CN114835115B - Preparation method and application of active mesophase carbon microspheres - Google Patents
Preparation method and application of active mesophase carbon microspheres Download PDFInfo
- Publication number
- CN114835115B CN114835115B CN202210524213.9A CN202210524213A CN114835115B CN 114835115 B CN114835115 B CN 114835115B CN 202210524213 A CN202210524213 A CN 202210524213A CN 114835115 B CN114835115 B CN 114835115B
- Authority
- CN
- China
- Prior art keywords
- mesocarbon microbeads
- heating
- mesocarbon
- activated
- drying
- 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.)
- Active
Links
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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a preparation method of active mesocarbon microbeads, which comprises the steps of pretreating the mesocarbon microbeads, including intercalation and dilatation, introducing more activators into the mesocarbon microbeads, removing volatile components in the mesocarbon microbeads through heat treatment, and reducing the dosage of the activators; secondly, in the activation stage, besides using an alkaline substance as an activator, a catalyst containing transition metal ions is added, so that the activation efficiency and the activation effect are improved; and finally, in the activation stage, programmed heating and segmented reaction are adopted, hydroxide ions and carbon are reacted to form a-C-OH structure in the first heating period, and-OH gradually leaves in the second heating period along with continuous heating to form a porous structure. The process can improve the reaction efficiency and achieve the purpose of high efficiency and energy saving. Compared with the traditional porous carbon material, the activated mesocarbon microbeads have better volume density and are widely applicable to the fields of energy storage, catalysis, adsorption materials and the like.
Description
Technical Field
The invention relates to the technical field of capacitor electrode materials, in particular to a preparation method of an active mesocarbon microbead and application of the mesocarbon microbead in different fields.
Background
Along with the continuous acceleration of the global industrialization process, the world population is continuously increased, and the traditional fossil energy is irreversibly consumed, so that the problem of serious environmental pollution is caused. Global temperature warming, rising sea level and other problems are more serious than one year, and alternative renewable energy sources are urgently needed to be searched. The emergence of environmentally friendly energy sources such as wind energy, solar energy, nuclear energy, and biological energy has brought a boon to global energy problems, but the supply of energy is limited to natural environments, and therefore it is important to develop clean renewable energy sources and portable energy storage devices to solve the current energy problems.
The super capacitor has the advantages of high power density, high charging/discharging speed, long cycle life, wide working temperature range and the like, and is widely applied to the fields of electronic communication, electric power traffic systems, aerospace and the like. The super capacitor can be divided into a double electric layer super capacitor and a Faraday pseudocapacitor according to an energy storage mechanism, the double electric layer super capacitor mainly stores energy through physical electrostatic absorption/desorption of electrolyte ions, and most of electrode materials are carbon materials.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of active mesocarbon microbeads, and the obtained mesocarbon microbeads have the characteristics of high mesoporosity, high strength coefficient and low expansion coefficient.
The second purpose of the invention is to provide the application of the active mesophase carbon microspheres prepared by the method in the fields of energy storage, catalysis, adsorption materials and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a preparation method of an active mesocarbon microbead, which comprises the following steps:
(1) Pretreating the mesocarbon microbeads;
preferably, the mesophase carbon microspheres are micron-sized spherical carbon materials formed by separating mesophase spherules from an asphalt matrix through a thermal polycondensation reaction to generate anisotropic mesophase spherules when the heat treatment is carried out on the pitch compounds. The mesocarbon microbeads are novel carbon materials and are mainly used as high-end lithium battery negative electrode materials. The mesocarbon microbeads used in the invention have the following physicochemical parameters: the grain diameter D50 is 15-35 mu m, the volatile component is less than 10%, the ash content is 0.1-0.4%, the toluene insoluble substance is more than 95%, and the quinoline insoluble substance is 95-98%.
Preferably, the pre-treatment comprises: sequentially carrying out oxidation intercalation, crushing and heating on the mesocarbon microbeads;
preferably, the oxidation intercalation comprises the steps of dipping the mesocarbon microbeads in concentrated sulfuric acid and then adding hydrogen peroxide. The process aims to solve the problems that the structure of the spherical mesocarbon microbeads is stable, and an activating agent and a catalyst are difficult to enter the materials, so that the traditional alkali activation process needs to adopt excessive activating agent and longer reaction time; the pretreatment process opens the spherical mesocarbon microbeads to form an oxidation intercalation layer, so that the mesocarbon microbeads form a channel for accommodating an activating agent to enter.
