassium carbonate solution mixed with the powdery low-grade carbon source at the rotating speed of 100r/min to 500r/min, and the temperature for drying the mixed solution is 80 ℃ to 200 ℃.
As a further improvement of the invention, in the step C, the content of nitrogen or argon in the atmosphere furnace gas is more than 90%, the purity of the nitrogen or argon filled in the atmosphere furnace is more than 99.999%, a small amount of hydrogen can be filled in the atmosphere furnace, and the content of hydrogen is less than 10%.
As a further improvement of the invention, the particle sizes of the lignite, the subbituminous coal, the rice hulls, the bamboo powder, the coconut shells, the wood powder, the leaves, the lignin and the cellulose in the step A are 80-200 meshes; the low-grade carbon source is dried at the temperature of 80-200 ℃ for 5-24 h.
As a further improvement of the invention, in the step D, hydrochloric acid or nitric acid is used for pickling, and the concentration of hydrochloric acid pickling solution or nitric acid pickling solution is 0.2-3 mol/L; and the step E, drying the cleaned activated product by utilizing hot air drying or vacuum drying, wherein the drying temperature is 80-200 ℃, and the drying time is 5-24 h.
As a further improvement of the invention, in the step A, the low-order carbon source is processed into powder by a ball mill, the rotating speed of the ball mill is 50 r/min-500 r/min, the ball milling time is 0.5 h-4 h, and the ball milling tank is made of agate, corundum or stainless steel.
Example 1
The invention discloses a preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon, which comprises the following steps:
A. processing the low-carbon source sub-bituminous coal into powder to obtain 80-100-mesh powder coal powder, namely the powder low-carbon source;
B. dissolving 3 parts by weight of potassium carbonate in water to obtain a potassium carbonate solution, then adding 1 part by weight of the powdery low-order carbon source obtained in the step A into the potassium carbonate solution, then placing the potassium carbonate solution mixed with the powdery low-order carbon source into a stirrer to be uniformly stirred, wherein the rotating speed of the stirrer is 300r/min, and then drying the mixed solution, wherein the drying temperature is 80 ℃, and the drying time is 20 hours; obtaining a mixture;
C. placing the mixture obtained in the step B into an atmosphere furnace, filling nitrogen into the atmosphere furnace, heating the atmosphere furnace at the speed of 5 ℃/min to 900 ℃, then preserving heat for 1h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain an activated product;
D. c, carrying out acid washing treatment on the activated product obtained in the step C for 3 times, wherein acid washing liquid adopted in the acid washing treatment is 2mol/L dilute hydrochloric acid, and then carrying out water washing treatment for 5 times to obtain the washed activated product;
E. and D, drying the cleaned activated product obtained in the step D at the temperature of 100 ℃ for 8 hours to obtain the potassium carbonate chemically activated low-order carbon source-based porous carbon.
The specific surface area of the low-order coal-based porous carbon is 1609m calculated by a nitrogen adsorption isotherm2Per g, pore volume of 0.94cm3(ii)/g; the microstructure observation shows that the microcrystalline structure of the porous carbon contains a large amount of amorphous carbon and has a graphite-like stripe structure.
Example 2:
the invention discloses a preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon, which comprises the following steps:
A. processing the low-carbon source sub-bituminous coal into powder to obtain 80-100-mesh powder coal powder, namely the powder low-carbon source;
B. dissolving 3 parts by weight of potassium carbonate in water to obtain a potassium carbonate solution, then adding 1 part by weight of the powdery low-order carbon source obtained in the step A into the potassium carbonate solution, then placing the potassium carbonate solution mixed with the powdery low-order carbon source into a stirrer to be uniformly stirred, wherein the rotating speed of the stirrer is 300r/min, and then drying the mixed solution, wherein the drying temperature is 80 ℃, and the drying time is 20 hours; obtaining a mixture;
C. placing the mixture obtained in the step B into an atmosphere furnace, filling nitrogen into the atmosphere furnace, heating the atmosphere furnace at the speed of 5 ℃/min to 1000 ℃, then preserving heat for 1h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain an activated product;
D. c, carrying out acid washing treatment on the activated product obtained in the step C for 3 times, wherein acid washing liquid adopted in the acid washing treatment is 2mol/L dilute hydrochloric acid, and then carrying out water washing treatment for 5 times to obtain the washed activated product;
E. and D, drying the washed activated product obtained in the step D at the temperature of 120 ℃ for 7 hours to obtain the potassium carbonate chemically activated low-order carbon source-based porous carbon.
