CN116102012B - Method for preparing hard carbon anode material by using waste thermosetting plastic - Google Patents
Method for preparing hard carbon anode material by using waste thermosetting plastic Download PDFInfo
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Abstract
The invention discloses a method for preparing a hard carbon anode material by using waste thermosetting plastics, which belongs to the technical field of battery materials and comprises the following steps: crushing waste thermosetting plastics; sequentially carbonizing and activating the crushed waste thermosetting plastics by water vapor to obtain active carbon, and sequentially crushing and jet milling the active carbon to obtain active carbon powder; coating an organic carbon source on the surface of the activated carbon powder by a liquid phase coating method to obtain activated carbon coated by the organic carbon source; carbonizing active carbon coated by an organic carbon source at high temperature to obtain carbonized material; and (3) pickling and drying the carbonized material to obtain the hard carbon anode material. The hard carbon anode material has the characteristics of high initial efficiency and high capacity, and the waste thermosetting plastic is used as the raw material, so that the environmental pressure can be effectively relieved, the problem that the waste plastic pollutes the environment can be effectively solved, and waste materials are changed into valuable materials.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a method for preparing a hard carbon anode material by using waste thermosetting plastics.
Background
Along with the rapid development of renewable energy technology, the demand for a green low-cost electrochemical power supply used in large-scale energy storage equipment is increasingly vigorous, the electrochemical reaction potential of a sodium ion battery is close to that of a lithium ion battery, but the cost of an electrode material is far lower than that of the lithium ion battery, so that the sodium ion battery has very excellent application prospect in the large-scale energy storage equipment; however, the ionic radius (0.102 nm) of sodium ions is much larger than that of lithium ions (0.076 nm), which seriously hinders the application of the intercalation anode material from the viewpoint of dynamics. For example, graphite anode materials used in commercial lithium ion batteries cannot be used in sodium ion batteries because they cannot form thermodynamically stable sodium-graphite intercalation compounds, and therefore, there is a need to find suitable anode materials to meet the application requirements of commercial sodium ion batteries.
In the sodium ion battery cathode material, the hard carbon has the advantages of good conductivity, high sodium storage capacity, small volume deformation after sodium intercalation, environmental friendliness, low oxidation-reduction potential and the like, and is the sodium ion battery cathode material with the most commercial application potential at present. The hard carbon material precursor at the present stage mainly comprises three main types: biomass materials (e.g., wood, starch, hulls, etc.), mineral materials (e.g., humic acid, lignite, anthracite, etc.), and man-made organics (e.g., phenolic resins, epoxy resins, polyacrylonitrile, etc.). The biomass material has the advantages of wide sources, low price and the like, but is influenced by sunlight, rainwater, soil components and the like to cause great difference of tissue structure and element composition, and is not suitable for being used as a large-scale mass production raw material. Mineral feeds are relatively stable, but their capacity to produce hard carbon is generally low. The artificial organic matter has single component and high structural controllability, is favorable for synthesizing the hard carbon material with stable performance, but has higher raw material cost and processing cost, and the novel synthesized artificial organic matter is directly used for preparing the hard carbon material and does not meet the requirement of low cost of the sodium ion battery electrode material.
