CN116514102A - Method for preparing carbon material based on failure activated carbon and application of method - Google Patents

Method for preparing carbon material based on failure activated carbon and application of method Download PDF

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CN116514102A
CN116514102A CN202310542121.8A CN202310542121A CN116514102A CN 116514102 A CN116514102 A CN 116514102A CN 202310542121 A CN202310542121 A CN 202310542121A CN 116514102 A CN116514102 A CN 116514102A
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carbon
acid
activated carbon
temperature
converter
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胡建森
骆雪尧
方国鸿
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Ningguo Fuxing New Material Technology Co ltd
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Ningguo Fuxing New Material Technology Co ltd
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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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a method for preparing a carbon material based on invalid activated carbon and application thereof, at least comprising the following steps: pretreatment of raw materials: crushing the raw materials, screening, taking 500-100 mesh particles, washing and purifying by low-temperature acid washing, and drying until the water content is below 5 (wt.)%; mixing: mixing the dried raw materials with a micromolecular carbon source material by using a mechanical or ball milling mode; and (3) heat treatment: adding the mixed materials into a converter, simultaneously introducing protective gas into the converter, heating the converter to 100-500 ℃ at a heating rate of 1-20 ℃/min, keeping the temperature for 0.2-4h, heating the converter to 1100-1600 ℃ at a heating rate of 1-20 ℃/min, and keeping the temperature for 0.5-10h, wherein the addition amount of the raw materials is not more than 30% of the volume of the converter. The invention takes industrial solid waste-invalid active carbon as raw material to prepare the high-value sodium ion battery hard carbon anode material, thereby bringing objective economic benefit to enterprises, responding to the call of national sustainable development and protecting the environment.

Description

Method for preparing carbon material based on failure activated carbon and application of method
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a method for preparing a carbon material based on invalid activated carbon and application thereof.
Background
The sodium ion battery has the advantages of abundant reserves, wide distribution, low industrialization cost and the like, and has great advantages in the fields of energy storage, low-speed electric vehicles, electric ships and the like. The commercial sodium ion battery cathode material is a hard carbon material, has more micropore structures inside, is favorable for intercalation and deintercalation of sodium ions, and has good structural stability and high reversible capacity. However, the existing preparation of the high-performance hard carbon anode material mostly uses biomass or polymer as raw materials, and objective factors such as complex process, low carbon yield, higher cost and the like increase the cost of the sodium ion battery.
Activated carbon is a commodity with higher value and is applied to various aspects of industrial and agricultural production. The waste active carbon is mainly from the processes of adsorption decolorization and purification treatment in the synthesis of organic chemicals in industrial enterprises, adsorption decolorization of industrial wastewater and adsorption separation of toxic pollutants, advanced treatment of sewage, adsorption purification treatment of organic waste gas and the like. At present, waste activated carbon serving as hazardous waste is generally disposed by adopting an incineration-solidification-safe landfill process, so that the cost is high, the resource waste is caused, and a high-value treatment method for the waste activated carbon is needed.
In view of the above, the invention provides a method for preparing a carbon material based on a failed activated carbon, and the carbon material prepared by the method is used as a negative electrode material of a sodium ion battery. The invention utilizes the self micropore structure in the active carbon to improve the sodium storage capacity of the hard carbon negative electrode, realizes the high-value recycling of the ineffective active carbon, reduces the resource waste, protects the environment and avoids the environmental pollution; the preparation method of the invention has the advantages of high carbon yield, low cost and the like, and is favorable for further reducing the preparation cost of the sodium ion battery.
Disclosure of Invention
The invention aims to provide a method for preparing a carbon material by using invalid activated carbon and application of the carbon material as a negative electrode material of a sodium ion battery. The invention takes the invalid active carbon as the raw material, and prepares the carbon material through the processes of crushing, screening, washing and purifying by low-temperature acid, mixing with a micromolecular carbon source, heat treatment and the like. The original abundant nano pore structure of the ineffective active carbon is fully utilized in the preparation process, and the pore structure of the active carbon is secondarily regulated and controlled by utilizing a small molecular carbon source so as to improve the sodium storage capacity. The prepared carbon material has abundant pore structures inside, so that sufficient sodium storage sites can be provided, and the specific capacity is further improved; after the pore structure is regulated and controlled by the micromolecular carbon source, the specific surface area of the carbon material in the nitrogen adsorption test is obviously reduced, which is favorable for reducing the decomposition of the electrolyte so as to improve the first coulomb efficiency.