The specific surface area of the low-order coal-based porous carbon is 1631m calculated by a nitrogen adsorption isotherm2Per g, pore volume of 1.06cm3The volume/g shows that the pore structure of the obtained low-order coal-based porous carbon is improved along with the increase of the reaction temperature. The microstructure observation shows that the surface of the porous carbon has an obvious sheet-like structure and an obvious long-range ordered graphite-like stripe structure, so that the graphitization degree of the prepared porous carbon is higher at the reaction temperature of 1000 ℃.
Example 3:
the invention discloses a preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon, which comprises the following steps:
A. processing the low-carbon source sub-bituminous coal into powder to obtain 80-100-mesh powder coal powder, namely the powder low-carbon source;
B. dissolving 3 parts by weight of potassium carbonate in water to obtain a potassium carbonate solution, then adding 1 part by weight of the powdery low-order carbon source obtained in the step A into the potassium carbonate solution, then placing the potassium carbonate solution mixed with the powdery low-order carbon source into a stirrer to be uniformly stirred, wherein the rotating speed of the stirrer is 300r/min, and then drying the mixed solution, wherein the drying temperature is 80 ℃, and the drying time is 20 hours; obtaining a mixture;
C. placing the mixture obtained in the step B into an atmosphere furnace, filling nitrogen into the atmosphere furnace, heating the atmosphere furnace at the speed of 5 ℃/min to 1200 ℃, then preserving heat for 1h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain an activated product;
D. c, carrying out acid washing treatment on the activated product obtained in the step C for 3 times, wherein acid washing liquid adopted in the acid washing treatment is 2mol/L dilute hydrochloric acid, and then carrying out water washing treatment for 5 times to obtain the washed activated product;
E. and D, drying the cleaned activated product obtained in the step D at the temperature of 100 ℃ for 8 hours to obtain the potassium carbonate chemically activated low-order carbon source-based porous carbon.
The specific surface area of the low-order coal-based porous carbon is 1575m calculated through a nitrogen adsorption isotherm2G, pore volume of 1.24cm3The reaction temperature is increased, the pore structure is developed, the pore size is widened, and the method is suitable for ion transmission of a larger organic electrolyte. The microscopic morphology observation shows that the porous carbon obtained in the embodiment also has an obvious graphene-like stripe structure and a high proportion, which indicates that the porous carbon has high graphitization degree and is suitable for being used as an electrode material of a double electric layer super capacitor. Therefore, the product obtained by the preparation method of the potassium carbonate chemically activated low-grade carbon source-based porous carbon has good application potential in the field of double-electric-layer supercapacitor electrode materials.
Example 4:
the invention discloses a preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon, which comprises the following steps:
A. processing the lignin powder of the low-order carbon source into powder, namely 80-100 meshes of the powdery lignin powder, namely the powdery low-order carbon source;
B. dissolving 3 parts by weight of potassium carbonate in water to obtain a potassium carbonate solution, then adding 1 part by weight of the powdery low-order carbon source obtained in the step A into the potassium carbonate solution, then placing the potassium carbonate solution mixed with the powdery low-order carbon source into a stirrer to be uniformly stirred, wherein the rotating speed of the stirrer is 300r/min, and then drying the mixed solution, wherein the drying temperature is 80 ℃, and the drying time is 20 hours; obtaining a mixture;
C. placing the mixture obtained in the step B into an atmosphere furnace, filling nitrogen into the atmosphere furnace, heating the atmosphere furnace at the speed of 5 ℃/min to 1000 ℃, then preserving heat for 1h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain an activated product;
D. c, carrying out acid washing treatment on the activated product obtained in the step C for 3 times, wherein acid washing liquid adopted in the acid washing treatment is 2mol/L dilute hydrochloric acid, and then carrying out water washing treatment for 5 times to obtain the washed activated product;
E. and D, drying the cleaned activated product obtained in the step D at the temperature of 100 ℃ for 8 hours to obtain the potassium carbonate chemically activated low-order carbon source-based porous carbon.
The specific surface area of the biomass-based porous carbon is 1644m through the calculation of a nitrogen adsorption isotherm2Per g, pore volume of 1.61cm3(ii) in terms of/g. Microstructure observation shows that the biomass-based porous carbon also has a large-area sheet-like structure and high graphitization degree. Compared with low-rank coal, the method has more obvious regulation and control effect on the biomass raw material, and can realize pore development and graphitized structure formation at relatively low temperature.
Comparative example 1:
the low-rank coal-based coke of the comparative example 1 is prepared according to a conventional high-temperature carbonization process, namely, no potassium carbonate activator is added in the preparation process, and the preparation method specifically comprises the following steps:
A. the east-west bituminous coal powder is crushed, ground, screened and dried in sequence to obtain 80-100 mesh powdery coal powder.
