CN114735679A - Method for preparing porous graphene electrode material by utilizing pyrolysis activation of mulberry stem carbon - Google Patents
Method for preparing porous graphene electrode material by utilizing pyrolysis activation of mulberry stem carbon Download PDFInfo
- Publication number
- CN114735679A CN114735679A CN202210393471.8A CN202210393471A CN114735679A CN 114735679 A CN114735679 A CN 114735679A CN 202210393471 A CN202210393471 A CN 202210393471A CN 114735679 A CN114735679 A CN 114735679A
- Authority
- CN
- China
- Prior art keywords
- carbon
- porous graphene
- electrode material
- mulberry
- activation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 230000004913 activation Effects 0.000 title claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 235000008708 Morus alba Nutrition 0.000 title claims abstract description 46
- 240000000249 Morus alba Species 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000007772 electrode material Substances 0.000 title claims abstract description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 16
- 230000003213 activating effect Effects 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012047 saturated solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000003990 capacitor Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 235000013162 Cocos nucifera Nutrition 0.000 description 6
- 244000060011 Cocos nucifera Species 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000053 physical method Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000012190 activator Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 241000218213 Morus <angiosperm> Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000003570 Phyllostachys pubescens Nutrition 0.000 description 1
- 244000302661 Phyllostachys pubescens Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000010675 chips/crisps Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for preparing a porous graphene electrode material by utilizing pyrolysis and activation of mulberry stem carbon, and belongs to the technical field of preparation of biomass activated carbon materials. According to the method, mulberry stems are carbonized to serve as a carbon source, superheated steam, carbon dioxide and potassium hydroxide serve as activating agents, the four substances are mixed and then uniformly conveyed to high-temperature pyrolysis equipment for pyrolysis activation, and finally the porous graphene electrode material is directly prepared. The porous graphene electrode material prepared by the method can be used as an energy storage electrode nano material for a supercapacitor, and shows higher power energy density and electric energy storage capacity.
Description
Technical Field
The invention belongs to the technical field of biomass activated carbon material preparation, and particularly relates to a method for preparing a porous graphene electrode material by utilizing pyrolysis activation of mulberry stem carbon.
Background
A supercapacitor is a new type of energy storage device between a conventional capacitor and a rechargeable battery, and its capacity can reach several hundreds to thousands of methods. Compared with the traditional capacitor, the capacitor has larger capacity, specific energy or capacity density, wider working temperature range and extremely long service life; compared with accumulator, it has higher specific power and no environmental pollution. Compared with a storage battery and a traditional physical capacitor, the super capacitor is mainly characterized in that: high power density, long cycle life, wide working temperature limit, high charging and discharging speed, safety, no maintenance, environmental protection and the like. A supercapacitor is a novel component that stores energy through an interfacial double layer formed between electrodes and an electrolyte. It is mainly composed of an electrode formed by loading porous nanometer materials on a current collector, a diaphragm arranged between two electrodes and electrolyte.
At present, the electrode material for domestic high-end supercapacitors is prepared from coconut shell activated carbon, the coconut shell is a high-quality activated carbon raw material, and the coconut shell activated carbon has excellent adsorption performance. The coconut shell activated carbon is the highest quality of shell activated carbon, is amorphous particles, and not only has good adsorption performance, but also has high mechanical strength. Coconut shell carbon has high adsorption capacity and large micropore volume, but the raw material source is mainly imported from southeast Asia countries (Malaysia, Indonesia, Vietnam and the like), and the raw material source is limited abroad, so that the cost is high.
Disclosure of Invention
The invention provides a method for preparing a porous graphene electrode material by utilizing pyrolysis activation of mulberry stem carbon, which aims at the problems of shortage and insufficient raw material source in the existing direct preparation technology of the porous graphene material, the raw material source is rich, the process for preparing activated carbon by pyrolysis activation is simple, the production cost is low, the method is suitable for industrial scale production, and the prepared porous graphene electrode material can be used as an energy storage electrode nano material for a supercapacitor.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the method for preparing the porous graphene electrode material by utilizing the pyrolysis activation of the mulberry stalk carbon comprises the following steps:
(1) collecting mulberry stems, carbonizing at high temperature, and pulverizing to obtain primary mulberry stem carbon pulverized powder with solid particle size below 3 mm.
