CN109524736B - Method for recovering graphite in waste battery and application thereof - Google Patents

Method for recovering graphite in waste battery and application thereof Download PDF

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CN109524736B
CN109524736B CN201811237243.1A CN201811237243A CN109524736B CN 109524736 B CN109524736 B CN 109524736B CN 201811237243 A CN201811237243 A CN 201811237243A CN 109524736 B CN109524736 B CN 109524736B
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graphite
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temperature
coating
carbon
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CN109524736A (en
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马锐
苗立孝
李现化
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Sander New Energy Technology Development Co ltd
Soundon New Energy Technology Co Ltd
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Soundon New Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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Abstract

The invention provides a method for recovering graphite in waste batteries and application thereof, relating to the field of battery recovery, and the method for recovering graphite in waste batteries comprises the following steps: s1) acid washing and purifying: providing graphite slag generated in waste battery recovery as a recovery raw material, and then carrying out acid washing to remove impurities to obtain primarily purified graphite; s2) removing the cracked carbon; s3) coating and carbonizing: and coating the graphite subjected to secondary purification by using a carbon source material which is heated and decomposed into carbon, and then carbonizing the coating layer to obtain the graphite material. By utilizing the recovery method, the technical problems of large specific surface area, poor processing performance and low battery first-time efficiency when the graphite material recovered by the conventional graphite recovery method is used as a negative electrode material can be solved.

Description

Method for recovering graphite in waste battery and application thereof
Technical Field
The invention relates to the field of battery recovery, in particular to a method for recovering graphite in waste batteries and application thereof.
Background
In recent years, as the country vigorously pushes new energy automobiles and energy storage markets, the output of lithium ion batteries is rapidly increased. However, the lithium ion batteries put on the market in large quantities inevitably cause the problem of recycling after the end of the battery life. The discard amount of the lithium ion battery in 2016 of China is about 5 to 8 tons, and the discard amount is estimated to reach 12 to 17 ten thousand tons by 2020. The reported waste lithium ion battery contains a large amount of scarce nonferrous metals such as cobalt, nickel, manganese, copper, aluminum and the like and toxic and harmful substances such as lithium hexafluorophosphate, carbonates and the like, and serious environmental pollution and resource waste can be caused if the battery is not recycled. Therefore, the method has great significance for resource recovery and harmless treatment, and can realize certain economic benefit.
After the waste lithium ion battery is subjected to the steps of crushing, sorting, pyrolysis, acid washing and the like, metals such as cobalt, nickel, manganese, lithium, copper, aluminum and the like with higher economic value are preferentially extracted, and the rest is slag mainly containing graphite. The method is difficult to solve the problem that the cathode recovery technology is immature, and a part of recovery factories directly bury or burn the residual graphite slag, so that the environment is polluted and the resource is greatly wasted. If the graphite in the slag can be recycled, not only can the graphite resource be saved, but also the maximum recovery benefit can be realized. At present, some recycling manufacturers can recycle graphite slag to obtain a graphite material again, but when the obtained graphite material is used as a negative electrode of a lithium ion battery, the first efficiency of the graphite material is lower than that of the graphite material used for the first time.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The core of the invention is that according to the existing graphite recovery process, a certain amount of cracked carbon is generated after pyrolysis of the scrapped lithium ion battery, but the part of cracked carbon cannot be effectively removed in the oxidation process in the existing graphite recovery process, and the incomplete removal of the cracked carbon causes the overlarge specific surface area (generally 3-5 m) of the recovered graphite material2The concentration of the graphite is lower than that of the graphite, and the graphite is easy to agglomerate and not easy to disperse in the pulping process, so that the processing performance of the graphite is influenced; in addition, since the surface area of graphite is large, when it is used as a negative electrode material, excessive lithium ions are inserted and consumed in the first charge and discharge process, thereby reducing the first efficiency of the battery.
The first purpose of the invention is to provide a method for recovering graphite from waste batteries, so as to relieve the technical problems of large specific surface area, poor processability and low battery first-time efficiency when the graphite material recovered by the conventional graphite recovery method is used as a negative electrode material.