Specifically, the invention firstly provides a method for preparing a carbon material based on invalid activated carbon, which comprises the following steps:
firstly, raw material pretreatment: crushing the raw materials, screening, taking particles below 500 meshes, washing and purifying by low-temperature acid washing, and drying until the water content is below 5 (wt.)%;
secondly, mixing: mixing the dried raw materials with a micromolecular carbon source material by using a mechanical or ball milling mode;
third, heat treatment: adding the mixed materials into a converter, simultaneously introducing protective gas into the converter, heating the mixed materials to the melting temperature of a micromolecular carbon source material at a heating rate of not more than 20 ℃/min, and preserving heat for a period of time to realize infiltration of the porous carbon internal pore structure, wherein the addition amount of the raw materials is not more than 30% of the volume of the converter; heating to above 1100 ℃ at a heating rate of not higher than 20 ℃/min, and preserving heat for a period of time, so that the regulation and control of the porous carbon structure are realized;
fourth, cooling: after reacting for a period of time at constant temperature, cooling to room temperature at a certain cooling rate under a protective atmosphere;
fifth, fine crushing and classification: the obtained material is finely divided and classified.
Preferably, in the first step, the raw material is a spent activated carbon, including one or a mixture of a plurality of coal-based activated carbon, biomass-based activated carbon, asphalt-based activated carbon, resin-based activated carbon and other high polymer-based activated carbon.
Preferably, in the first step, the size of the crushed raw material particles is 500-100 mesh particles. The invention discovers that the gram capacity, the cycle life times and the first charge and discharge efficiency performance of the obtained carbon anode material are more excellent by adopting the raw materials with the particle size range.
Preferably, in the first step, the concentration of acid in the low-temperature acid washing purification treatment is 8% -95%.
Preferably, in the first step, the acid in the low-temperature acid washing purification treatment comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, hypochlorous acid, oxalic acid, sulfurous acid, nitrous acid, perchloric acid, hydroiodic acid and hydrobromic acid.
Preferably, in the first step, the mass of the acid used in the low-temperature acid washing purification treatment is 0.2 to 25 times of the mass of the raw material.
Preferably, in the first step, the reaction time of the acid solution and the raw materials in the low-temperature pickling purification treatment is 0.2-20 h.
Preferably, in the first step, deionized water is added for repeated washing after the pickling is finished in the low-temperature pickling purification treatment until the pH value of the slurry is 6-8;
preferably, in the first step, the solution temperature in the low-temperature acid washing purification treatment is preferably 0-32 ℃, and in the second step, the small molecule carbon source material is one or more of glucose, sucrose, fructose, citric acid, dopamine, vitamin C and perylene tetracarboxylic dianhydride (PTCDA); adding a small molecular carbon source material and a carbon material in a mass ratio of 0.1-8: 1, a step of;
preferably, in the third step, the shielding gas is at least one of argon, nitrogen, hydrogen and helium, and the flow rate of the shielding gas is 1-1000mL/min.
Preferably, in the third step, the temperature rising rate is 1-20 ℃/min.
Preferably, in the third step, the temperature is raised to 100-500 ℃ for 0.2-4 hours when the melting temperature of the micromolecular carbon source material is raised.
Preferably, in the third step, the temperature is raised to 1100-1600 ℃ for 0.5-10 hours.
Preferably, in the fourth step, the cooling rate is 0.1-20 ℃/min.
The invention also provides a carbon anode material which is prepared by the preparation method.
Preferably, the carbon material is characterized in that the carbon material has a D50 of 4-16 μm and a D100 of less than 160 μm; the specific surface area of the hard carbon anode material obtained by 77K nitrogen isothermal adsorption test is not more than 9m 2 /g; a specific surface area of 700-3900m as measured by small angle X-ray scattering 2 Per gram, tap density is not less than 0.82g/cm 3 。
The invention further provides a sodium ion battery, wherein the negative electrode of the sodium ion battery comprises the carbon negative electrode material or the carbon negative electrode material prepared by the preparation method.
Preferably, in the present invention, the positive electrode active material of the sodium ion battery may be at least one of a transition metal layered oxide, a polyanion compound, prussian blue, prussian white, and the like.
Preferably, in the present invention, the negative electrode of the sodium ion battery includes a negative electrode active material, a conductive agent, a binder, and the like, wherein the negative electrode active material is the carbon material in the present invention; the conductive agent can be at least one of SUPER-P, KS-6, conductive graphite, carbon nanotube, graphene, carbon fiber VGCF, acetylene black, ketjen black, etc.; the adhesive may be at least one of PVDF, CMC, SBR, PTFE, SA, PAA, PAN and the like.
Preferably, in the present invention, the electrolyte solution of the sodium ion battery contains electrolyte sodium salt and an organic solvent, wherein the electrolyte sodium salt is sodium hexafluorophosphate (NaPF 6 ) Sodium perchlorate (NaClO) 4 ) Sodium tetrafluoroborate (NaBF) 4 ) Sodium bis (fluorosulfonyl) imide (Na [ (FSO) 2 ) 2 N]NaFSI), sodium triflate (NaSO) 3 CF 3 NaOTf), sodium bis (trifluoromethylsulfonyl) imide (Na [ (CF) 3 SO 2 ) 2 N]Naffsi) one or more of the following; the organic solvent is one or more selected from the group consisting of ethylene glycol dimethyl ether (DME), ethylene Carbonate (EC), propylene Carbonate (PC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC) and diethyl carbonate (DEC). The electrolyte comprises organic solvent and sodium salt, wherein the organic solvent can be EC/PC and DMC, DEC, EAt least one of MC, EA, etc.; the sodium salt may be NaClO 4 、NaPF 6 、NaBF 4 At least one of NaFSI, naffsi, etc.
Advantageous effects of the invention
The invention takes industrial solid waste-invalid active carbon as raw material to prepare the high-value sodium ion battery hard carbon anode material, thereby bringing objective economic benefit to enterprises, responding to the call of national sustainable development and protecting the environment.
The carbon material prepared based on the invalid activated carbon has rich nano-pore structure, and the specific surface area of the material obtained based on 77K nitrogen adsorption test is lower than 9m 2 And/g. The pore structure of the ineffective active carbon is modulated by utilizing the micromolecular carbon source material, so that the prepared carbon material has rich pore structure, and further sufficient sodium storage sites are provided to improve the specific capacity of the carbon negative electrode material; meanwhile, the specific surface area of the carbon material subjected to pore-adjusting nitrogen adsorption test is low, so that the decomposition of the electrolyte is reduced, and the first coulomb efficiency is improved. The reversible discharge capacity of the carbon anode material prepared by the invention is higher than 320mAh/g, and the initial coulomb efficiency is not lower than 85%.
The raw materials used by the carbon anode material prepared by the invention have low price, mature preparation procedures and equipment, high carbon yield and suitability for mass production.
Drawings
The present invention and its advantageous technical effects will be described in detail below with reference to the accompanying drawings and detailed description.
Fig. 1 is a Transmission Electron Microscope (TEM) image of a carbon material in example 1 of the present invention.
FIG. 2 is a graph showing the adsorption and desorption of nitrogen (77K) from the carbon material in example 1 of the present invention.
Fig. 3 is a graph showing the small angle X-ray scattering curve in example 1 of the present invention.
Fig. 4 is a raman diagram of a carbon material in example 1 of the present invention.
Fig. 5 is an X-ray diffraction chart of the carbon material in example 1 of the present invention.
Fig. 6 is a half cell first-turn charge-discharge curve of the carbon negative electrode material in example 1 of the present invention.
Fig. 7 is a full-cell first-turn charge-discharge curve of the carbon anode material in example 1 of the present invention.
Detailed Description
The following specific examples are given to illustrate the technical aspects of the present invention, but the scope of the present invention is not limited thereto.
Example 1
The embodiment firstly provides a preparation method of a hard carbon anode material.
(1) Pretreatment of raw materials: crushing and screening the invalid coal-based activated carbon, taking 400-200 mesh particles, treating the raw material particles by using hydrochloric acid with the concentration of 8%, wherein the addition amount of the hydrochloric acid is 1.5 times of the mass of the raw material particles, repeatedly washing with clear water after 3.5 hours of reaction until the pH value of the liquid is 6.8, and drying the material until the water content of the material is 2 (wt.)%;
(2) Mixing: uniformly mixing 1kg of dried material with 1kg of glucose by using a mechanical mixing mode;
(3) And (3) heat treatment: adding the mixed materials into a converter, simultaneously adding nitrogen into the converter, controlling the flow rate of the nitrogen to be 200mL/min, heating the mixed materials to the glucose melting temperature of 146 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 2 hours, wherein the added amount is not more than 30% of the volume of the converter; then heating to the temperature of 1250 ℃ above the pore-regulating temperature at the heating rate of 5 ℃/min, and preserving heat for 5 hours;
(4) And (3) cooling: after the hole adjustment is finished, controlling the nitrogen flow to be 200mL/min, and cooling to room temperature at a cooling rate of 10 ℃/min;
(5) Finely crushing and classifying: the obtained material is finely divided and classified.