(2) Pulverizing the primary crushed mulberry stalk carbon powder into superfine carbon powder with the granularity D501500 meshes or more (below 10 mu m).
(3) Adding a chemical activating agent into the superfine carbon powder, soaking, mixing, stirring and activating for 1 hour, then mixing the obtained chemical activating mixture with physical activating gas, carrying out pyrolysis activation treatment at the temperature of 500-800 ℃, and finally cooling under the protection of inert gas to obtain the porous graphene electrode material.
Further optimizing, in the step (1), the mulberry stems are heated and decomposed at a high temperature of more than 500 ℃ under the condition of air isolation to obtain carbonized raw material products.
Further optimizing, in the step (1), the water content of the primary mulberry stalk charcoal crushed powder is less than 5%.
Further preferably, in the step (3), the chemical activating agent is a potassium hydroxide saturated solution.
Further optimizing, in the step (3), the mass ratio of the chemical activating agent to the superfine carbon powder is 2: 1.
further preferably, in step (3), the physically activated gas comprises superheated steam and carbon dioxide.
Further optimizing, mixing the superheated steam and the carbon dioxide according to the volume ratio of 1:1, and maintaining the pressure of the carbon powder after chemical activation and the mixed gas under the condition of differential pressure for pyrolysis activation air flow conveying.
Further optimizing, wherein the superheated steam pressure is 0.5-2.5 MPa, and the temperature is 250-600 ℃.
Further preferably, in the step (3), the inert protective gas is nitrogen.
Further optimization, in the step (3), the thermal medium in the thermal cracking equipment is heated by an external electromagnetic heating mode through the pyrolysis activation treatment at the temperature of 500-800 ℃.
Compared with the prior other preparation technologies of the active carbon, the invention has the following technical advantages:
1. the invention provides a method for preparing a porous graphene electrode material by using mulberry stem resources which are specially and widely planted in Guangxi and rich in sources as raw materials after carbonization treatment and utilizing pyrolysis activation of mulberry stem carbon, and the method has the advantages of rich and easily-obtained raw materials, high carbon content, simple process, environmental friendliness, low cost, high comprehensive utilization rate, suitability for industrial mass production and the like.
2. The pressure and temperature of steam in the process of pyrolysis activation of the superfine carbon powder in a tubular furnace of a thermal cracking reactor can be adjusted at will, the activation mode adopts a physical method of carbon dioxide gas activation and a chemical method of potassium hydroxide saturated solution activation to be simultaneously used in a composite way, the activation effect is better, and the product quality is better.
3. In the pyrolysis activation preparation process, wet thermal mixing is adopted, the porous graphene is directly pyrolyzed and activated, the process is simple, the activation speed is high, the energy consumption is effectively reduced, and the industrial and large-scale production is easy to realize.
4. The porous graphene material product prepared by the method has the advantages of large specific surface area, strong adsorption capacity, high adsorption speed, low impurity content and the like, wherein the average specific surface area is 1200-2500 m2Between/g; the average pore diameter is between 0.5 and 3 nm; the thickness (1-10 layers) is 0.35-10 nm on average; the average particle diameter is 0.5 to 1 μm.
5. The graphene material of the porous activated carbon prepared by the invention has the advantages of both the porous activated carbon material and the graphene material, and can be used as an energy storage electrode material of a super capacitor, the developed pore structure of the graphene material can improve the ion conduction rate and the energy density of the graphene material, and the highly graphitized thin layer of the graphene material also improves the electron transfer rate, so that the electrochemical performance of the super capacitor is effectively improved.