The second purpose of the present invention is to provide a use of the above recovery method in waste battery recovery, so as to effectively recover the negative electrode material in the waste battery.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method for recovering graphite in waste batteries comprises the following steps:
s1) acid washing and purifying: providing graphite slag generated in waste battery recovery as a recovery raw material, and then carrying out acid washing to remove impurities to obtain primarily purified graphite;
s2) removing cracked carbon: placing the primarily purified graphite in a reaction kettle, and oxidizing at 350-640 ℃, wherein the stirring speed in the oxidation process is 10-100 r/min, the air flow rate is 1-50L/min, and the heat preservation time is 1-6 h, so as to obtain secondarily purified graphite;
s3) coating and carbonizing: and coating the graphite subjected to secondary purification by using a carbon source material which is heated and decomposed into carbon, and then carbonizing the coating layer to obtain the graphite material.
Further, in step S1), the graphite slag is acid-washed with hydrofluoric acid, wherein the concentration of the hydrofluoric acid is 0.1-2 mol/L.
Furthermore, the mass ratio of the graphite slag to the hydrofluoric acid is 1 (5-50), and the reaction time in the acid washing process is 1.5-2.5 h.
Further, in the step S2), the temperature rise rate of the reaction kettle is 1-10 ℃/min.
Further, in the step S3), the carbon source material is asphalt, and the softening point of the asphalt is 230-300 ℃.
Further, adding the asphalt and the graphite subjected to secondary purification into a mixer for mixing to complete the coating of the graphite;
wherein the adding amount of the asphalt is 1-20% of the weight of the graphite.
Furthermore, the carbonization temperature in the carbonization process is 900-1200 ℃, and the carbonization time is 1-5 h.
The recycling method is applied to recycling of waste batteries.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for recovering graphite from waste batteries, which comprises the steps of removing metal impurities in graphite slag by acid washing, oxidizing at a specific temperature, a specific stirring speed, a specific air flow rate and a specific heat preservation time to completely remove cracked carbon in the graphite, and finally coating and carbonizing to obtain a recovered graphite material. By using the method, the cracked carbon in the graphite slag can be fully contacted with the air so as to completely remove the cracked carbon in the graphite slag; meanwhile, the oxidation reaction can be controlled in the reaction region of the cracking carbon by accurately controlling the oxidation temperature and the air flow, so that excessive oxidation of graphite is avoided.
The graphite material obtained by the recovery method has a small specific surface area (generally 1-2 m)2The graphite slurry is not easy to agglomerate and is easy to disperse in the pulping process, so that the graphite slurry with better performance can be obtained; in addition, since the specific surface area is reduced, less conductive ions are consumed during the first charge and discharge of the battery, and thus the first efficiency of the battery can be improved.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
On one hand, the invention provides a method for recovering graphite in waste batteries, which comprises the following steps:
s1) acid washing and purifying: providing graphite slag generated in waste battery recovery as a recovery raw material, and then carrying out acid washing to remove impurities to obtain primarily purified graphite;
s2) removing cracked carbon: placing the primarily purified graphite in a reaction kettle, and oxidizing at 350-640 ℃, wherein the stirring speed in the oxidation process is 10-100 r/min, the air flow rate is 1-50L/min, and the heat preservation time is 1-6 h, so as to obtain secondarily purified graphite;
s3) coating and carbonizing: and coating the graphite subjected to secondary purification by using a carbon source material which is heated and decomposed into carbon, and then carbonizing the coating layer to obtain the graphite material.
The invention provides a method for recovering graphite from waste batteries, which comprises the steps of removing metal impurities in graphite slag by acid washing, oxidizing at a specific temperature, a specific stirring speed, a specific air flow rate and a specific heat preservation time to completely remove cracked carbon in the graphite, and finally coating and carbonizing to obtain a recovered graphite material. By using the method, the cracked carbon in the graphite slag can be fully contacted with the air so as to completely remove the cracked carbon in the graphite slag; meanwhile, the oxidation reaction can be controlled in the reaction region of the cracking carbon by accurately controlling the oxidation temperature and the air flow, so that excessive oxidation of graphite is avoided.
The graphite material obtained by the recovery method has a small specific surface area (generally 1-2 m)2The graphite slurry is not easy to agglomerate and is easy to disperse in the pulping process, so that the graphite slurry with better performance can be obtained; in addition, since the specific surface area is reduced, less conductive ions are consumed during the first charge and discharge of the battery, and thus the first efficiency of the battery can be improved.
Because a small amount of metal impurities exist in the graphite slag, the metal impurities in the graphite slag can be effectively removed by utilizing an acid washing method. In the present invention, the acid solution used in the acid washing process may be, for example, hydrofluoric acid, hydrochloric acid, or sulfuric acid.
