CN113594567A - Method for recycling graphite cathode material of lithium ion battery - Google Patents

Method for recycling graphite cathode material of lithium ion battery Download PDF

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Publication number
CN113594567A
CN113594567A CN202110819094.5A CN202110819094A CN113594567A CN 113594567 A CN113594567 A CN 113594567A CN 202110819094 A CN202110819094 A CN 202110819094A CN 113594567 A CN113594567 A CN 113594567A
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lithium ion
negative electrode
ion battery
sample
nano silicon
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崔大祥
葛美英
刘鹏飞
李梦飞
张芳
卢玉英
王亚坤
王金
张放为
焦靖华
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Shanghai National Engineering Research Center for Nanotechnology 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • 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 discloses a method for recycling a graphite cathode material of a lithium ion battery, which comprises the steps of taking a disabled lithium ion battery, disassembling the disabled lithium ion battery in an environment with the humidity of below 10%, collecting the cathode material, placing the cathode material in an inert gas atmosphere for heat treatment, crushing an obtained sample, and sieving the crushed sample with a 200-mesh sieve to obtain a nano silicon @ carbon @ graphite composite material. The gram capacity loss of the failed battery is serious, and the recovered negative electrode material needs to be reprocessed to remove surface impurities due to lithium precipitation, electrolyte deposition and the like on the surface, and then the recovered negative electrode material is modified by utilizing the characteristic of high specific capacity of nano silicon to prepare the composite material, so that the capacity loss problem of the recovered negative electrode material is solved, the nano silicon @ carbon @ graphite composite material is prepared, and the performance attenuation problem caused by volume expansion in the charge-discharge cycle process of nano silicon is solved. The method can recycle the failed cathode material, and has the advantages of simple process, low preparation cost, stable performance and wide application prospect.

Description

Method for recycling graphite cathode material of lithium ion battery
Technical Field
The invention relates to a treatment problem of waste lithium ion batteries, in particular to a method for recycling a graphite cathode material of a lithium ion battery, and belongs to the field of lithium ion batteries.
Background
In recent years, with the widespread use of lithium ion batteries, the recycling of waste batteries has become a major problem.
The invention relates to a method for preparing a lithium ion battery cathode material, which is characterized in that graphite is taken as a main material of the current commercial lithium ion battery cathode material, the graphite still has very good telephone performance after the battery cathode material after failure is recovered due to high stability, however, materials such as conductive agents, binders and the like are introduced in the process of manufacturing a pole piece, so that the capacity of the recovered cathode material is obviously reduced compared with the specific capacity of the commercial graphite material, and in order to improve the specific capacity of the recovered cathode material, the invention compounds the recovered cathode material with a nano silicon material, fully utilizes the characteristic of high specific capacity of the nano silicon material, and improves the specific capacity of the recovered cathode, thereby promoting the problem of recycling the waste battery cathode material.
The invention provides a simple method for recycling and improving the performance of a waste battery cathode material, solves the problem of capacity reduction in the process of recycling the recycled cathode material as a lithium ion battery cathode, and has practical application value for promoting the recycling of the waste battery.
Disclosure of Invention
The invention aims to provide a method for recycling a graphite cathode material of a lithium ion battery. A simple and feasible method for improving the performance of a negative electrode material of a failed lithium ion battery.
The purpose of the invention is realized by the following scheme:
a method for recycling a graphite cathode material of a lithium ion battery is characterized in that the cathode material is recycled and compounded with a nano silicon material to realize recycling of the failed cathode material of the lithium ion battery, and comprises the following steps:
step one, recycling the anode material: taking the lithium ion battery after failure, disassembling the lithium ion battery in an environment with the humidity of below 10%, and collecting a negative electrode material; dispersing the collected negative electrode material in dehydrated ethanol, performing ultrasonic treatment for 30min, performing suction filtration, dispersing the powder material in deionized water, performing ultrasonic treatment for 30min, performing suction filtration, and drying to obtain a negative electrode material;
step two, recovering the carbon material: placing the negative electrode material obtained in the first step in an inert gas atmosphere for heat treatment, wherein the heat treatment temperature is 650-750 ℃, the heat preservation time is 1-2h, the temperature rise speed is 3-6 ℃/min, and when the temperature is reduced to room temperature, obtaining a recovered carbon material, and marking the recovered carbon material as a sample A;
step three: dissolving a proper amount of glucose in deionized water, adding nano silicon, stirring and dispersing, and then carrying out spray drying, wherein the mass ratio of the glucose to the nano silicon is (2-5): 1, and the obtained sample is marked as a sample B;
step four: and (3) mixing the sample A and the sample B in a mechanical mixing mode according to a mass ratio of 10 (0.1-1), placing the mixture in a tube furnace for heat treatment, heating to 650-800 ℃ at a heating rate of 3-6 ℃/min under the protection of argon, preserving heat for 2-4 h, naturally cooling, crushing the obtained sample, and sieving with a 200-mesh sieve to obtain the nano silicon @ carbon @ graphite composite material.