Preferably, after the oxidation intercalation is finished, the oxidation intercalation material is cleaned and then crushed into 50-400 meshes, and then heated for 1-8 hours at 100-400 ℃. The crushing aims at improving the contact area of the material, the activator and the catalyst so that the activator permeates into the material crystal lattice; the heating aims to remove the volatile components in the mesocarbon microbeads, reduce the dosage of the activating agent and improve the activating efficiency.
Preferably, the concentration of concentrated sulfuric acid in the oxidation intercalation process is 2-18 mol/L, and the mass of the concentrated sulfuric acid is 10-1000 times of that of the mesocarbon microbeads; the concentration of hydrogen peroxide is 0.10 to 9.79mol/L, and the mass of the hydrogen peroxide is 0.1 to 2 times of that of the mesocarbon microbeads; the immersion time was 2h.
Preferably, the grinding is carried out by adopting a sand grinding or ball milling process, the rotation speed of the sand grinding or ball milling is 50-500 rpm, and the time is 0.5-20 h.
(2) Adding an alkaline substance into the pretreated mesocarbon microbeads, and activating under a heating condition;
preferably, the alkaline substance is used as an activator and is selected from one or more of potassium carbonate, potassium hydroxide, potassium bicarbonate, sodium carbonate, sodium hydroxide and sodium bicarbonate.
Preferably, the mass ratio of the mesocarbon microbeads to the alkaline substances is 5:1-1:5.
Preferably, the pretreated mesocarbon microbeads are mixed with alkaline substances and then ground for 0.5 to 2 hours, and then activated.
Preferably, a catalyst is added during the activation process, the catalyst being a carbonate, nitrate or chloride of a transition metal, in particular cobalt or nickel, such as cobalt carbonate, cobalt nitrate, cobalt chloride, nickel carbonate, nickel nitrate, nickel chloride. Preferably, the mass ratio of the catalyst to the pretreated mesocarbon microbeads is (0.01-0.1): 1. The catalyst has the function of enabling transition metal ions to enter gaps of the graphite layers at high temperature, improving the crystal lattice size and facilitating the penetration of an activating agent for activation reaction, thereby improving the activation efficiency and the activation effect.
Preferably, the heating adopts a segmented temperature programming process. Wherein the first stage of temperature rise: the temperature rise rate is 1-5 ℃/min at the temperature of 0-200 ℃, and the second stage of temperature rise: the temperature rise rate is 3-20 ℃/min at 200-600 ℃, the temperature rise in the third stage is as follows: the heating rate is 1-20 ℃/min at 600-1000 ℃, and the activation is carried out for 3-6 h after the temperature is raised to 600-1000 ℃. The process is programmed heating and segmented reaction, and the programmed heating aims at controlling the reaction rate; in the segmented reaction process, the temperature is raised in the first segment, the activating agent further permeates into the mesocarbon microbead crystal lattice, and the crystal lattice size is continuously increased in the process that the catalyst enters the mesocarbon microbead crystal lattice, so that the pre-reaction of the activating agent and the mesocarbon microbead is promoted; and in the second stage of temperature rise, hydroxyl ions in the activator react with carbon to form a-C-OH structure, and along with the continuous temperature rise, the-OH gradually leaves during the third stage of temperature rise to form a porous structure. The process can improve the reaction efficiency and achieve the purpose of high efficiency and energy saving.
(3) Cleaning and drying the activated mesocarbon microbeads;
preferably, the cleaning comprises: and (3) washing the activated mesocarbon microbeads for 5-6 times by using deionized water, then washing for 2-4 times by using hydrochloric acid with the concentration of 0.1-2 mol/L, and then washing for 5-6 times by using deionized water.
Preferably, the drying comprises: and (3) placing the washed mesocarbon microbeads in a drying box, wherein the drying temperature is 50-150 ℃ and the drying time is 0.5-5 h.
The invention also relates to the application of the mesocarbon microbeads in the fields of energy storage, catalysis and adsorption materials.