In the present invention, the oxidation temperature in the oxidation process for removing the cracked carbon may be, for example, 350 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, 620 ℃ or 640 ℃; the stirring rate may be typically, but not limited to, for example, 10r/min, 15r/min, 20r/min, 25r/min, 30r/min, 35r/min, 40r/min, 45r/min, 50r/min, 55r/min, 60r/min, 65r/min, 70r/min, 75r/min, 80r/min, 85r/min, 90r/min, 95r/min or 100 r/min; the air flow rate may be, for example, typically but not by way of limitation, 1L/min, 5L/min, 10L/min, 15L/min, 20L/min, 25L/min, 30L/min, 35L/min, 40L/min, 45L/min, or 50L/min; typical but non-limiting incubation times may be, for example, 1h, 2h, 3h, 4h, 5h or 6 h.
In the recovery method of the present invention, the carbon source material that is decomposed by heating to carbon may be, for example, pitch, phenol resin, epoxy resin, urea resin, or furan resin.
In some embodiments of the invention, in step S1), the graphite slag is acid-washed with hydrofluoric acid, and the concentration of the hydrofluoric acid is 0.1-2 mol/L.
The inventor of the invention finds that some silicate inorganic minerals are inevitably introduced in the transferring, recovering and transferring processes of the waste batteries, so that the hydrofluoric acid is selected to carry out acid washing on the graphite slag, and not only can metal impurities be removed, but also inorganic mineral impurities such as silicate and the like can be removed. In this embodiment, the concentration of hydrofluoric acid may be, for example, 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.7mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.7mol/L, or 2 mol/L.
In some embodiments of the invention, the mass ratio of the graphite slag to the hydrofluoric acid is 1 (5-50), and the reaction time of the acid cleaning process is 1.5-2.5 h. By limiting the mass ratio and the reaction time of the graphite slag and the hydrofluoric acid, the acid cleaning effect can be improved, and non-carbon impurities in the graphite slag can be further removed. In this embodiment, the mass ratio of the graphite slag to the hydrofluoric acid may be, for example, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, or 1: 50; the reaction time in the acid washing process may be, for example, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2.0h, 2.1h, 2.2h, 2.3h, 2.4h or 2.5 h.
In some embodiments of the invention, in step S2), the temperature increase rate of the reaction kettle is 1 to 10 ℃/min. The reation kettle intensifies temperature and mainly relies on the electric plate heating of reation kettle outer wall, and the heat passes through the powder transmission of solid phase in the cauldron, if the programming rate too fast can lead to local overheat, easily causes the thermal runaway, and the intensification can reduce production efficiency too slowly.
In the embodiment, the graphite treated in the step S1) is added into a high-temperature stirring reaction kettle, the stirring speed is controlled to be 10-100 r/min, air is continuously introduced, the air flow rate is 1-50L/min, and the temperature is increased to the temperature: keeping the temperature at 350-650 ℃ for 1-6 h. Strictly monitoring the temperature in the kettle in the reaction process, immediately closing the air inlet and the air outlet after the temperature exceeds a set value by 5-10 ℃, and stopping heating; after the reaction is finished, continuously stirring and cooling to room temperature, and then discharging.
In some embodiments of the invention, in step S3), the carbon source material is asphalt, and the softening point of the asphalt is 230 to 300 ℃. The asphalt with the softening point is selected, so that in the carbonization process, small molecules are less volatilized, the surface of the obtained coating layer cannot form too many air holes, the coating layer is uniform and smooth, the coating effect is good, and the first efficiency of the battery taking the graphite obtained by recycling as the negative electrode can be further improved. The softening point of the asphalt may be, for example, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃ or 300 ℃.
In some embodiments of the invention, the pitch and the graphite after the secondary purification are added into a mixer to be mixed, and the coating of the graphite is completed;
wherein the adding amount of the asphalt is 1 to 20 percent of the weight of the graphite.
In the above embodiment, the specific weight of the asphalt is added to the graphite, and the asphalt coating layer is formed on the surface of the graphite by mixing, which is simple and easy to implement, and can form a uniform asphalt coating layer on the surface of the graphite.