In the first step, the failed lithium ion battery is a lithium ion battery with the capacity reduced to below 60% of the initial capacity.
In the second step, the inert gas atmosphere is high-purity argon or high-purity nitrogen.
In the third step, the nano silicon is a nano silicon material with the granularity dispersed in 80-105 nm.
The gram capacity loss of the failed battery is serious, and lithium precipitation, electrolyte deposition and the like are carried out on the surface of the recovered negative electrode material, so that the recovered negative electrode material needs to be reprocessed to remove surface impurities, and then the recovered negative electrode material is modified to prepare the composite material by utilizing the characteristic of high specific capacity of nano silicon, so that the capacity loss problem of the recovered negative electrode material is solved, and the nano silicon @ carbon @ graphite composite material is prepared by carbon coating, so that the performance attenuation problem caused by volume expansion in the charge-discharge cycle process of nano silicon is solved. The method has the advantages that the invalid cathode material can be recycled, the preparation process is simple, the preparation cost is low, the performance is stable, and the method has wide application prospect.
Drawings
Fig. 1 shows the cycle data of the nano silicon @ carbon @ graphite composite material.
Detailed Description
Example 1:
a method for recycling a graphite cathode material of a lithium ion battery comprises the following steps of taking a failed lithium ion battery, disassembling the lithium ion battery in an environment with the humidity of below 10%, collecting the cathode material, placing the cathode material in an inert gas atmosphere for heat treatment, crushing an obtained sample, sieving the crushed sample with a 200-mesh sieve, and preparing a nano silicon @ carbon @ graphite composite material according to the following steps:
step one, recycling the anode material: taking the lithium ion battery with the capacity reduced to 60% of the initial capacity after circulation, disassembling the lithium ion battery in an environment with the humidity of below 10%, and collecting a negative electrode material; dispersing the collected negative electrode material in dehydrated ethanol, performing ultrasonic treatment for 30min, performing suction filtration, dispersing the powder material in deionized water, performing ultrasonic treatment for 30min, performing suction filtration, and drying to obtain a recovered negative electrode material;
step two, recovering the carbon material: placing the negative electrode material obtained in the first step in an argon gas atmosphere for heat treatment, wherein the heat treatment temperature is 650 ℃, the heat preservation time is 2 hours, the temperature rising speed is 5 ℃/min, and after the temperature is reduced to the room temperature, a recovered carbon material is obtained and is marked as a sample A;
step three: dissolving a proper amount of glucose in deionized water, adding nano silicon with the granularity dispersed at 80 nm, wherein the mass ratio of the glucose to the nano silicon is 5:1, stirring for dispersion, and then performing spray drying to obtain a sample B;
step four: and (2) sampling a sample A and a sample B according to the mass ratio of 10:1, mixing in a mechanical mixing mode, placing in a tubular furnace for heat treatment, heating to 800 ℃ at the heating rate of 6 ℃/min under the protection of argon, preserving the temperature for 2h, naturally cooling, crushing the obtained samples, and sieving with a 200-mesh sieve to obtain the nano @ silicon @ carbon @ graphite composite material.
The nano silicon @ carbon @ graphite composite material prepared in the embodiment is mixed with a binder (CMC), a conductive agent (SP) and SBR in a mass ratio of 8: 0.5: 1: 0.5, preparing the working electrode into slurry, assembling the working electrode into a button battery, standing for more than 10 hours, and performing charge and discharge test at the ambient temperature of 25 ℃, wherein the gram volume is 537.8 mAh/g.