The embodiment also provides a carbon anode material, which is prepared by the method, has the particle size distribution of 5-35 mu m and the D50 particle size of 8.2 mu m. When the material is used as a negative electrode material of a sodium ion battery, the first-circle reversible discharge capacity reaches 416mAh/g, the first coulomb efficiency reaches 85%, and after 1600 weeks of circulation, the specific capacity still keeps 87%.
The embodiment also provides a sodium ion battery, which comprises a positive electrode, a negative electrode and electrolyte. The positive electrode material is sodium vanadium phosphate and the negative electrodeThe material is the carbon anode material, and the electrolyte is NaClO with the concentration of 1mol/L 4 The Ethylene Carbonate (EC)/dimethyl carbonate (DEC) solution is electrolyte (molar volume ratio of EC to DMC is 1:1), and fluoroethylene carbonate (FEC) is electrolyte additive (molar ratio of FEC to EC+DMC is 1:20).
TEM image of sodium ion battery hard carbon negative electrode material provided in example 1. As shown in fig. 2, it can be seen that: the carbon sheet layer of the prepared sodium ion battery anode material presents a short-range ordered state and a long-range disordered state, and a large number of micropores exist. The dispersed diffraction rings were hazy, indicating that the material had broken graphite-like crystallites.
The nitrogen (77K) adsorption and desorption curves of the hard carbon anode material of the sodium ion battery provided in example 1 are shown in fig. 3, and it can be seen that: the specific surface area of the prepared sodium ion battery anode material is about 5.6m 2 /g。
The small-angle X-ray scattering curve of the hard carbon anode material of the sodium ion battery provided in example 1 is shown in FIG. 4, and the specific surface area is 1298m 2 And/g, the inside of the porous membrane is rich in nano pore channels.
The first-turn charge-discharge curve of the hard carbon negative electrode material of the sodium ion battery provided in example 1 is shown in fig. 5, and it can be seen that: the prepared hard carbon negative electrode material of the sodium ion battery has the first coulomb efficiency of up to 85 percent, the reversible specific capacity of up to 416mAh/g, and the specific capacity of a low potential platform is 300mAh/g.
Example 2
Unlike example 1, the following is:
the raw material of the first step is dead biomass-based active carbon, 400-300 mesh particles are taken after crushing and screening, sulfuric acid with the concentration of 14% is used for carrying out acid washing reaction for 4.5 hours, wherein the adding amount of sulfuric acid is 1.8 times of the mass of the raw material of the particles, and then clear water is repeatedly used for washing until the pH value of liquid is 6.9. The water content of the dried material is 1.5 (wt.)%; the small molecular carbon source material mixed in the second step is sucrose, and the adding amount is 1.2kg. In the third step of heat treatment, firstly, heating to the sucrose melting temperature of 190 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours; then heating to 1450 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5 hours; the remainder is the same as in example 1 and will not be described again here.
The embodiment also provides a carbon anode material, which is prepared by the method, has the particle size distribution of 6-34 mu m and the D50 particle size of 9.2 mu m. When the material is used as a negative electrode material of a sodium ion battery, the first-circle reversible discharge capacity reaches 342mAh/g, the first coulomb efficiency reaches 87%, and the specific capacity still maintains 90% after 1600 weeks of circulation.
The embodiment also provides a sodium ion battery, which comprises a positive electrode, a negative electrode and electrolyte. The positive electrode material is Prussian white analogues, the negative electrode material is the carbon negative electrode material, and the electrolyte is NaPF with the concentration of 1mol/L 6 The Ethylene Carbonate (EC)/dimethyl carbonate (DEC) solution is electrolyte (molar volume ratio of EC to DMC is 1:1), and fluoroethylene carbonate (FEC) is electrolyte additive (molar ratio of FEC to EC+DMC is 1:20).