Drawings
Fig. 1 is a flow chart of a pyrolysis activation production process of a porous graphene material according to an embodiment of the present invention, in which:
1. the system comprises a superheated steam boiler, 2, an ultrafine grinding and grading machine, 3, a slurry plunger pump, 4, a carbon dioxide activator tank, 5, a material mixer, 6, a pyrolysis activation reactor, 7, a cyclone separator, 8, a tube cooler, 9, a negative pressure pulse dust collector, 10 and a nitrogen protection product cooling bin.
Fig. 2 is a transmission electron micrograph of the porous graphene electrode material prepared according to the embodiment of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described in detail with reference to the following examples and drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the present invention, the expressions "less than", "above" and "below" all include the present numbers.
Examples
Referring to fig. 1, the method for preparing a porous graphene electrode material by utilizing pyrolysis activation of mulberry stalk carbon according to the present invention includes:
firstly, collecting mulberry stem raw material high-temperature carbonization
Charring is a process of thermochemical processing of solid fuels or the thermal decomposition of organic compounds into carbon and other products in the absence of air.
The mulberry resources in Guangxi are very rich, the mulberry planting area reaches more than 300 ten thousand mu in 2020, the annual resource amount of mulberry stems reaches 100 ten thousand tons, and the method is recyclable and has the advantages of low price, easy obtainment, less impurities, low ash content, high carbon content and the like.
According to the invention, mulberry stems are collected from a field of a mulberry planting area by an organizer, carbonized raw material products are processed by high-temperature heating decomposition at the temperature of more than 500 ℃ under the condition of air isolation, generally the carbonized raw materials are rod-shaped, strip-shaped and crushed charcoals, and the carbonized raw materials are processed and crushed by a crusher to primary mulberry stem carbon crushed powder of solid particles with the particle size of less than 3mm and the water content of less than 5%.
Second, ultrafine grinding mulberry stem carbon into pre-treated carbon powder
Crushing the primary mulberry stalk carbon obtained after crushing in the step one, collecting and transporting the crushed primary mulberry stalk carbon to an active carbon production workshop, and carrying out ultrafine crushing and classification by a classifier 2 to obtain pretreated carbon powder (ultrafine carbon powder) with the particle size D50 of more than 1500 meshes (less than 10 mu m) (the crushed particle size of the embodiment is 2000 meshes/6.5 mu m).
Thirdly, the ultrafine carbon powder is treated by mixed pyrolysis activation (physical method/chemical method)
Adding a potassium hydroxide saturated solution into the pretreated carbon powder (superfine carbon powder) obtained by crushing in the second step for dipping, mixing and stirring, wherein the activation time is 1 hour, then conveying the chemical activation mixture to a material mixer 5 through a slurry plunger pump 3, mixing and colliding superheated steam (the pressure is 2.0MPa and the temperature is 600 ℃) generated by a superheated steam boiler 1 and a carbon dioxide activator stored in a carbon dioxide activator tank 4 in the material mixer 5, conveying the high-temperature mixture to a pyrolysis activation reactor 6 tubular furnace, and carrying out pyrolysis and activation treatment at the temperature of 500-800 ℃ under high temperature and high pressure.
The method adopts the mulberry stem carbon as the raw material, is different from other additional purification and activation preparation methods, and is carried out by utilizing a physical method and a chemical method for simultaneous mixed activation, taking a potassium hydroxide saturated solution as a chemical activating agent and taking (superheated steam and carbon dioxide, the mixed volume ratio is 1: 1) as a gas gasifying agent of the physical method. The granularity of the carbon powder is more than 1500 meshes, the superheated steam pressure is 0.5-2.5 MPa, the temperature is 250-600 ℃, and the mass ratio of (the superfine carbon powder and the potassium hydroxide saturated solution) to the alkali carbon is 2: adding carbon powder and a potassium hydroxide saturated solution into the mixture to perform dipping, mixing and stirring, wherein the activation time is 1 hour, the activation temperature is 800 ℃, the collision activation is performed by adopting high-efficiency high-speed fluid, the activation time is short, the efficiency is high, the speed is high, the activation time is about 5-10 seconds, the energy is saved, the efficiency is high, the environment is protected, the pores are developed, the specific surface area is large, and high-efficiency high-quality activated carbon can be produced.