Example 2:
a method for recycling a graphite anode material of a lithium ion battery is similar to the step of the embodiment 1, and the nano silicon @ carbon @ graphite composite material is prepared by the following steps:
step one, recycling the anode material: taking the lithium ion battery with the capacity reduced to 50% of the initial capacity after circulation, disassembling the lithium ion battery in an environment with the humidity of below 10%, and collecting a negative electrode material; dispersing the collected negative electrode material in dehydrated ethanol, performing ultrasonic treatment for 30min, performing suction filtration, dispersing the powder material in deionized water in a laboratory under the common temperature and humidity condition, performing ultrasonic treatment for 30min, performing suction filtration, and drying to obtain a recovered negative electrode material;
step two, recovering the carbon material: placing the negative electrode material obtained in the first step in an argon gas atmosphere for heat treatment, wherein the heat treatment temperature is 750 ℃, the heat preservation time is 2 hours, the temperature rising speed is 3 ℃/min, and after the temperature is reduced to the room temperature, a recovered carbon material is obtained and is marked as a sample A;
step three: dissolving a proper amount of glucose in deionized water, adding nano silicon with the granularity dispersed at 100 nm, wherein the mass ratio of the glucose to the nano silicon is 4.5:1, stirring for dispersion, and then performing spray drying to obtain a sample, namely a sample B;
step four: and (2) sampling a sample A and a sample B according to the mass ratio of 10:0.5, mixing in a mechanical mixing mode, placing in a tubular furnace for heat treatment, heating to 800 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 2 hours, naturally cooling, crushing the obtained samples, and sieving with a 200-mesh sieve to obtain the nano silicon @ carbon @ graphite composite material.
The nano silicon @ carbon @ graphite composite material prepared in the embodiment is mixed with a binder (CMC), a conductive agent (SP) and SBR in a mass ratio of 8: 0.5: 1: 0.5, preparing the slurry into a working electrode, assembling the working electrode into a button battery, standing for more than 10 hours, and performing charge and discharge tests at the ambient temperature of 25 ℃, wherein the gram volume is 435.2 mAh/g.
Example 3:
a method for recycling a graphite anode material of a lithium ion battery is similar to the step of the embodiment 1, and the nano silicon @ carbon @ graphite composite material is prepared by the following steps:
step one, recycling the anode material: taking the failed lithium ion battery with the capacity reduced to 50% of the initial capacity after circulation, disassembling the lithium ion battery in an environment with the humidity of below 10%, and collecting a negative electrode material; dispersing the collected negative electrode material in dehydrated alcohol, performing ultrasonic treatment for 30min, performing suction filtration, dispersing the powder material in deionized water in a laboratory under the common temperature and humidity condition, performing ultrasonic treatment for 30min, performing suction filtration, and drying the recovered negative electrode material;
step two, recovering the carbon material: placing the obtained negative electrode material in an argon gas atmosphere for heat treatment, wherein the heat treatment temperature is 650 ℃, the heat preservation time is 1h, the heating rate is 3 ℃/min, and after the temperature is reduced to the room temperature, obtaining a recovered carbon material, and marking as a sample A;
step three: dissolving a proper amount of glucose in deionized water, adding nano silicon with the granularity dispersed at 100 nm, wherein the mass ratio of the glucose to the nano silicon is 2:1, stirring for dispersion, and then performing spray drying to obtain a sample, namely a sample B;
step four: and (2) sampling a sample A and a sample B according to the mass ratio of 10:0.1, mixing in a mechanical mixing mode, placing in a tubular furnace for heat treatment after mixing, heating to 700 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 4h, naturally cooling, crushing the obtained sample, and sieving with a 200-mesh sieve to obtain the nano silicon @ carbon @ graphite composite material.
The nano silicon @ carbon @ graphite composite material prepared in the embodiment is mixed with a binder (CMC), a conductive agent (SP) and SBR in a mass ratio of 8: 0.5: 1: 0.5, preparing the slurry into a working electrode, assembling the working electrode into a button battery, standing the button battery for more than 10 hours, and performing charge and discharge test at the ambient temperature of 25 ℃, wherein the gram capacity of the button battery is 378.5 mAh/g, FIG. 1 shows the cycle data of the nano silicon @ carbon @ graphite composite material obtained in the embodiment, and as can be seen from FIG. 1, the specific capacity retention rate of a sample after 200 cycles is 88.3%.