In some embodiments of the present invention, the carbonization temperature during the carbonization process is 900 to 1200 ℃, and the carbonization time is 1 to 5 hours. The carbonization process is facilitated to carry out carbonization, so that the asphalt can be completely carbonized, and forms an integral structure with the graphite, thereby perfecting the surface defects of the graphite and improving the surface performance of the graphite material.
In a second aspect of the invention, there is provided the use of the above recovery method in the recovery of spent batteries.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
The embodiment is a method for recovering graphite in waste batteries, which comprises the following steps:
s1) putting the recovered 1kg of graphite slag into an acid washing reactor, adding 5L of hydrofluoric acid solution with the concentration of 2mol/L, continuously stirring, reacting for 2h, filtering the slurry in the acid washing reactor, washing the slurry to be neutral by deionized water, and then putting filter residues into an oven for drying;
s2) taking 4kg of filter residue dried in the step S1), putting the filter residue into a 15L high-temperature stirring reaction kettle, adjusting the stirring speed to be 100r/min, introducing air, controlling the air flow rate to be 50L/min, simultaneously heating to 450 ℃ at the speed of 10 ℃/min, and carrying out heat preservation reaction for 2h at 450 ℃; strictly monitoring the temperature in the kettle in the reaction process, immediately closing the air inlet and the air outlet after the temperature exceeds a set value by 10 ℃, and simultaneously stopping heating; after the reaction is finished, continuously stirring, and discharging after the temperature is reduced to room temperature to obtain purified graphite;
s3) adding 1kg of purified graphite and 100g of asphalt with the softening point of 260 ℃ into a 3L high-speed mixer, and mixing for 20 min; then putting the mixture into a high-temperature furnace for high-temperature carbonization, wherein the temperature rise rate during carbonization is 3 ℃/min, the carbonization temperature is 1100 ℃, and the temperature is kept for 2 h; and cooling and sieving to obtain the regenerated graphite material.
Comparative example 1
The comparative example is a method for recovering graphite in waste batteries, and comprises the following steps:
s1) putting 1kg of recovered graphite slag into an acid washing reactor, adding 5L of hydrofluoric acid solution with the concentration of 2mol/L, continuously stirring, reacting for 2h, filtering slurry in the acid washing reactor, washing with deionized water to be neutral, and then putting filter residues into an oven for drying;
s2) taking 4kg of filter residue dried in the step S1), placing the filter residue into a sagger, placing the sagger into a muffle furnace, introducing air, controlling the air flow rate to be 50L/min, simultaneously heating to 450 ℃ at the speed of 10 ℃/min, preserving the heat at 450 ℃ for 2h, cooling along with the furnace after the reaction is finished, and discharging to obtain purified graphite;
s3) adding 1kg of purified graphite and 100g of asphalt with the softening point of 260 ℃ into a 3L high-speed mixer, and mixing for 20 min; then putting the mixture into a high-temperature furnace for high-temperature carbonization, wherein the temperature rise rate during carbonization is 3 ℃/min, the carbonization temperature is 1100 ℃, and the temperature is kept for 2 h; and cooling and sieving to obtain the regenerated graphite material.
Example 2
The embodiment is a method for recovering graphite in waste batteries, which comprises the following steps:
s1) putting the recovered 1kg of graphite slag into an acid washing reactor, adding 20L of hydrofluoric acid solution with the concentration of 1mol/L, continuously stirring, reacting for 2 hours, filtering the slurry in the acid washing reactor, washing the slurry to be neutral by deionized water, and then putting filter residues into an oven for drying;
s2) taking 4kg of filter residue dried in the step S1), putting the filter residue into a 15L high-temperature stirring reaction kettle, adjusting the stirring speed to be 50r/min, introducing air, controlling the air flow rate to be 20L/min, simultaneously heating to 500 ℃ at the speed of 3 ℃/min, and carrying out heat preservation reaction for 2h at 500 ℃; strictly monitoring the temperature in the kettle in the reaction process, immediately closing the air inlet and the air outlet after the temperature exceeds a set value by 5 ℃, and simultaneously stopping heating; after the reaction is finished, continuously stirring, and discharging after the temperature is reduced to room temperature to obtain purified graphite;
s3) adding 1kg of purified graphite and 50g of asphalt with the softening point of 280 ℃ into a 3L high-speed mixer, and mixing for 20 min; then putting the mixture into a high-temperature furnace for high-temperature carbonization and carbonization, wherein the heating rate is 3 ℃/min, the carbonization temperature is 1200 ℃, and the temperature is kept for 1 h; and cooling and sieving to obtain the regenerated graphite material.