B. And C, placing the powdered coal powder in the step A into an atmosphere furnace, heating the atmosphere furnace to 1000 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain a carbonized product.
C. And (3) sequentially carrying out acid washing treatment on the carbonized product for 3 times, wherein the acid washing solution adopted in the acid washing treatment is 0.5mol/L dilute hydrochloric acid, and then carrying out water washing treatment for 3 times to obtain the washed carbonized product.
D. Carrying out hot air drying treatment on the washed carbonized product at the temperature of 100 ℃ for 8 hours to obtain low-rank coal-based coke;
the specific surface area of the low-rank coal-based coke is only 176m calculated by a nitrogen adsorption isotherm2Per g, pore volume of 0.13cm3The low-rank coal-based coke obtained by microstructure observation is typically amorphous in structure. Both porosity and graphitization are much lower than in the various embodiments of the present invention. It can be seen that when no potassium carbonate activator is added, the synergistic development of pore and microcrystalline structure cannot be realized only by the direct carbonization process.
Claims (6)
1. The preparation method of the potassium carbonate chemically activated low-order carbon source based porous carbon is characterized by comprising the following steps of: the method comprises the following steps:
A. processing a low-order carbon source into powder, and drying, wherein the low-order carbon source comprises lignite, subbituminous coal, rice hulls, bamboo powder, coconut shells, wood powder, leaves, lignin and cellulose;
B. dissolving 2-5 parts by weight of potassium carbonate in water to obtain a potassium carbonate solution, adding 1 part by weight of the powdery low-order carbon source obtained in the step A into the potassium carbonate solution, placing the potassium carbonate solution mixed with the powdery low-order carbon source in a stirrer for uniformly stirring, and drying the mixed solution to obtain a mixture;
C. placing the mixture obtained in the step B into an atmosphere furnace, filling nitrogen or argon into the atmosphere furnace, heating the atmosphere furnace at the speed of 3-20 ℃/min, heating the atmosphere furnace to 900-1300 ℃, then preserving heat for 0.5-6 h, and naturally cooling the atmosphere furnace to room temperature after the heat preservation is finished to obtain an activated product;
D. c, carrying out acid washing treatment on the activated product obtained in the step C, and then carrying out water washing treatment to obtain a washed activated product;
E. and D, drying the cleaned activated product obtained in the step D to obtain the potassium carbonate chemically activated low-order carbon source based porous carbon.
2. The method for preparing potassium carbonate chemically-activated low-order carbon source-based porous carbon according to claim 1, wherein the method comprises the following steps: and in the step B, 2.5 to 4.5 parts by weight of potassium carbonate is dissolved in water to obtain a potassium carbonate solution, 1 part by weight of the powdery low-order carbon source obtained in the step A is added into the potassium carbonate solution, the stirring machine stirs the potassium carbonate solution mixed with the powdery low-order carbon source at the rotating speed of 100r/min to 500r/min, and the temperature for drying the mixed solution is 80 ℃ to 200 ℃.
3. The method for preparing potassium carbonate chemically activated low-order carbon source-based porous carbon according to claim 2, wherein the method comprises the following steps: and C, the content of nitrogen or argon in the atmosphere furnace gas in the step C is more than 90%, the purity of the nitrogen or argon filled in the atmosphere furnace is more than 99.999%, hydrogen is also contained in the atmosphere furnace, and the content of the hydrogen is less than 10%.
4. The method for preparing potassium carbonate chemically activated low-order carbon source-based porous carbon according to claim 3, wherein the method comprises the following steps: in the step A, the particle sizes of lignite, subbituminous coal, rice hulls, bamboo powder, coconut shells, wood powder, leaves, lignin and cellulose are 80-200 meshes; the low-grade carbon source is dried at the temperature of 80-200 ℃ for 5-24 h.
5. The method for preparing potassium carbonate chemically-activated low-order carbon source-based porous carbon according to claim 4, wherein the method comprises the following steps: in the step D, hydrochloric acid or nitric acid is used for pickling, and the concentration of hydrochloric acid pickling solution or nitric acid pickling solution is 0.2-3 mol/L; and the step E, drying the cleaned activated product by utilizing hot air drying or vacuum drying, wherein the drying temperature is 80-200 ℃, and the drying time is 5-24 h.
6. The method for preparing a potassium carbonate chemically-activated low-order-carbon-source-based porous carbon as claimed in any one of claims 1 to 5, wherein: and in the step A, the low-order carbon source is processed into powder by using a ball mill, the rotating speed of the ball mill is 50 r/min-500 r/min, the ball milling time is 0.5 h-4 h, and the ball milling tank is made of agate, corundum or stainless steel.
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