The mulberry stem carbon activated product is nano activated carbon, is one of important carbon sources of porous graphene, is directly synthesized into graphene activated carbon with high added value from the activation of the mulberry stem carbon, especially the porous graphene, and can realize the high added value utilization of the activated carbon activated by the mulberry stem carbon.
Fourthly, cooling and collecting for producing porous graphene products
And step three, after high-temperature and high-pressure pyrolysis and activation treatment, the product of the porous graphene produced in the tubular furnace of the pyrolysis activation reactor 6 is finally conveyed to a tubular cooler 8 through a cyclone separator 7 to be subjected to waste heat recovery of activated carbon cooling and cooling water heat exchange heat absorption, and the hot water recovered by the activated carbon heat exchanger is supplied to the superheated steam boiler 1 for recycling, so that waste heat utilization, energy conservation and emission reduction are realized. And (3) conveying the activated carbon product with the temperature of about 150-250 ℃ after cooling to a negative pressure pulse dust collector 9 for powder collection, discharging the hot waste gas reaching the environmental standard outdoors by a draught fan, conveying the porous graphene powder to a nitrogen protection product cooling bin 10 by the negative pressure pulse dust collector 9 under the protection of inert gas nitrogen for storage, and finally obtaining the porous graphene product, wherein the transmission electron microscope picture of the porous graphene product is shown in figure 2.
Fifthly, detecting performance indexes of porous graphene products
The performance detection and parameter index results of the porous graphene product obtained in the embodiment are shown in the following table:
therefore, the method can prepare a green and environment-friendly porous material graphene product with high specific surface area and high quality, and the activated carbon product has the advantages of large specific surface area, strong adsorption capacity, high adsorption speed, low impurity content and the like.
It should be noted that the preparation method of the embodiment is not only suitable for preparing the porous graphene electrode material for the supercapacitor by using the pyrolysis activation of the mulberry stalk carbon, but also can be used for preparing other wood (wood chips, mulberry trees, moso bamboos and the like) carbon source porous graphene activated carbon; shell (coconut shell, walnut shell, apricot shell, rice hull, etc.) carbon source porous graphene activated carbon; coal (lignite, peat, soft coal, anthracite and the like) type carbon source porous graphene activated carbon; organic matter (starch, white sugar, rock sugar and the like) carbon source porous graphene activated carbon and the like.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications can be made on the basis of the above description, and all the implementation methods cannot be exhaustive, and the obvious variations or modifications introduced in the technical scheme of the present invention are within the protection scope of the present invention.
Claims (10)
1. The method for preparing the porous graphene electrode material by utilizing the pyrolysis activation of the mulberry stalk carbon comprises the following steps:
(1) collecting mulberry stems, carbonizing at high temperature, and pulverizing to obtain primary mulberry stem carbon crushed powder with solid particle size of less than 3 mm;
(2) crushing the primary mulberry stalk carbon crushed powder into superfine carbon powder with the granularity D501500 meshes;
(3) adding a chemical activating agent into the superfine carbon powder, soaking, mixing, stirring and activating for 1 hour, then mixing the obtained chemical activating mixture with physical activating gas, carrying out pyrolysis activation treatment at the temperature of 500-800 ℃, and finally cooling under the protection of inert gas to obtain the porous graphene electrode material.
2. The method for preparing a porous graphene electrode material by utilizing mulberry stalk carbon pyrolysis activation as claimed in claim 1, wherein in the step (1), the mulberry stalk is heated and decomposed at a high temperature of more than 500 ℃ under the condition of air isolation to process a carbonized raw material product.
3. The method for preparing the porous graphene electrode material by utilizing the pyrolysis activation of the mulberry stalk carbon as claimed in claim 1, wherein in the step (1), the water content of the primary mulberry stalk carbon crushed powder is less than 5%.
4. The method for preparing the porous graphene electrode material by utilizing the pyrolysis activation of the mulberry stalk carbon according to claim 1, wherein in the step (3), the chemical activating agent is a potassium hydroxide saturated solution.
5. The method for preparing the porous graphene electrode material by utilizing the pyrolysis activation of the mulberry stalk carbon according to claim 1 or 4, wherein in the step (3), the mass ratio of the chemical activating agent to the ultrafine carbon powder is 2: 1.
6. the method for preparing a porous graphene electrode material by utilizing pyrolysis activation of mulberry stalk carbon according to claim 1, wherein in the step (3), the physical activation gas comprises superheated steam and carbon dioxide.
7. The method for preparing the porous graphene electrode material by utilizing the mulberry stem carbon through pyrolysis activation according to claim 6, wherein superheated steam and carbon dioxide are mixed according to a volume ratio of 1:1, and the carbon powder after chemical activation and the mixed gas are subjected to pressure maintaining under a pressure difference condition for pyrolysis activation air flow conveying.
8. The method for preparing the porous graphene electrode material by utilizing the pyrolysis activation of the mulberry stalk carbon according to claim 6, wherein the superheated steam pressure is 0.5-2.5 MPa, and the temperature is 250-600 ℃.
9. The method for preparing a porous graphene electrode material by utilizing pyrolysis activation of mulberry stalk carbon according to claim 1, wherein in the step (3), the inert protective gas is nitrogen.
10. The method for preparing a porous graphene electrode material by utilizing pyrolysis activation of mulberry stalk carbon according to any one of claims 1 to 9, wherein in the step (3), the pyrolysis activation treatment at a temperature of 500 to 800 ℃ is carried out, and an external electromagnetic heating manner is used for heating a thermal medium in a pyrolysis device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210393471.8A CN114735679A (en) | 2022-04-14 | 2022-04-14 | Method for preparing porous graphene electrode material by utilizing pyrolysis activation of mulberry stem carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210393471.8A CN114735679A (en) | 2022-04-14 | 2022-04-14 | Method for preparing porous graphene electrode material by utilizing pyrolysis activation of mulberry stem carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114735679A true CN114735679A (en) | 2022-07-12 |
Family
ID=82282309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210393471.8A Pending CN114735679A (en) | 2022-04-14 | 2022-04-14 | Method for preparing porous graphene electrode material by utilizing pyrolysis activation of mulberry stem carbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114735679A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723352A (en) * | 2009-11-20 | 2010-06-09 | 上海奥威科技开发有限公司 | Height ratio capacity organic mixed type super capacitor anode material and preparation method thereof |
| CN103824701A (en) * | 2014-03-11 | 2014-05-28 | 中国第一汽车股份有限公司 | Active graphene composite electrode material |
| WO2017181826A1 (en) * | 2016-04-19 | 2017-10-26 | 广西大学 | Method for manufacturing three-dimensional hierarchical porous graphene powder |
| WO2017219943A1 (en) * | 2016-06-20 | 2017-12-28 | 山东欧铂新材料有限公司 | Composite petroleum coke-based activated carbon and preparation method therefor, and supercapacitor |
| CN107758646A (en) * | 2017-11-20 | 2018-03-06 | 华南理工大学 | A kind of method that grapheme material is prepared using bamboo wood leftover bits and pieces |
| CN107848805A (en) * | 2015-05-19 | 2018-03-27 | 建添企业有限公司 | The method that graphene is prepared using coal as raw material |
| CN113307254A (en) * | 2021-06-24 | 2021-08-27 | 武汉科技大学 | Method for preparing three-dimensional porous graphene sheet by using low-temperature double-salt compound and application |
-
2022
- 2022-04-14 CN CN202210393471.8A patent/CN114735679A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723352A (en) * | 2009-11-20 | 2010-06-09 | 上海奥威科技开发有限公司 | Height ratio capacity organic mixed type super capacitor anode material and preparation method thereof |
| CN103824701A (en) * | 2014-03-11 | 2014-05-28 | 中国第一汽车股份有限公司 | Active graphene composite electrode material |
| CN107848805A (en) * | 2015-05-19 | 2018-03-27 | 建添企业有限公司 | The method that graphene is prepared using coal as raw material |
| WO2017181826A1 (en) * | 2016-04-19 | 2017-10-26 | 广西大学 | Method for manufacturing three-dimensional hierarchical porous graphene powder |
| WO2017219943A1 (en) * | 2016-06-20 | 2017-12-28 | 山东欧铂新材料有限公司 | Composite petroleum coke-based activated carbon and preparation method therefor, and supercapacitor |
| CN107758646A (en) * | 2017-11-20 | 2018-03-06 | 华南理工大学 | A kind of method that grapheme material is prepared using bamboo wood leftover bits and pieces |
| CN113307254A (en) * | 2021-06-24 | 2021-08-27 | 武汉科技大学 | Method for preparing three-dimensional porous graphene sheet by using low-temperature double-salt compound and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | A critical review on the application and recent developments of post-modified biochar in supercapacitors | |
| Manasa et al. | Recent progress on biomass waste derived activated carbon electrode materials for supercapacitors applications—A review | |
| Senthil et al. | Biomass-derived biochar materials as sustainable energy sources for electrochemical energy storage devices | |
| Tiwari et al. | Methods for the conversion of biomass waste into value-added carbon nanomaterials: Recent progress and applications | |
| CN113651307B (en) | Sodium ion battery carbon negative electrode material prepared based on waste wood chips and preparation method thereof | |
| Gao et al. | A cross-disciplinary overview of naturally derived materials for electrochemical energy storage | |
| Wang et al. | Rice husk-derived carbon anodes for lithium ion batteries | |
| CN108101051B (en) | Preparation method of seaweed-based activated carbon precursor for supercapacitor | |
| CN111017927A (en) | Preparation and application method of nitrogen-doped porous carbon based on straw hydrothermal carbonization | |
| CN107298441A (en) | A kind of method that use waste biomass material prepares super capacitor material | |
| CN105870422A (en) | C@SiOx material, preparation method thereof and application of C@SiOx material taken as negative electrode material of lithium ion battery | |
| CN112420402B (en) | Nitrogen-doped biochar, preparation method and application thereof, electrode and preparation method | |
| KR101565036B1 (en) | 3D hierachical nanosized activated carbon and method thereof | |
| CN109019598A (en) | A kind of mixing biomass prepares the method and manufactured three-dimensional porous carbon material and its application of the three-dimensional porous carbon material of high specific capacitance | |
| CN106395816A (en) | Method for extracting humic acid from lignite and then using residues to prepare adsorbent | |
| CN114477172A (en) | Preparation method and application of straw-based porous carbon with honeycomb-shaped pore structure | |
| CN108715447A (en) | A kind of camphor tree Quito mesoporous activated carbon and preparation method thereof and the application in electrochemical energy storage | |
| CN108358203B (en) | Preparation method of biomass porous graphene structure activated carbon | |
| CN113149000A (en) | Preparation method of rice husk carbon-based graphitized carbon material | |
| CN102442664A (en) | Production method for bamboo electric double layer capacitor electrode active carbon | |
| CN112194132B (en) | Preparation method and application of iron-modified carbon microsphere/carbon nanosheet composite porous carbon based on moso bamboo hydrothermal carbonization | |
| Li et al. | Solar pyrolysis of algae in molten salt for capacitive carbon preparation | |
| CN106629722A (en) | Preparation method of rice husk/coal asphalt-based porous graphitized carbon nano sheet used for supercapacitors | |
| CN108010749A (en) | A kind of preparation method based on kelp biomass charcoal super capacitor electrode material | |
| CN117106472A (en) | Manufacturing method and comprehensive utilization technology of biomass charcoal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220712 |
|
| RJ01 | Rejection of invention patent application after publication |