The structure of waste thermosetting plastic is stable, the waste thermosetting plastic is difficult to recycle, a large amount of discarded thermosetting plastic after use becomes a serious hazard for damaging the environment, and CN114597404 discloses a preparation method of a long-cycle hard carbon negative electrode material of a lithium ion battery, which improves the stability of a hard carbon structure by oxidizing a resin precursor, ensures sufficient strength of particles in a long-cycle process, reduces the electrochemical activity specific surface area of the material by liquid phase coating, and further improves the first coulombic efficiency and long-cycle dynamics performance of the hard carbon material. The method is characterized in that mixed gas is formed by introducing oxygen-containing gas, under the condition of the mixed gas, the hard carbon resin precursor is subjected to oxidation treatment in a dynamic heat treatment process, oxygen atoms are inserted into molecular chain segments of the hard carbon resin precursor, the space structure of molecular chain winding is expanded, the thermal stability of powder is improved, solid-phase carbonization is carried out at high temperature, the structural strength and the residual carbon value of a hard carbon material are improved, and the preparation method is complex, uncontrollable in process and unfavorable for industrial production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing a hard carbon anode material by using waste thermosetting plastics, by taking waste thermosetting plastics as raw materials, the environmental pressure can be effectively relieved, and the hard carbon negative electrode material has the characteristics of high first efficiency and high capacity.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A method for preparing a hard carbon anode material by using waste thermosetting plastics comprises the following steps:
Crushing waste thermosetting plastics;
Sequentially carbonizing and activating the crushed waste thermosetting plastics by water vapor to obtain active carbon, and sequentially crushing and jet milling the active carbon to obtain active carbon powder;
Coating an organic carbon source on the surface of the activated carbon powder by a liquid phase coating method to obtain activated carbon coated by the organic carbon source;
carbonizing active carbon coated by an organic carbon source at high temperature to obtain carbonized material;
And (3) pickling and drying the carbonized material to obtain the hard carbon anode material.
According to the invention, waste thermosetting plastic is used as a raw material, the waste thermosetting plastic is carbonized, an organic high polymer material is converted into a carbon material, then the carbon material reacts with water vapor (C+H 2O→CO+H2) at high temperature, the purpose of activating and pore-forming is achieved, the closed pore volume in the carbon material can be accurately regulated and controlled through the water vapor flow and the reaction time, the purpose of regulating and controlling the capacity of a hard carbon material is achieved, the size of the carbon material is controlled through crushing and air flow grinding refining, the specific surface area of the hard carbon is reduced through organic carbon source cladding and high-temperature carbonization, and the high-efficiency and high-capacity hard carbon anode material is prepared through acid washing.
The invention takes the waste thermosetting plastic as the raw material, can effectively relieve the environmental pressure, and effectively solve the problem that the waste plastic pollutes the environment, thereby changing waste into valuable.
It should be noted that the liquid phase coating method is a coating method conventional in the art, and may be implemented by a hydrothermal method, a precipitation method, a sol-gel method, or an electroless plating method. In the present invention, a hydrothermal method is preferably used, that is, in the present invention, a preferred liquid phase coating method is: and uniformly mixing the activated carbon powder with an organic carbon source, placing the mixture in a solvent, stirring and evaporating to dryness to obtain the activated carbon coated with the organic carbon source.
As a preferred embodiment of the invention, the waste thermosetting plastic comprises at least one of waste phenolic resin plastic, waste urea-formaldehyde plastic, waste epoxy resin plastic and waste polyimide plastic. When the waste plastics are adopted, the hard carbon anode material with high first efficiency and high capacity can be prepared.
As a preferred embodiment of the invention, the waste thermosetting plastic is crushed to a particle size <5mm.
As a preferred embodiment of the present invention, the carbonization temperature is 600 to 800 ℃ and the carbonization time is1 to 3 hours. Carbonization is carried out at the temperature and the time, so that the conversion of the organic polymer material into the carbon material can be effectively promoted.
As a preferred embodiment of the invention, the water vapor activation temperature is 600-1000 ℃, the activation time is 1-6 h, and the flow rate of the water vapor is 50-90 g/min. At the temperature, time and flow rate, the purpose of activating and pore-forming is achieved, and the closed pore volume inside the carbon material can be accurately regulated and controlled through the water vapor flow and the reaction time.
As a preferred embodiment of the invention, the water vapor activation temperature is 600-800 ℃, the activation time is 3-5 h, and the flow rate of the water vapor is 60-80 g/min. Particularly, under the temperature, time and flow rate, the pore-forming effect is better, and the closed pore volume in the carbon material is better.
The carbonization and the steam activation are carried out in a carbonization and activation furnace under the protection of inert atmosphere.
As a preferred embodiment of the invention, the crushing is to a particle size <2mm.
As a preferred embodiment of the present invention, the air stream is pulverized to have a particle size of Dv50 of 8 to 12. Mu.m, dv10 of 1 to 4. Mu.m, and Dv99 of 25 to 30. Mu.m.
As a preferred embodiment of the present invention, the organic carbon source includes at least one of phenolic resin, epoxy resin, citric acid, glucose, and citric acid, and the mass ratio of the organic carbon source to activated carbon powder is 1: 8-15.
As a preferred embodiment of the present invention, the mass ratio of the organic carbon source to the activated carbon powder is 1: 8-10.
As a preferred embodiment of the present invention, the organic carbon source phenolic resin and epoxy resin. The specific surface area of the hard carbon is reduced by coating the organic carbon source, so that the first effect and the capacity are improved.
As a preferred embodiment of the invention, the high-temperature carbonization temperature is 1200-1600 ℃, the high-temperature carbonization time is 1-3 h, and the heating rate is 5-10 ℃/min. The specific surface area of the hard carbon is reduced by high-temperature carbonization, so that the first effect and the capacity are improved.
As a preferred embodiment of the present invention, the pickling solution is a sulfuric acid solution of 3 to 5 mol/L.
The invention has the beneficial effects that: according to the invention, waste thermosetting plastic is used as a raw material, the waste thermosetting plastic is carbonized, an organic high polymer material is converted into a carbon material, then the carbon material reacts with water vapor (C+H 2O→CO+H2) at high temperature, the purpose of activating and pore-forming is achieved, the closed pore volume in the carbon material can be accurately regulated and controlled through the water vapor flow and the reaction time, the purpose of regulating and controlling the capacity of a hard carbon material is achieved, the size of the carbon material is controlled through crushing and air flow grinding refining, the specific surface area of the hard carbon is reduced through organic carbon source cladding and high-temperature carbonization, and the high-efficiency and high-capacity hard carbon anode material is prepared through acid washing.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specific dispersing and stirring treatment method in the present invention is not particularly limited.
The reagents or apparatus used in the present invention are conventional products commercially available without the manufacturer's knowledge.
Example 1
A method for preparing a hard carbon anode material by using waste thermosetting plastics comprises the following steps:
(1) Crushing waste phenolic resin plastic in a plastic crusher to a particle size of less than 5mm;
(2) Placing 10kg of crushed waste phenolic resin plastic into a carbonization and activation furnace, carbonizing for 2 hours at 600 ℃ under nitrogen atmosphere, then introducing water vapor at 800 ℃ for activation for 4 hours, wherein the water vapor flow is 70g/min, cooling to room temperature after the reaction is completed to obtain activated carbon, crushing the activated carbon to a particle size of <2mm by using a roller machine, and refining the crushed activated carbon to a Dv50 of 8 mu m, a Dv10 of 3 mu m and a Dv99 of 25 mu m by using an air flow mill to obtain activated carbon powder;
(3) Uniformly mixing active carbon powder and phenolic resin according to a mass ratio of 10:1 to obtain mixed powder, then placing the mixed powder into alcohol (the mass ratio of the mixed powder to the alcohol is 1:3), stirring at 60 ℃ and evaporating the alcohol to obtain the active carbon coated by an organic carbon source;
(4) Placing active carbon coated by an organic carbon source in a graphite sagger, heating to 1500 ℃ at a speed of 5 ℃/min under the protection of nitrogen, preserving heat for 2 hours, and cooling to room temperature to obtain carbonized material;
(5) And (3) placing the carbonized material into a 3mol/L H 2SO4 solution for reaction for 3 hours, carrying out acid washing, carrying out suction filtration and washing until filtrate is neutral after the reaction is finished, obtaining an acid washing product, and finally, baking the acid washing product in an oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Example 2
Example 2 differs from example 1 in that the steam flow of example 2 is 60g/min, all other things being equal.
Example 3
Example 3 differs from example 1 in that the steam flow of example 3 is 50g/min, all other things being equal.
Example 4
Example 4 differs from example 1 in that the steam flow of example 4 is 80g/min, all other things being equal.
Example 5
Example 5 differs from example 1 in that the steam flow of example 5 is 90g/min, all other things being equal.
Example 6
Example 6 differs from example 1 in that the water vapor activation time of example 6 is 1h, all other things being equal.
Example 7
Example 7 differs from example 1 in that the water vapor activation time of example 7 is 6h, all other things being equal.
Example 8
Example 8 differs from example 1 in that the steam activation temperature of example 8 is 600 ℃, all other things being equal.
Example 9
Example 9 differs from example 1 in that the steam activation temperature of example 9 is 1000 ℃, all other things being equal.
Example 10
Example 10 differs from example 1 in that the mass ratio of activated carbon powder to phenolic resin in example 10 is 8:1, all others being identical.
Example 11
Example 11 differs from example 1 in that the mass ratio of activated carbon powder to phenolic resin in example 11 is 15:1, all others being identical.
Example 12
Example 12 differs from example 1 in that acetone is used in place of alcohol in example 12, all of which are identical.
Example 13
Example 13 differs from example 1 in that water is used instead of alcohol in example 13, all of which are identical.
Example 14
Example 14 differs from example 1 in that example 14 uses glucose instead of phenolic resin and water instead of alcohol during coating, all of which are identical.
Example 15
Example 15 differs from example 1 in that example 15 uses waste urea formaldehyde plastic instead of waste phenolic resin, all of which are identical.
Example 16
Example 16 differs from example 1 in that example 16 uses waste epoxy resin plastic instead of waste phenolic resin, all of which are identical.
Example 17
Example 17 differs from example 1 in that example 17 uses waste polyimide plastic instead of waste phenolic resin, all of which are identical.
Comparative example 1
Comparative example 1 differs from example 1 in that comparative example 1 was not subjected to the water vapor activation treatment, and all other things were the same.
A method for preparing a hard carbon anode material by using waste thermosetting plastics comprises the following steps:
(1) Crushing waste phenolic resin in a plastic crusher until the particle size is less than 5mm;
(2) Placing 10kg of crushed waste phenolic resin plastic in a graphite sagger, heating to 1500 ℃ at 5 ℃/min under the protection of nitrogen, keeping the temperature for 2 hours, cooling to room temperature to obtain high-temperature carbonized material, crushing the high-temperature carbonized material to a particle size of <2mm by using a roller, and refining the crushed activated carbon to have a Dv50 of 8 mu m, a Dv10 of 3 mu m and a Dv99 of 25 mu m by using an air flow mill to obtain activated carbon powder;
(3) Uniformly mixing active carbon powder and phenolic resin according to a mass ratio of 10:1 to obtain mixed powder, then placing the mixed powder into alcohol (the mass ratio of the mixed powder to the alcohol is 1:3), stirring at 60 ℃ and evaporating the alcohol to obtain the active carbon coated by an organic carbon source;
(4) Placing active carbon coated by an organic carbon source in a graphite sagger, heating to 1500 ℃ at a speed of 5 ℃/min under the protection of nitrogen, preserving heat for 2 hours, and cooling to room temperature to obtain carbonized material;
(5) And (3) placing the carbonized material into a 3mol/L H 2SO4 solution for reaction for 3 hours, carrying out acid washing, carrying out suction filtration and washing until filtrate is neutral after the reaction is finished, obtaining an acid washing product, and finally, baking the acid washing product in an oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Comparative example 2
Comparative example 2 is different from example 1 in that comparative example 2 is not subjected to the liquid phase coating treatment, and all other are the same.
A method for preparing a hard carbon anode material by using waste thermosetting plastics comprises the following steps:
(1) Crushing waste phenolic resin in a plastic crusher until the particle size is less than 5mm;
(2) Placing 10kg of crushed waste phenolic resin plastic into a carbonization and activation furnace, carbonizing for 2 hours at 600 ℃ under nitrogen atmosphere, then introducing water vapor at 800 ℃ for activation for 4 hours, wherein the water vapor flow is 70g/min, cooling to room temperature after the reaction is completed to obtain activated carbon, crushing the activated carbon to a particle size of <2mm by using a roller machine, and refining the crushed activated carbon to a Dv50 of 8 mu m, a Dv10 of 3 mu m and a Dv99 of 25 mu m by using an air flow mill to obtain activated carbon powder;
(3) Placing activated carbon powder into a graphite sagger, heating to 1500 ℃ at a speed of 5 ℃/min under the protection of nitrogen, preserving heat for 2 hours, and cooling to room temperature to obtain carbonized material;
(4) And (3) placing the carbonized material into a 3mol/L H 2SO4 solution for reaction for 3 hours, carrying out acid washing, carrying out suction filtration and washing until filtrate is neutral after the reaction is finished, obtaining an acid washing product, and finally, baking the acid washing product in an oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Comparative example 3
Comparative example 3 is different from example 1 in that comparative example 3 is not subjected to high temperature carbonization treatment, and all other things are the same.
A method for preparing a hard carbon anode material by using waste thermosetting plastics comprises the following steps:
(1) Crushing waste phenolic resin in a plastic crusher until the particle size is less than 5mm;
(2) Placing 10kg of crushed waste phenolic resin plastic into a carbonization and activation furnace, carbonizing for 2 hours at 600 ℃ under nitrogen atmosphere, then introducing water vapor at 800 ℃ for activation for 4 hours, wherein the water vapor flow is 70g/min, cooling to room temperature after the reaction is completed to obtain activated carbon, crushing the activated carbon to a particle size of <2mm by using a roller machine, and refining the crushed activated carbon to a Dv50 of 8 mu m, a Dv10 of 3 mu m and a Dv99 of 25 mu m by using an air flow mill to obtain activated carbon powder;
(3) Uniformly mixing active carbon powder and phenolic resin according to a mass ratio of 10:1 to obtain mixed powder, then placing the mixed powder into alcohol (the mass ratio of the mixed powder to the alcohol is 1:3), stirring at 60 ℃ and evaporating the alcohol to obtain the active carbon coated by an organic carbon source;
(4) And (3) placing the activated carbon coated by the organic carbon source into a 3mol/L H 2SO4 solution for reaction for 3 hours, carrying out acid washing, carrying out suction filtration and washing until filtrate is neutral after the reaction is finished, obtaining an acid washing product, and finally, baking the acid washing product in an oven at 80 ℃ for 12 hours, and drying to obtain the hard carbon anode material.
Test case
1. The specific surface areas of the activated carbons prepared in examples 1 to 9 and 15 to 17 are shown in Table 1, wherein the specific surface areas were measured by a specific surface area meter.
TABLE 1
As can be seen from comparative examples 1 to 5, the specific surface area of the activated carbon increases with the increase of the water vapor flow rate during the activation; comparative examples 1, 6 and 7 show that the specific surface area of activated carbon increases with the increase of the activation time, and comparative examples 1, 8 and 9 show that the specific surface area of activated carbon increases with the increase of the activation temperature.
2. The specific surface area, the true density and the closed cell volume density of the hard carbon of examples 1 to 17 and comparative examples 1 to 6 are shown in table 2, wherein the specific surface area is measured by a specific surface area measuring instrument, the true density is measured by a true density measuring instrument, and the calculation formula of the closed cell volume density is: closed cell bulk density= (1/true density) - (1/2.26).
TABLE 2
As can be seen from table 2, it is seen from table 2 that the specific surface area of the material is significantly reduced by liquid phase coating and high temperature carbonization, and the larger the specific surface area of the activated carbon is, the larger the specific surface area of the corresponding hard carbon product is, and from examples 1, 10 and 11, the larger the ratio of activated carbon to organic carbon source is, the larger the specific surface area of the corresponding hard carbon product is, and the specific surface areas of examples 13 and 14 are larger than examples 1 and 12, which indicates that the coating effect of the small molecules is not as good as that of the large polymer; examples 15-17 show that the method has positive effects in improving the closed cell bulk density of hard carbon prepared from other waste thermosetting plastics.
3. And (5) testing electrochemical performance.
Table 3 shows the electrochemical performance of the examples and comparative examples, using button cells for the electrochemical performance test. The working electrode is prepared by uniformly mixing active substances, conductive carbon and sodium carboxymethylcellulose in deionized water according to a mass ratio of 95:2:3, then coating the mixture on a copper foil, wherein a sodium foil is used as a counter electrode, naClO 4 with an electrolyte of 1mol/L is dissolved in an EC/PC (volume ratio of 1:1) mixed solvent, 5wt% of FEC is added, a glass fiber is used as a diaphragm, the assembly of a button cell is carried out in a glove box with oxygen and water content of less than 1ppm, and the electrochemical performance test of the cell is carried out on an electrochemical workstation. The test voltage is 0.01-2.0V and the current density is 30mA g-1.
TABLE 3 Table 3
As can be seen from table 3, examples 1 to 9 show that the larger the specific surface area of the activated carbon obtained after activation, the higher the specific capacity of the corresponding hard carbon at the first discharge, but the lower the first coulombic efficiency, examples 1, 10, 11 show that the larger the ratio of the activated carbon to the organic carbon source, the lower the first coulombic efficiency of the corresponding hard carbon product, examples 1, 12, 13, 14 show that the first coulombic efficiency of the hard carbon obtained by coating small molecules is lower than the first coulombic efficiency of the hard carbon obtained by coating large molecules, and therefore, in the present invention, in order to obtain a hard carbon anode material with high first efficiency and high capacity, it is necessary to control the water vapor activation temperature to be 600 to 800 ℃, the activation time to be 3 to 5 hours, and the flow rate of the water vapor to be 60 to 80g/min; and controlling the mass ratio of the organic carbon source to the activated carbon powder to be 1: 8-10, and adopting phenolic resin or epoxy resin as a coating agent; if other water vapor activation temperatures, activation times, flow rates, and other ratios of organic carbon source to activated carbon powder and other coating agents are used, either the initial coulombic efficiency is low or the specific discharge capacity is low.
Examples 15-17 show that the method has positive effects on improving the first discharge specific capacity and the first coulombic efficiency of hard carbon prepared from other waste thermosetting plastics.
As can be seen from comparative example 1 and comparative example 1, the hard carbon negative electrode material prepared without the water vapor activation treatment has a significantly improved true density although the specific surface area is further reduced, a significantly reduced closed cell volume density, and a significantly reduced first discharge specific capacitance although having a relatively good first coulombic efficiency, which is not satisfactory.
As is clear from comparative examples 1 and 2, the liquid phase coating was not performed, resulting in a significant decrease in both the first discharge specific capacitance and the first coulombic efficiency.
As is clear from comparative examples 1 and 3, the liquid phase coating does not undergo high temperature carbonization treatment, which results in a significant decrease in both the first discharge specific capacitance and the first coulombic efficiency.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The method for preparing the hard carbon anode material by using the waste thermosetting plastic is characterized by comprising the following steps of:
Crushing waste thermosetting plastics;
Sequentially carbonizing and activating the crushed waste thermosetting plastics by water vapor to obtain active carbon, and sequentially crushing and jet milling the active carbon to obtain active carbon powder;
Coating an organic carbon source on the surface of the activated carbon powder by a liquid phase coating method to obtain activated carbon coated by the organic carbon source;
carbonizing active carbon coated by an organic carbon source at high temperature to obtain carbonized material;
acid washing and drying the carbonized material to obtain a hard carbon anode material;
The water vapor activation temperature is 600-1000 ℃, the activation time is 1-6 h, and the flow rate of the water vapor is 50-90 g/min.
2. The method for preparing a hard carbon negative electrode material by using waste thermosetting plastics according to claim 1, wherein the waste thermosetting plastics comprise at least one of waste phenolic resin plastics, waste urea-formaldehyde plastics, waste epoxy resin plastics and waste polyimide plastics.
3. The method for preparing a hard carbon negative electrode material by using waste thermosetting plastics according to claim 1, wherein the waste thermosetting plastics are crushed to a particle size of <5mm.
4. The method for preparing the hard carbon anode material by utilizing the waste thermosetting plastic, which is disclosed in claim 1, is characterized in that the carbonization temperature is 600-800 ℃ and the carbonization time is 1-3 h.
5. The method for preparing a hard carbon negative electrode material by using waste thermosetting plastic according to claim 1, wherein the crushing is performed until the particle size is <2mm.
6. The method for preparing the hard carbon anode material by utilizing the waste thermosetting plastic, which is disclosed in claim 1, is characterized in that the air flow grinding is performed until the particle size Dv50 is 8-12 mu m, the Dv10 is 1-4 mu m and the Dv99 is 25-30 mu m.
7. The method for preparing a hard carbon negative electrode material by using waste thermosetting plastics according to claim 1, wherein the organic carbon source comprises at least one of phenolic resin, epoxy resin, citric acid, glucose and citric acid, and the mass ratio of the organic carbon source to activated carbon powder is 1: 8-15.
8. The method for preparing the hard carbon anode material by utilizing the waste thermosetting plastic, which is disclosed in claim 1, is characterized in that the high-temperature carbonization temperature is 1200-1600 ℃, the high-temperature carbonization time is 1-3 h, and the heating rate is 5-10 ℃/min.
9. The method for preparing the hard carbon anode material by utilizing the waste thermosetting plastic, which is disclosed in claim 1, is characterized in that the pickling solution is sulfuric acid solution with the concentration of 3-5 mol/L.
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| CN202310010877.8A CN116102012B (en) | 2023-01-03 | 2023-01-03 | Method for preparing hard carbon anode material by using waste thermosetting plastic |
| PCT/CN2023/080858 WO2024145994A1 (en) | 2023-01-03 | 2023-03-10 | Method for preparing hard carbon negative electrode material from waste thermosetting plastic |
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| CN118790980B (en) * | 2024-09-13 | 2024-12-13 | 山东埃尔派粉体科技股份有限公司 | Preparation method and application of biomass hard carbon material and precursor thereof |
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| CN111293295A (en) * | 2020-01-13 | 2020-06-16 | 宁夏博尔特科技有限公司 | Electrode material for waste rubber material-based secondary battery and preparation method thereof |
| CN114639809A (en) * | 2022-03-18 | 2022-06-17 | 上海电力大学 | A composite hard carbon negative electrode material, preparation method and application |
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| CN104098095A (en) * | 2013-04-11 | 2014-10-15 | 济南圣泉集团股份有限公司 | Method for preparing active carbon from phenolic foam wastes |
| CN104310392B (en) * | 2014-09-28 | 2016-08-24 | 大连理工大学 | A kind of preparation method of porous carbon material |
| CN108231423A (en) * | 2017-12-08 | 2018-06-29 | 上海奥威科技开发有限公司 | Lithium-ion capacitor negative material particle and preparation method thereof |
| CN108963254B (en) * | 2018-09-18 | 2020-07-07 | 杭州致德新材料有限公司 | Hard carbon negative electrode material and preparation method thereof |
| CN111564630B (en) * | 2020-06-09 | 2021-10-15 | 厦门理工学院 | A kind of hard carbon material and preparation method thereof |
| CN115249799A (en) * | 2022-07-12 | 2022-10-28 | 广东凯金新能源科技股份有限公司 | Rosin-based nitrogen doping coated hard carbon anode material for sodium ion battery and preparation method thereof |
| CN115207320A (en) * | 2022-08-11 | 2022-10-18 | 多氟多新材料股份有限公司 | A kind of preparation method of lithium/sodium ion battery negative electrode material |
| CN115084531B (en) * | 2022-08-19 | 2022-11-15 | 溧阳紫宸新材料科技有限公司 | Method for generating carbon coating layer on surface of hard carbon material, carbon coating material and application |
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