Example 3
Unlike example 1, the following is:
the raw material of the first step is ineffective asphalt-based active carbon, 500-300 meshes of particles are taken after crushing and screening, nitric acid with the concentration of 16% is used for pickling for 4.2 hours, wherein the adding amount of nitric acid is 1.2 times of the mass of the raw material of the particles, and then clear water is repeatedly used for cleaning until the pH value of liquid is 6.8. The water content of the dried material is 1.4 (wt.)%; the small molecular carbon source material mixed in the second step is fructose, and the adding amount is 1.6kg. In the third step of heat treatment, firstly, heating to the fructose melting temperature of 110 ℃ at a heating rate of 3 ℃/min, and preserving heat for 3 hours; heating to 1380 ℃ at a heating rate of 2 ℃/min, and preserving heat for 6 hours; the remainder is the same as in example 1 and will not be described again here.
The embodiment also provides a carbon anode material, which is prepared by the method, has the particle size distribution of 3-28 mu m and the D50 particle size of 7.3 mu m. When the material is used as a negative electrode material of a sodium ion battery, the first-circle reversible discharge capacity reaches 346mAh/g, the first coulomb efficiency reaches 87%, and the specific capacity still maintains 90% after 1600 weeks of circulation.
The embodiment also provides a sodium ion battery, which comprises a positive electrode, a negative electrode and electrolyte. The positive electrode material is sodium vanadium fluorophosphate, the negative electrode material is the hard carbon negative electrode material, and the electrolyte is 1mol/LNaPF 6 The Ethylene Carbonate (EC)/dimethyl carbonate (DEC) solution is electrolyte (molar volume ratio of EC to DMC is 1:1), and fluoroethylene carbonate (FEC) is electrolyte additive (molar ratio of FEC to EC+DMC is 1:20).
Example 4
Unlike example 1, the following is:
the raw material of the first step is failure resin-based active carbon, 400-300 mesh particles are taken after crushing and screening, hydrochloric acid with the concentration of 10% is used for carrying out acid washing reaction for 5 hours, wherein the adding amount of hydrochloric acid is 1.2 times of the mass of the raw material of the particles, and then clear water is repeatedly used for washing until the pH value of liquid is 6.8. The water content of the dried material is 1.1 (wt.)%; the small molecular carbon source material mixed in the second step is perylene tetracarboxylic dianhydride, and the addition amount is 1.6kg. In the third step of heat treatment, firstly, heating to 420 ℃ of the melting temperature of the perylene tetracarboxylic dianhydride at a heating rate of 3 ℃/min, and preserving heat for 3 hours; then heating to 1450 ℃ at a heating rate of 2 ℃/min, and preserving heat for 6 hours; the remainder is the same as in example 1 and will not be described again here.
The embodiment also provides a carbon anode material, which is prepared by the method, has the particle size distribution of 4-32 mu m and the D50 particle size of 8.2 mu m. When the material is used as a negative electrode material of a sodium ion battery, the first-circle reversible discharge capacity reaches 355mAh/g, the first coulomb efficiency reaches 87%, and the specific capacity still maintains 90% after 1600 weeks of circulation.
The embodiment also provides a sodium ion battery, which comprises a positive electrode, a negative electrode and electrolyte. The positive electrode material is sodium vanadium fluorophosphate, the negative electrode material is the hard carbon negative electrode material, and the electrolyte is NaClO with the concentration of 1mol/L 4 The Ethylene Carbonate (EC)/dimethyl carbonate (DEC) solution is electrolyte (molar volume ratio of EC to DMC is 1:1), and fluoroethylene carbonate (FEC) is electrolyte additive (molar ratio of FEC to EC+DMC is 1:20).
Table 1: examples 1-4 test results.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.

Claims (13)

1. A method for preparing a carbon material based on spent activated carbon, comprising at least the steps of:
firstly, raw material pretreatment: crushing the raw materials, screening, taking 500-100 mesh particles, washing and purifying by low-temperature acid washing, and drying until the water content is below 5 (wt.)%;
secondly, mixing: mixing the dried raw materials with a micromolecular carbon source material by using a mechanical or ball milling mode;
third, heat treatment: adding the mixed materials into a converter, simultaneously introducing protective gas into the converter, heating the converter to 100-500 ℃ at a heating rate of 1-20 ℃/min, keeping the temperature for 0.2-4h, heating the converter to 1100-1600 ℃ at a heating rate of 1-20 ℃/min, and keeping the temperature for 0.5-10h, wherein the addition amount of the raw materials is not more than 30% of the volume of the converter;
fourth, cooling: after reacting for a period of time at constant temperature, cooling to room temperature at a certain cooling rate under a protective atmosphere;
fifth, fine crushing and classification: the obtained material is finely divided and classified.