The invention has the beneficial effects that:
the invention provides a preparation method of active mesocarbon microbeads, which comprises the steps of firstly pretreating the mesocarbon microbeads, including intercalation and dilatation, introducing more activating agents into the mesocarbon microbeads, and then removing volatile components in the mesocarbon microbeads through heat treatment to reduce the using amount of the activating agents;
secondly, in the activation stage, besides the alkaline substance as an activator, a catalyst containing transition metal ions is added, so that the activator can easily permeate into the mesocarbon microbeads to carry out activation reaction, thereby improving the activation efficiency and the activation effect;
and finally, in the activation stage, programmed heating and segmented reaction are adopted, hydroxide ions and carbon are reacted to form a-C-OH structure in the first heating period, and-OH gradually leaves in the second heating period along with continuous heating to form a porous structure. The process can improve the reaction efficiency and achieve the purpose of high efficiency and energy saving.
The specific surface area of the mesocarbon microbeads prepared by the method can reach 3371.3m 2 The material has the characteristics of high mesoporous rate, high strength coefficient and low expansion coefficient compared with the activated carbon material. The specific capacitance can reach 840F/g, compared with the traditional porous carbon material, the activated mesophase carbon microsphere has better volume density, and is widely applicable to the fields of energy storage, catalysis, adsorption materials and the like.
Drawings
FIG. 1 is a scanning electron micrograph of the unactivated mesophase carbon microspheres of comparative example 1.
FIG. 2 is a scanning electron micrograph of the activated mesocarbon microbeads of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
A preparation method of active mesophase carbon microspheres comprises the following steps:
(1) Pretreating the mesocarbon microbeads: adding 20g of mesocarbon microbeads into 500ml of sulfuric acid with the concentration of 18.3mol/L, mixing and stirring for 2 hours, dropwise adding 100ml of hydrogen peroxide with the concentration of 2mol/L, and reacting for 2 hours after dropwise adding. And (3) cleaning the solid phase substance after the reaction is finished, wherein the solid phase substance is cleaned by adopting excessive distilled water until the pH value is more than 3, and the cleaned sample is dried for later use.
After cleaning and drying, a ball milling process is adopted to crush the mesocarbon microbeads to 200 meshes, and then the mesocarbon microbeads are heated in a drying oven at 180 ℃ for 6 hours. The mesocarbon microbeads used in the embodiment of the invention are produced by Baotailong New Material Co., ltd.
(2) Activating mesocarbon microbeads: mixing the dried potassium hydroxide powder with the pretreated mesocarbon microbeads according to the mass ratio of 3:1, grinding for 2 hours, and gradually adding cobalt nitrate in the grinding process, wherein the mass ratio of the cobalt nitrate to the mesocarbon microbeads is 0.02. And (2) placing the ground sample in a high-temperature furnace, performing activation treatment by adopting a programmed heating mode, wherein the heating rate is 5 ℃/min at 0-200 ℃, the heating rate is 10 ℃/min at 200-600 ℃, the heating rate is 2 ℃/min at 600-1000 ℃, activating for 4 hours after the temperature is raised to 1000 ℃, and cooling the product to room temperature after the reaction is finished.
(3) Cleaning the activated mesocarbon microbead material: and cleaning and drying the activated mesocarbon microbeads. The cleaning comprises the following steps: the cleaning is carried out for 6 times by adopting deionized water, then the cleaning is carried out for 4 times by adopting hydrochloric acid with the concentration of 0.5mol/L, and then the cleaning is carried out for 6 times by adopting the deionized water.
The drying comprises the following steps: and (3) placing the washed mesocarbon microbeads in a drying box, heating to 120 ℃, and drying for 4 hours to obtain the active mesocarbon microbeads.
The following performance tests were carried out on the activated mesocarbon microbeads prepared as described above:
the specific surface area of the solid substance is determined according to the national standard GB/T19587-2004 principle of gas adsorption BET. Using BELSORP MAThe specific surface area of the material is 3371.3m by an X II specific surface area tester 2 /g。
According to the national standard GB/T37386-2019 activated carbon for the super capacitor, a Hiden Analytical/IGA 001 weight analyzer is adopted to determine that the total pore volume of the material is 1.41m 3 Per g, average pore volume of 2.39m 3 The mesopore ratio was 86.67%.
Determining the specific capacitance of the material by cyclic voltammetry, comprising: preparing the activated mesocarbon microbeads and Polytetrafluoroethylene (PTFE) into electrode slices according to the mass ratio of 9:1, forming three electrodes with a platinum electrode and an Hg/HgO electrode, and testing in a 3M KOH solution. The specific capacitance at a current density of 1A/g was 839.7F/g, and at a current density of 10A/g was 679.2F/g.