Comparative example:
the method for recycling the negative electrode material comprises the following steps:
taking a failed lithium ion battery with the capacity reduced to 60% of the initial capacity after circulation, disassembling the lithium ion battery in an environment with the humidity of below 10%, and collecting a negative electrode material; dispersing the collected negative electrode material in dehydrated ethanol, performing ultrasonic treatment for 30min, performing suction filtration, dispersing the powder material in deionized water in a laboratory under the common temperature and humidity condition, performing ultrasonic treatment for 30min, performing suction filtration, and drying to obtain a recovered negative electrode material;
step two, recovering the carbon material: and placing the obtained negative electrode material in an argon gas atmosphere for heat treatment, wherein the heat treatment temperature is 650 ℃, the heat preservation time is 2h, the heating speed is 5 ℃/min, and the recovered negative electrode material is obtained after the temperature is reduced to the room temperature.
The recycled negative electrode material prepared in the comparative example, a binder (CMC), a conductive agent (SP) and SBR were mixed in a mass ratio of 8: 0.5: 1: 0.5, preparing the slurry into a working electrode, assembling the working electrode into a button battery, standing for more than 10 hours, and performing charge and discharge tests at the ambient temperature of 25 ℃, wherein the gram volume is 285.8 mAh/g.
The nano silicon @ carbon @ graphite composite material has higher gram capacity than a battery prepared from a recycled negative electrode material in a comparative ratio.

Claims (7)

1. A method for recycling a graphite cathode material of a lithium ion battery is characterized in that the cathode material is recycled and compounded with a nano silicon material to realize recycling of the failed cathode material of the lithium ion battery, and comprises the following steps:
step one, recycling the anode material: taking the lithium ion battery after failure, disassembling the lithium ion battery in an environment with the humidity of below 10%, and collecting a negative electrode material; dispersing the collected negative electrode material in dehydrated ethanol, performing ultrasonic treatment for 30min, performing suction filtration, dispersing the powder material in deionized water, performing ultrasonic treatment for 30min, performing suction filtration, and drying to obtain a negative electrode material;
step two, recovering the carbon material: placing the negative electrode material obtained in the first step in an inert gas atmosphere for heat treatment, wherein the heat treatment temperature is 650-750 ℃, the heat preservation time is 1-2h, the temperature rise speed is 3-6 ℃/min, and when the temperature is reduced to room temperature, obtaining a recovered carbon material, and marking the recovered carbon material as a sample A;
step three: dissolving a proper amount of glucose in deionized water, adding nano silicon, stirring and dispersing, and then carrying out spray drying, wherein the mass ratio of the glucose to the nano silicon is (2-5): 1, and the obtained sample is marked as a sample B;
step four: and (3) mixing the sample A and the sample B in a mechanical mixing mode according to a mass ratio of 10 (0.1-1), placing the mixture in a tube furnace for heat treatment, heating to 650-800 ℃ at a heating rate of 3-6 ℃/min under the protection of argon, preserving heat for 2-4 h, naturally cooling, crushing the obtained sample, and sieving with a 200-mesh sieve to obtain the nano silicon @ carbon @ graphite composite material.
2. The method for recycling the graphite negative electrode material of the lithium ion battery according to claim 1, wherein the method comprises the following steps: and step one, the failed lithium ion battery is a lithium ion battery with the capacity reduced to the initial capacity of less than 60%.
3. The method for recycling the graphite negative electrode material of the lithium ion battery according to claim 1, wherein the method comprises the following steps: and the inert gas atmosphere in the second step is high-purity argon or high-purity nitrogen.
4. The method for recycling the graphite negative electrode material of the lithium ion battery according to claim 1, wherein the method comprises the following steps: and step three, the nano silicon is a nano silicon material with the granularity dispersed in 80-105 nm.
5. The method for recycling the graphite anode material of the lithium ion battery according to any one of claims 1 to 4, wherein the nano silicon @ carbon @ graphite composite material is prepared by the following steps:
step one, recycling the anode material: taking the lithium ion battery with the capacity reduced to 60% of the initial capacity after circulation, disassembling the lithium ion battery in an environment with the humidity of below 10%, and collecting a negative electrode material; dispersing the collected negative electrode material in dehydrated ethanol, performing ultrasonic treatment for 30min, performing suction filtration, dispersing the powder material in deionized water, performing ultrasonic treatment for 30min, performing suction filtration, and drying to obtain a recovered negative electrode material;
step two, recovering the carbon material: placing the negative electrode material obtained in the first step in an argon gas atmosphere for heat treatment, wherein the heat treatment temperature is 650 ℃, the heat preservation time is 2 hours, the temperature rising speed is 5 ℃/min, and after the temperature is reduced to the room temperature, a recovered carbon material is obtained and is marked as a sample A;
step three: dissolving a proper amount of glucose in deionized water, adding nano silicon with the granularity dispersed at 80 nm, wherein the mass ratio of the glucose to the nano silicon is 5:1, stirring for dispersion, and then performing spray drying to obtain a sample B;
step four: and (2) sampling a sample A and a sample B according to the mass ratio of 10:1, mixing in a mechanical mixing mode, placing in a tubular furnace for heat treatment, heating to 800 ℃ at the heating rate of 6 ℃/min under the protection of argon, preserving the temperature for 2h, naturally cooling, crushing the obtained samples, and sieving with a 200-mesh sieve to obtain the nano @ silicon @ carbon @ graphite composite material.
6. The method for recycling the graphite anode material of the lithium ion battery according to any one of claims 1 to 4, wherein the nano silicon @ carbon @ graphite composite material is prepared by the following steps:
step one, recycling the anode material: taking the lithium ion battery with the capacity reduced to 50% of the initial capacity after circulation, disassembling the lithium ion battery in an environment with the humidity of below 10%, and collecting a negative electrode material; dispersing the collected negative electrode material in dehydrated ethanol, performing ultrasonic treatment for 30min, performing suction filtration, dispersing the powder material in deionized water in a laboratory under the common temperature and humidity condition, performing ultrasonic treatment for 30min, performing suction filtration, and drying to obtain a recovered negative electrode material;
step two, recovering the carbon material: placing the negative electrode material obtained in the first step in an argon gas atmosphere for heat treatment, wherein the heat treatment temperature is 750 ℃, the heat preservation time is 2 hours, the temperature rising speed is 3 ℃/min, and after the temperature is reduced to the room temperature, a recovered carbon material is obtained and is marked as a sample A;
step three: dissolving a proper amount of glucose in deionized water, adding nano silicon with the granularity dispersed at 100 nm, wherein the mass ratio of the glucose to the nano silicon is 4.5:1, stirring for dispersion, and then performing spray drying to obtain a sample, namely a sample B;
step four: and (2) sampling a sample A and a sample B according to the mass ratio of 10:0.5, mixing in a mechanical mixing mode, placing in a tubular furnace for heat treatment, heating to 800 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 2 hours, naturally cooling, crushing the obtained samples, and sieving with a 200-mesh sieve to obtain the nano silicon @ carbon @ graphite composite material.
7. The method for recycling the graphite anode material of the lithium ion battery according to any one of claims 1 to 4, wherein the nano silicon @ carbon @ graphite composite material is prepared by the following steps:
step one, recycling the anode material: taking the failed lithium ion battery with the capacity reduced to 50% of the initial capacity after circulation, disassembling the lithium ion battery in an environment with the humidity of below 10%, and collecting a negative electrode material; dispersing the collected negative electrode material in dehydrated alcohol, performing ultrasonic treatment for 30min, performing suction filtration, dispersing the powder material in deionized water in a laboratory under the common temperature and humidity condition, performing ultrasonic treatment for 30min, performing suction filtration, and drying the recovered negative electrode material;
step two, recovering the carbon material: placing the obtained negative electrode material in an argon gas atmosphere for heat treatment, wherein the heat treatment temperature is 650 ℃, the heat preservation time is 1h, the heating rate is 3 ℃/min, and after the temperature is reduced to the room temperature, obtaining a recovered carbon material, and marking as a sample A;
step three: dissolving a proper amount of glucose in deionized water, adding nano silicon with the granularity dispersed at 100 nm, wherein the mass ratio of the glucose to the nano silicon is 2:1, stirring for dispersion, and then performing spray drying to obtain a sample, namely a sample B;
step four: and (2) sampling a sample A and a sample B according to the mass ratio of 10:0.1, mixing in a mechanical mixing mode, placing in a tubular furnace for heat treatment after mixing, heating to 700 ℃ at the heating rate of 5 ℃/min under the protection of argon, preserving heat for 4h, naturally cooling, crushing the obtained sample, and sieving with a 200-mesh sieve to obtain the nano silicon @ carbon @ graphite composite material.
CN202110819094.5A 2021-07-20 2021-07-20 Method for recycling graphite cathode material of lithium ion battery Pending CN113594567A (en)

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