2. The method of claim 1, wherein the activated carbon comprises one or more of coal-based activated carbon, biomass-based activated carbon, pitch-based activated carbon, resin-based activated carbon, and other polymer-based activated carbon.
3. The method for producing a carbon material based on a spent activated carbon according to claim 1, wherein the concentration of the acid during the low-temperature acid washing and water washing purification treatment in the first step is 5% to 85%.
4. The method for producing a carbon material based on spent activated carbon according to claim 1, wherein the acid in the low-temperature acid washing and water washing purification treatment in the first step comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, hypochlorous acid, oxalic acid, sulfurous acid, nitrous acid, perchloric acid, hydroiodic acid, hydrobromic acid.
5. The method for preparing a carbon material based on a spent activated carbon according to claim 1, wherein the mass of the acid used in the low-temperature acid washing and water washing purification treatment in the first step is 0.5 to 25 times the mass of the raw material, and the reaction time is 0.5 to 24 hours.
6. The method for preparing carbon materials based on ineffective activated carbon as claimed in claim 1, wherein in the first step, deionized water is added for repeated washing after the pickling is completed until the pH of the slurry is 6-8.
7. The method for producing a carbon material based on a spent activated carbon according to claim 1, wherein the solution temperature in the low-temperature acid washing and water washing purification treatment in the first step is 0 to 38 ℃.
8. The method for preparing carbon material based on spent activated carbon according to claim 1, wherein the small molecule carbon source material in the second step is one or more of glucose, sucrose, fructose, citric acid, dopamine, vitamin C, perylene tetracarboxylic dianhydride (PTCDA); adding a small molecular carbon source material and a carbon material in a mass ratio of 0.1-8: 1.
9. the method for preparing a carbon material based on the failed activated carbon according to claim 1, wherein the shielding gas is at least one of argon, nitrogen, hydrogen and helium, and the flow rate of the shielding gas is 1-1000mL/min.
10. The method for preparing a carbon material based on deactivated activated carbon according to claim 1, wherein in the third step, the cooling rate is 0.1-20 ℃/min.
11. A carbon material, characterized in that it is produced by the production method according to any one of claims 1 to 10, the D50 of which is 4 to 16 μm and D100 is less than 160 μm; the specific surface area of the hard carbon anode material obtained by 77K nitrogen isothermal adsorption test is not more than 9m 2 /g; a specific surface area of 700-3900m as measured by small angle X-ray scattering 2 Per gram, tap density is not less than 0.82g/cm 3 。
12. The sodium ion battery is characterized by comprising a positive pole piece, a negative pole piece, an isolating film arranged between the positive pole piece and the negative pole piece and electrolyte; the negative electrode plate comprises a negative electrode current collector and negative electrode slurry arranged on the negative electrode current collector; the negative electrode slurry includes: the hard carbon negative electrode material according to any one of claims 11 and 12, a conductive agent, a binder, and a solvent.
13. The sodium ion battery of claim 12, wherein the electrolyte comprises an electrolyte sodium salt and an organic solvent, wherein the electrolyte sodium salt is sodium hexafluorophosphate (NaPF 6 ) Sodium perchlorate (NaClO) 4 ) Sodium tetrafluoroborate (NaBF) 4 ) Sodium bis (fluorosulfonyl) imide (Na [ (FSO) 2 ) 2 N]NaFSI), sodium triflate (NaSO) 3 CF 3 NaOTf), sodium bis (trifluoromethylsulfonyl) imide (Na [ (CF) 3 SO 2 ) 2 N]Naffsi) one or more of the following; the organic solvent is one or more selected from the group consisting of ethylene glycol dimethyl ether (DME), ethylene Carbonate (EC), propylene Carbonate (PC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC) and diethyl carbonate (DEC).
CN202310542121.8A 2023-05-12 2023-05-12 Method for preparing carbon material based on failure activated carbon and application of method Pending CN116514102A (en)

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CN118005003A (en) * 2024-04-09 2024-05-10 成都锂能科技有限公司 Ultra-micro porous hard carbon material and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118005003A (en) * 2024-04-09 2024-05-10 成都锂能科技有限公司 Ultra-micro porous hard carbon material and preparation method and application thereof
CN118005003B (en) * 2024-04-09 2024-06-18 成都锂能科技有限公司 Ultra-micro porous hard carbon material and preparation method and application thereof

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