Example 2
A preparation method of active mesophase carbon microspheres comprises the following steps:
(1) Pretreating the mesocarbon microbeads: adding 20g of mesocarbon microbeads into 500ml of sulfuric acid with the concentration of 15mol/L, mixing and stirring for 2 hours, dropwise adding 150ml of hydrogen peroxide with the concentration of 1mol/L, and reacting for 2 hours after dropwise adding. And (3) cleaning the solid phase substance after the reaction is finished, wherein the solid phase substance is cleaned by adopting excessive distilled water until the pH value is more than 3, and the cleaned sample is dried for later use.
The intermediate phase carbon microspheres are crushed to 100 meshes by adopting a ball milling process and then heated in a drying oven at 200 ℃ for 4 hours.
(2) Mixing the dried sodium hydroxide powder with the pretreated mesocarbon microbeads according to the mass ratio of 5:1, grinding for 2 hours, and gradually adding nickel chloride in the grinding process, wherein the mass ratio of the nickel chloride to the mesocarbon microbeads is 0.05. And (2) placing the ground sample in a high-temperature furnace, activating by adopting a programmed heating mode, heating at 0-200 ℃ at a heating rate of 3 ℃/min, heating at 200-600 ℃ at a heating rate of 5 ℃/min, heating at 600-1000 ℃ at a heating rate of 1 ℃/min, heating to 800 ℃, activating for 5 hours, and cooling the product to room temperature after the reaction is finished.
(3) And cleaning and drying the activated mesocarbon microbeads. The cleaning comprises the following steps: and (3) washing with deionized water for 5 times, then washing with 1mol/L hydrochloric acid for 3 times, and then washing with deionized water for 6 times. The drying comprises the following steps: and (3) placing the washed mesocarbon microbeads in a drying box, heating to 100 ℃, and drying for 5 hours to obtain the active mesocarbon microbeads.
Example 3
A preparation method of active mesophase carbon microspheres comprises the following steps:
(1) Pretreating the mesocarbon microbeads: adding 20g of mesocarbon microbeads into 500ml of 17mol/L sulfuric acid, mixing and stirring for 2 hours, dropwise adding 300ml of 0.5mol/L hydrogen peroxide, and reacting for 2 hours after dropwise addition. And (3) cleaning the solid phase substance after the reaction is finished, wherein the solid phase substance is cleaned by adopting excessive distilled water until the pH value is more than 3, and the cleaned sample is dried for later use.
The intermediate phase carbon microspheres are crushed to 150 meshes by adopting a ball milling process and then heated in a drying oven at 150 ℃ for 5 hours.
(2) Mixing the dried sodium carbonate powder with the pretreated mesocarbon microbeads according to the mass ratio of 1:3, grinding for 2 hours, and gradually adding cobalt carbonate in the grinding process, wherein the mass ratio of the cobalt carbonate to the mesocarbon microbeads is 0.01. And (2) placing the ground sample in a high-temperature furnace, performing activation treatment by adopting a programmed heating mode, wherein the heating rate is 5 ℃/min at the temperature of 0-200 ℃, 10 ℃/min at the temperature of 200-600 ℃, 2 ℃/min at the temperature of 600-1000 ℃, activating for 4 hours after heating to 1000 ℃, and cooling the product to room temperature after the reaction is finished.
(3) And cleaning and drying the activated mesocarbon microbeads. The washing and drying process was the same as in example 1.
Comparative example 1
Step (1) is not subjected to oxidation intercalation treatment, namely: pretreatment the preferable intermediate phase carbon microspheres are ground into 200 meshes by adopting a ball milling process, and then heated in a drying oven at 180 ℃ for 6 hours. The other preparation process is the same as that of example 1.
Comparative example 2
Step (2) no potassium hydroxide powder is added, namely: grinding the pretreated mesocarbon microbeads for 2 hours, gradually adding cobalt nitrate in the grinding process, wherein the mass ratio of the cobalt nitrate to the mesocarbon microbeads is 0.02. The other preparation process is the same as that of example 1.
Comparative example 3
The step (2) does not add cobalt nitrate, namely: mixing the dried potassium hydroxide powder with the pretreated mesocarbon microbeads according to the mass ratio of 3:1, grinding for 2 hours, and then carrying out activation treatment. The other preparation process is the same as that of example 1.
Comparative example 4
The intermediate phase carbon microsphere is not activated.