Example 3
The embodiment is a method for recovering graphite in waste batteries, which comprises the following steps:
s1) putting 1kg of recovered graphite slag into an acid washing reactor, adding 20L of mixed solution of 0.5mol/L sulfuric acid and 0.5mol/L hydrogen peroxide solution, continuously stirring, reacting for 2h, filtering slurry in the acid washing reactor, washing with deionized water to be neutral, and then putting filter residues into an oven for drying;
s2) taking 4kg of filter residue dried in the step S1), putting the filter residue into a 15L high-temperature stirring reaction kettle, adjusting the stirring speed to be 50r/min, introducing air, controlling the air flow rate to be 20L/min, simultaneously heating to 500 ℃ at the speed of 3 ℃/min, and carrying out heat preservation reaction for 2h at 500 ℃. Strictly monitoring the temperature in the kettle in the reaction process, immediately closing the air inlet and the air outlet after the temperature exceeds a set value by 5 ℃, and simultaneously stopping heating; after the reaction is finished, continuously stirring, and discharging after the temperature is reduced to room temperature to obtain purified graphite;
s3) adding 1kg of purified graphite and 50g of asphalt with the softening point of 280 ℃ into a 3L high-speed mixer, and mixing for 20 min; then putting the mixture into a high-temperature furnace for high-temperature carbonization, wherein the temperature rise rate during carbonization is 3 ℃/min, the carbonization temperature is 1200 ℃, and the temperature is kept for 1 h; and cooling and sieving to obtain the regenerated graphite material.
Example 4
The embodiment is a method for recovering graphite in waste batteries, which comprises the following steps:
s1) putting 1kg of recovered graphite slag into an acid washing reactor, adding 50L of hydrofluoric acid solution with the concentration of 0.1mol/L, continuously stirring, reacting for 2 hours, filtering slurry in the acid washing reactor, washing with deionized water to be neutral, and then putting filter residues into an oven for drying;
s2) taking 4kg of filter residue dried in the step S1), putting the filter residue into a 15L high-temperature stirring reaction kettle, adjusting the stirring speed to 10r/min, introducing air, controlling the air flow rate to be 20L/min, simultaneously heating to 640 ℃ at the speed of 1 ℃/min, and carrying out heat preservation reaction for 1h at 640 ℃; strictly monitoring the temperature in the kettle in the reaction process, immediately closing the air inlet and the air outlet after the temperature exceeds a set value by 5 ℃, and simultaneously stopping heating; after the reaction is finished, continuously stirring, and discharging after the temperature is reduced to room temperature to obtain purified graphite;
s3) adding 1kg of purified graphite and 200g of asphalt with the softening point of 230 ℃ into a 3L high-speed mixer, and mixing for 20 min; then putting the mixture into a high-temperature furnace for high-temperature carbonization, wherein the heating rate is 3 ℃/min, the carbonization temperature is 900 ℃, and the temperature is kept for 5 hours; and cooling and sieving to obtain the regenerated graphite material.
Example 5
The embodiment is a method for recovering graphite in waste batteries, which comprises the following steps:
s1) putting the recovered 1kg of graphite slag into an acid washing reactor, adding 50L of hydrofluoric acid solution with the concentration of 0.1mol/L, continuously stirring, filtering the slurry in the container after reacting for 2h, washing the slurry to be neutral by deionized water, and then putting the filter residue into an oven for drying;
s2) taking 4kg of filter residue dried in the step S1), putting the filter residue into a 15L high-temperature stirring reaction kettle, adjusting the stirring speed to 10r/min, introducing air, controlling the air flow rate to be 20L/min, simultaneously heating to 650 ℃ at the speed of 1 ℃/min, and carrying out heat preservation reaction at 650 ℃ for 1 h; strictly monitoring the temperature in the kettle in the reaction process, immediately closing the air inlet and the air outlet after the temperature exceeds a set value by 5 ℃, and simultaneously stopping heating; after the reaction is finished, continuously stirring, and discharging after the temperature is reduced to room temperature to obtain purified graphite;
s3) adding 1kg of purified graphite and 200g of asphalt with the softening point of 150 ℃ into a 3L high-speed mixer, and mixing for 20 min; then putting the mixture into a high-temperature furnace for high-temperature carbonization, wherein the heating rate is 3 ℃/min, the carbonization temperature is 900 ℃, and the temperature is kept for 5 hours; and cooling and sieving to obtain the regenerated graphite material.
Example 6
The embodiment is a method for recovering graphite from waste batteries, and is different from the embodiment 5 in the step S3, in the step S3) of the embodiment, 1kg of purified graphite and 200g of phenolic resin are added into a 3L high-speed mixer and mixed for 20 min; then putting the mixture into a high-temperature furnace for high-temperature carbonization, wherein the heating rate is 3 ℃/min, the carbonization temperature is 900 ℃, and the temperature is kept for 5 hours; and cooling and sieving to obtain the regenerated graphite material. The remaining steps were the same as in example 5.
In order to verify whether the properties of the recovered graphite meet the battery material standards, the samples of examples 1 to 6 and comparative example 1 were subjected to tests in terms of specific surface area, ash content, particle size, and the like, and the results are shown in table 1. Meanwhile, the samples of examples 1-6 and comparative example 1 were assembled into button cells to test their electrochemical properties, and the test results are shown in table 2. The button cell is prepared from the same raw materials except graphite materials and by the same preparation method.
TABLE 1 specific surface area, Ash content and particle size parameters of the graphites in the examples and comparative examples
Figure BDA0001838253800000111
TABLE 2 test results of graphite withholding after regeneration
Figure BDA0001838253800000112
Figure BDA0001838253800000121
With reference to tables 1 and 2, it can be seen from the data in table 1 that, by comparing example 1 with comparative example 1, the specific surface area of graphite can be significantly reduced by using the method for removing cracked carbon provided by the present invention, and the graphite can be more easily dispersed during pulping to form stable graphite slurry; meanwhile, as can be seen from the data in table 2, the first disengagement capacity is effectively improved and the first efficiency is improved by 5.5% by using the method provided by the present invention compared with the conventional muffle furnace method.
As can be seen from the data in table 1, a comparison between example 2 and example 3 shows that the inorganic impurities in the graphite slag can be more effectively removed by hydrofluoric acid, and the purity of the graphite obtained by recovery can be further improved. Meanwhile, as can be seen from the data in table 2, the first stripping capacity and the first efficiency of the battery can be further improved by using hydrofluoric acid as the pickling solution.
As can be seen from the data in table 2, it is understood from comparison between example 4 and example 5 that the first efficiency of the battery can be further improved by selecting an asphalt having a softening point of 230 ℃ as compared with an asphalt having a softening point of 150 ℃.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (7)

1. A method for recovering graphite in waste batteries is characterized by comprising the following steps:
s1) acid washing and purifying: providing graphite slag generated in waste battery recovery as a recovery raw material, and then carrying out acid washing to remove impurities to obtain primarily purified graphite;
s2) removing cracked carbon: placing the primarily purified graphite in a reaction kettle, oxidizing at 350-640 ℃, wherein the stirring speed in the oxidation process is 10-100 r/min, the air flow rate is 1-50L/min, and the heat preservation time is 1-6 h to obtain secondarily purified graphite;
s3) coating and carbonizing: coating the graphite subjected to secondary purification by using a carbon source material which is heated and decomposed into carbon, and then carbonizing the coating layer to obtain a graphite material; wherein the carbon source material is asphalt, the softening point of the asphalt is 230-300 ℃, and the addition amount of the asphalt is 1-20% of the weight of the graphite.
2. The recovery method according to claim 1, wherein in step S1), the graphite slag is acid-washed with hydrofluoric acid, and the concentration of the hydrofluoric acid is 0.1 to 2 mol/L.
3. The recovery method according to claim 2, wherein the mass ratio of the graphite slag to the hydrofluoric acid is 1 (5-50), and the reaction time in the acid washing process is 1.5-2.5 h.
4. The recycling method according to any one of claims 1 to 3, wherein in the step S2), the temperature rising rate of the reaction kettle is 1 to 10 ℃/min.
5. The recycling method according to claim 1, wherein the coating of the graphite is completed by mixing the pitch and the secondarily purified graphite in a mixer.
6. The recycling method according to claim 1, wherein the carbonization temperature in the carbonization process is 900 to 1200 ℃ and the carbonization time is 1 to 5 hours.
7. Use of the recovery process according to any one of claims 1 to 6 in the recovery of spent batteries.
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