The activated mesocarbon microbeads obtained in the above examples and comparative examples were subjected to cyclic voltammetry in the same manner as in example 1, and the specific capacitances obtained at a current density of 1A/g and a current density of 10A/g were shown in Table 1.
TABLE 1
As can be seen from the above test data of examples and comparative examples, comparative examples 1 to 3 changed the manufacturing process, and the specific surface area and specific capacitance were reduced compared to those of examples. Comparative example 4 is an unactivated mesocarbon microbead with an extremely low specific surface area and no porous structure.
FIG. 1 is an electron micrograph of mesophase carbon microbeads before activation, corresponding to comparative example 4; FIG. 2 is an electron micrograph of the activated carbon, which corresponds to example 1. It can be seen that the surface appearance of the activated mesocarbon microbeads is greatly changed, the surface is rough and the surface of the microbeads is clustered. The performance characterization result of the material is comprehensively considered, the specific surface area of the activated mesocarbon microbeads is greatly increased, and the material is proved to become a porous material after being treated by the activation process.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A preparation method of active mesocarbon microbeads is characterized by comprising the following steps:
(1) Pretreating the mesocarbon microbeads, sequentially oxidizing, intercalating and crushing the mesocarbon microbeads, heating at 100-400 deg.C for 1-8 hr,
the oxidation intercalation comprises the steps of dipping the mesocarbon microbeads in concentrated sulfuric acid, then adding hydrogen peroxide, wherein,
the concentration of concentrated sulfuric acid is 2-18 mol/L, and the mass of the concentrated sulfuric acid is 10-1000 times of that of the mesocarbon microbeads; the concentration of hydrogen peroxide is 0.10 to 9.79mol/L, and the mass of the hydrogen peroxide is 0.1 to 2 times of that of the mesocarbon microbeads; the dipping time is 2h;
(2) Adding an alkaline substance into the pretreated mesocarbon microbeads, and activating under a heating condition;
the heating adopts a segmented temperature programming process, wherein,
first-stage heating: the temperature rise rate is 1-5 ℃/min at the temperature of 0-200 ℃, and the second stage of temperature rise: the temperature rise rate is 3-20 ℃/min at 200-600 ℃, the temperature rise in the third stage is as follows: the heating rate is 1-20 ℃/min at 600-1000 ℃, and the activation is carried out for 3-6 h after the temperature is raised to 600-1000 ℃;
(3) And cleaning and drying the activated mesocarbon microbeads to obtain the activated mesocarbon microbeads.
2. The method according to claim 1, wherein in the step (1), the mesocarbon microbeads have the following physicochemical parameters: the grain diameter D50 is 15-35 mu m, the volatile component is less than 10%, the ash content is 0.1-0.4%, the toluene insoluble substance is more than 95%, and the quinoline insoluble substance is 95-98%.
3. The method according to claim 1, wherein in the step (1), after the oxidative intercalation is completed, the obtained oxidative intercalation material is washed and crushed to 50-400 mesh, and then heated at 100-400 ℃ for 1-8 hours.
4. The method according to claim 1, wherein in the step (2), the alkaline substance is selected from one or more of potassium carbonate, potassium hydroxide, potassium bicarbonate, sodium carbonate, sodium hydroxide and sodium bicarbonate;
and/or the mass ratio of the mesocarbon microbeads to the alkaline substances is 5:1-1:5.
5. The method according to claim 1, wherein in the step (2), the pretreated mesocarbon microbeads are mixed with the alkaline substance, ground for 0.5 to 2 hours, and then activated.
6. The method according to claim 1, wherein in the step (2), a catalyst is added in the activation process, and the catalyst is selected from one or more of cobalt carbonate, cobalt nitrate, cobalt chloride, nickel carbonate, nickel nitrate and nickel chloride;
and/or the mass ratio of the catalyst to the pretreated mesocarbon microbeads is (0.01-0.1): 1.
7. The method of claim 1, wherein in step (3), the cleaning comprises: washing the activated mesocarbon microbeads with deionized water for 5-6 times, then washing with hydrochloric acid with the concentration of 0.1-2 mol/L for 2-4 times, and then washing with deionized water for 5-6 times;
and/or, the drying comprises: and (3) placing the washed mesocarbon microbeads in a drying box, wherein the drying temperature is 50-150 ℃ and the drying time is 0.5-5 h.
8. The application of the mesocarbon microbeads prepared by the method of any one of claims 1 to 7 in the fields of energy storage, catalysis and adsorption materials.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210524213.9A CN114835115B (en) | 2022-05-13 | 2022-05-13 | Preparation method and application of active mesophase carbon microspheres |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210524213.9A CN114835115B (en) | 2022-05-13 | 2022-05-13 | Preparation method and application of active mesophase carbon microspheres |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114835115A CN114835115A (en) | 2022-08-02 |
CN114835115B true CN114835115B (en) | 2023-03-24 |
Family
ID=82569473
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210524213.9A Active CN114835115B (en) | 2022-05-13 | 2022-05-13 | Preparation method and application of active mesophase carbon microspheres |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114835115B (en) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101393800B (en) * | 2008-10-11 | 2010-12-01 | 广西师范大学 | Electrode material for super capacitor and preparing method thereof |
CN102631915A (en) * | 2011-12-07 | 2012-08-15 | 天津市贝特瑞新能源材料有限责任公司 | Fuel-cell catalyst with intermediate-phase carbon microspheres load Pt (platinum) and preparation method and application of fuel-cell catalyst |
CN104098078B (en) * | 2013-04-07 | 2016-09-28 | 中国科学院长春应用化学研究所 | Activation MCMB, its preparation method and ultracapacitor |
CN104045080A (en) * | 2014-06-27 | 2014-09-17 | 福州大学 | Activated graphene sheet and preparation method thereof |
-
2022
- 2022-05-13 CN CN202210524213.9A patent/CN114835115B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN114835115A (en) | 2022-08-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108483442B (en) | Preparation method of nitrogen-doped carbon electrode material with high mesoporous rate | |
CN105869912B (en) | A kind of preparation method and applications of starch base Monodispersed activated carbon microballon material | |
CN110467182B (en) | Reaction template-based hierarchical porous carbon-based material and preparation method and application thereof | |
CN106914265A (en) | A kind of method for preparing N doping porous nano carbon material as carbon source gel method with biomass | |
CN109133030A (en) | A kind of preparation method and applications of nitrogen-doped porous carbon material | |
Chen et al. | Porous hard carbon spheres derived from biomass for high-performance sodium/potassium-ion batteries | |
CN109678153A (en) | The preparation method and its catalytic applications in fuel battery negative pole of a kind of N doping porous carbon | |
CN107658474A (en) | A kind of nitrogen sulphur codope porous carbon microsphere and preparation method, purposes and oxygen reduction electrode | |
CN110330016A (en) | An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole | |
CN109796003A (en) | A kind of coal base hard carbon Surface Oxygen functional group orientation regulation method for storing up sodium cathode | |
CN109037625A (en) | The composite material of a kind of multi-stage porous carbon and cobalt sulfide, preparation method and lithium sulfur battery anode material and lithium-sulfur cell containing it | |
CN110518245B (en) | Carbon material prepared from water-absorbing resin and application of carbon material in positive electrode of lithium-sulfur battery | |
CN113135568A (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
CN103441246A (en) | Preparation method and application of three-dimensional nitrogen-doped graphene base tin dioxide composite material | |
CN108630911A (en) | A kind of SnO of oxygen-containing vacancy defect2Graphene nanocomposite material and application in room temperature sodium-ion battery cathode | |
CN112265990A (en) | Preparation method and application of furfural residue porous activated carbon material | |
CN114956037A (en) | Carbon material for sodium ion battery negative electrode, preparation method of carbon material, sodium ion battery negative electrode piece and sodium ion battery | |
CN113307254A (en) | Method for preparing three-dimensional porous graphene sheet by using low-temperature double-salt compound and application | |
CN109346732A (en) | A kind of porous C catalyst of N doping and its preparation and application using potato preparation | |
Zhang et al. | Nitrogen and oxygen co-doped carbon micro-foams derived from gelatin as high-performance cathode materials of Zn-ion capacitors | |
CN103964433A (en) | Preparation method of coal-based activated carbon for electrode material of supercapacitor | |
CN113201759B (en) | Three-dimensional porous carbon supported bismuth sulfide/bismuth oxide composite catalyst and preparation method and application thereof | |
CN110534750B (en) | Positive electrode material, preparation method thereof and carbon dioxide battery | |
CN113078327A (en) | Preparation method of carbon aerogel containing bimetallic site and application of aluminum-air battery | |
CN114835115B (en) | Preparation method and application of active mesophase carbon microspheres |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |