CN113582171A - Method for recovering graphite cathode of lithium ion battery - Google Patents
Method for recovering graphite cathode of lithium ion battery Download PDFInfo
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- CN113582171A CN113582171A CN202110813255.XA CN202110813255A CN113582171A CN 113582171 A CN113582171 A CN 113582171A CN 202110813255 A CN202110813255 A CN 202110813255A CN 113582171 A CN113582171 A CN 113582171A
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
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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
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
Abstract
The invention discloses a method for recovering a graphite cathode of a lithium ion battery, which comprises the steps of collecting a lithium ion battery after failure, collecting a cathode material, and fully washing the collected cathode material to obtain a recovered cathode material. In order to alleviate the problem of poor cycle stability caused by volume expansion of a silicon material in the process of charging and discharging, the silicon material is coated with carbon to be used as a buffer layer. The method has the advantages of simple preparation process, low preparation cost and stable performance, solves the problem of treatment of waste batteries, and has wide application prospect. The method solves the problem of recycling the anode material of the waste battery.
Description
Technical Field
The invention relates to a treatment problem of waste lithium ion batteries, in particular to a method for recovering graphite negative electrodes of lithium ion batteries, and a method for recycling negative electrode materials of waste batteries.
Background
In recent years, with the widespread use of lithium ion batteries, the recycling of waste batteries has become a major problem. The waste lithium ion batteries are recycled and disassembled, and the anode and cathode materials are recycled after treatment, so that the method is an important direction for further promoting energy conservation and emission reduction.
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 silica material, fully utilizes the characteristic of high specific capacity of the silica material, and improves the specific capacity of the recovered cathode, thereby promoting the recycling problem of the waste battery cathode material.
Disclosure of Invention
The invention aims to provide a method for recycling a lithium ion battery graphite cathode, which is simple and feasible for preparing SiOxA modified graphite material.
Yet another object of the present invention is to: providing the SiOxUse of a modified graphite material.
The purpose of the invention is realized by the following technical scheme: a method for recycling graphite negative electrodes of lithium ion batteries is characterized in that a negative electrode material (mainly a graphite material) is recycled, and the recycled negative electrode material is reused by compounding the recycled negative electrode material with a silicon material, and comprises the following steps:
the method comprises the following steps: taking a lithium ion battery negative pole piece after the circulation failure, collecting a negative pole material on the surface of a current collector, dispersing the negative pole material in deionized water, performing ultrasonic treatment for 10min, performing suction filtration, then dispersing in ethanol, performing ultrasonic treatment for 10min, performing suction filtration, performing ultrasonic-suction filtration treatment for 5-10 times respectively by using the deionized water and the ethanol, drying the negative pole material, then soaking the negative pole material in dilute hydrochloric acid (HCl) with the concentration of 0.08-0.2M for 2-3 h, performing suction filtration, soaking and suction filtration for multiple times by using deionized water, and drying the obtained negative pole material in a blast drying box; obtaining a recovered negative electrode material;
step two: 0 to 1g of Silica (SiO) having a particle size distribution in the range of D50 of 3 to 4 μmx，0<x<2) Grinding the carbon source and a carbon source in a ball mill, wherein the carbon source is at least one of asphalt or sucrose, and the mass ratio of the carbon source to the silicon monoxide is (4-5): 100, so as to obtain a ground sample;
step three: premixing the ground sample obtained in the second step with 10g of the recycled negative electrode material obtained in the first step, placing the mixed sample in a tube furnace, performing heat treatment in a high-purity argon atmosphere at the heat treatment temperature of 650-750 ℃ for 2-4 h, at the heat treatment temperature of 900-950 ℃ for 2-3 h, at the heating rate of 3-6 ℃/min, cooling to room temperature, taking out to obtain SiOxA modified graphite material.
The method realizes the reutilization of the recycled negative electrode material by compounding the recycled negative electrode material with the silicon material.
And (3) taking the negative pole piece, namely disassembling the lithium ion battery in an environment with the humidity lower than 10% to obtain the negative pole piece.
The invention also provides the obtained SiOxThe modified graphite material can be used for the negative electrode of a lithium ion battery. Test results show that the material can improve the specific capacity and rate capability of the recycled negative electrode.
The invention provides a simple method for recycling and expanding the capacity of the anode material of the waste battery, which can greatly improve the specific capacity of the recycled anode, has simple preparation process and low preparation cost, and has practical application value for promoting the recycling of the waste battery. The method solves the problem of recycling the waste battery cathode material, and the problem of capacity loss in the recycling process of the failed cathode material. In order to alleviate the problem of poor cycle stability caused by volume expansion of a silicon material in the process of charging and discharging, the silicon material is coated with carbon to be used as a buffer layer. The method has the advantages of simple preparation process, low preparation cost, stable performance of the obtained product, solving the problem of treatment of the waste battery and having wide application prospect.
Drawings
FIG. 1 is SiOxCycle data for the modified graphite material.
Detailed Description
Example 1:
a method for recovering graphite cathode of lithium ion battery is characterized in that the recovered cathode material is attached to a silicon material to realize the reutilization of the recovered cathode, and SiO is prepared according to the following stepsxModified graphite material:
the method comprises the following steps: taking a lithium ion battery negative pole piece which is subjected to cyclic failure, collecting a negative pole material on the surface of a current collector, dispersing the negative pole material in deionized water, performing ultrasonic treatment for 10min, performing suction filtration, then dispersing in ethanol, performing ultrasonic treatment for 10min, performing suction filtration, performing ultrasonic-suction filtration treatment for 5 times respectively by using the deionized water and the ethanol, drying the negative pole material, then soaking the negative pole material for 3 hours by using dilute hydrochloric acid (HCl) with the concentration of 0.1M, performing suction filtration, repeatedly soaking and suction filtration by using the deionized water, and drying the obtained negative pole material in a blast drying box; obtaining a recovered negative electrode material;
step two: 1g of Silica (SiO) having a particle size distribution in the range D50 of 3 μm was takenx，0<x<2) Grinding the carbon source pitch and the carbon source pitch in a ball mill, wherein the mass ratio of the pitch to the silicon monoxide is 5:100 to obtain the ground pitchA sample;
step three: premixing the sample ground in the step two with 10g of the recycled negative electrode material obtained in the step one, placing the mixed sample in a tube furnace, carrying out heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 650 ℃ for 2h, keeping the heat treatment temperature at 900 ℃ for 3h, keeping the temperature at the temperature rising speed of 5 ℃/min, cooling to room temperature, taking out, and obtaining SiOxA modified graphite material.
SiO produced in this examplexThe modified graphite material, a binder (CMC), a conductive agent (SP) and SBR are mixed according to the 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 479.4 mAh/g. Fig. 1 shows cycling data of the button cell, and it can be seen that the capacity retention rate of the cell after 300 cycles is 87.2%.
Example 2:
a method for recycling a graphite cathode of a lithium ion battery is similar to the step of the embodiment 1, and SiO is prepared according to the following stepsxModified graphite material:
the method comprises the following steps: taking a lithium ion battery negative pole piece which is subjected to cyclic failure, collecting a negative pole material on the surface of a current collector, dispersing the negative pole material in deionized water, performing ultrasonic treatment for 10min, performing suction filtration, then dispersing in ethanol, performing ultrasonic treatment for 10min, performing suction filtration, performing ultrasonic-suction filtration treatment for 10 times respectively by using deionized water and ethanol, drying the negative pole material, then soaking the negative pole material for 3 hours by using dilute hydrochloric acid (HCl) with the concentration of 0.2M, performing suction filtration, repeatedly soaking and suction filtration by using deionized water, and drying the obtained negative pole material in a blast drying box; obtaining a recovered negative electrode material;
step two: 0.5g of Silica (SiO) having a particle size distribution in the range D50 of 4 μm was takenx，0<x<2) Grinding the carbon source pitch and the pitch in a ball mill, wherein the mass ratio of the pitch to the silicon monoxide is 5:100, and obtaining a ground sample;
step three: premixing the sample ground in the step two with 10g of the recycled negative electrode material obtained in the step one, placing the mixed sample in a tube furnace, carrying out heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 650 ℃ for 2h and at 900 ℃ for 3h, and keeping the temperature rise speed at 5 ℃/min until the temperature is loweredCooling to room temperature, taking out to obtain SiOxA modified graphite material.
SiO produced in this examplexThe modified graphite material, a binder (CMC), a conductive agent (SP) and SBR are mixed according to the 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 408.7 mAh/g.
Example 3:
a method for recycling a graphite cathode of a lithium ion battery is similar to the step of the embodiment 1, and SiO is prepared according to the following stepsxModified graphite material:
the method comprises the following steps: taking a lithium ion battery negative pole piece which is subjected to cyclic failure, collecting a negative pole material on the surface of a current collector, dispersing the negative pole material in deionized water, performing ultrasonic treatment for 10min, performing suction filtration, then dispersing in ethanol, performing ultrasonic treatment for 10min, performing suction filtration, performing ultrasonic-suction filtration treatment for 5 times respectively by using deionized water and ethanol, drying the negative pole material, then soaking the negative pole material for 3 hours by using dilute hydrochloric acid (HCl) with the concentration of 0.2M, performing suction filtration, repeatedly soaking and suction filtration by using deionized water, and drying the obtained negative pole material in a blast drying box; obtaining a recovered negative electrode material;
step two: 0.1g of Silica (SiO) having a particle size distribution in the range D50 of 4 μm was takenx，0<x<2) Grinding the carbon source asphalt or sucrose in a ball mill with the mass ratio of asphalt to silicon monoxide being 4:100 to obtain a ground sample;
step three: premixing the sample ground in the step two with 10g of the recycled negative electrode material obtained in the step one, placing the mixed sample in a tube furnace, carrying out heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 750 ℃ for 2h and at 950 ℃ for 3h, keeping the temperature at the temperature rising speed of 5 ℃/min, cooling to room temperature, taking out, and obtaining SiOxA modified graphite material.
SiO produced in this examplexThe modified graphite material, a binder (CMC), a conductive agent (SP) and SBR are mixed according to the mass ratio of 8: 0.5: 1: 0.5 is mixed into slurry to prepare a working electrode, the working electrode is assembled into a button battery and then is kept stand for more than 10 hours, the charge and discharge test is carried out at the ambient temperature of 25 ℃, and the gram volume is 338.7mAh/g。
Example 4:
a method for recovering graphite cathode of lithium ion battery is similar to the step of the embodiment 1, only the silicon monoxide is 0, namely the original step two is omitted, and the SiO is prepared by the following stepsxModified graphite material:
the method comprises the following steps: taking a lithium ion battery negative pole piece which is subjected to cyclic failure, collecting a negative pole material on the surface of a current collector, dispersing the negative pole material in deionized water, performing ultrasonic treatment for 10min, performing suction filtration, then dispersing in ethanol, performing ultrasonic treatment for 10min, performing suction filtration, performing ultrasonic-suction filtration treatment for 5 times respectively by using the deionized water and the ethanol, drying the negative pole material, then soaking the negative pole material for 3 hours by using dilute hydrochloric acid (HCl) with the concentration of 0.1M, performing suction filtration, repeatedly soaking and suction filtration by using the deionized water, and drying the obtained negative pole material in a blast drying box; obtaining a recovered negative electrode material;
step two: putting the recycled negative electrode material obtained in the step one into a tubular furnace, carrying out heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 650 ℃ for 2h and 900 ℃ for 3h, raising the temperature at 5 ℃/min, cooling to room temperature, taking out to obtain SiOxA modified graphite material.
The material obtained in this example is SiO-freexThe modified recycled negative electrode material is prepared by mixing the modified recycled negative electrode material, a binder (CMC), a conductive agent (SP) and SBR according to the mass ratio of 8: 0.5: 1: 0.5, preparing the 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 293.4 mAh/g.
Claims (8)
1. A method for recycling a graphite cathode of a lithium ion battery is characterized in that a lithium ion battery cathode material is recycled, and the recycled cathode material is compounded with a silicon material to realize recycling of the recycled cathode, and the method comprises the following steps:
the method comprises the following steps: taking a lithium ion battery negative pole piece after the circulation failure, collecting a negative pole material on the surface of a current collector, dispersing the negative pole material in deionized water, performing ultrasonic treatment for 10min, performing suction filtration, then dispersing in ethanol, performing ultrasonic treatment for 10min, performing suction filtration, performing ultrasonic-suction filtration treatment for 5-10 times respectively by using the deionized water and the ethanol, drying the negative pole material, then soaking the negative pole material in dilute hydrochloric acid (HCl) with the concentration of 0.08-0.2M for 2-3 h, performing suction filtration, soaking and suction filtration for multiple times by using deionized water, and drying the obtained negative pole material in a blast drying box; obtaining a recovered negative electrode material;
step two: 0 to 1g of Silica (SiO) having a particle size distribution in the range of D50 of 3 to 4 μmx，0<x<2) Grinding the carbon source and a carbon source in a ball mill, wherein the carbon source is at least one of asphalt or sucrose, and the mass ratio of the carbon source to the silicon monoxide is (4-5): 100, so as to obtain a ground sample;
step three: premixing the ground sample obtained in the second step with 10g of the recycled negative electrode material obtained in the first step, placing the mixed sample in a tube furnace, performing heat treatment in a high-purity argon atmosphere at the heat treatment temperature of 650-750 ℃ for 2-4 h, at the heat treatment temperature of 900-950 ℃ for 2-3 h, at the heating rate of 3-6 ℃/min, cooling to room temperature, taking out to obtain SiOxA modified graphite material.
2. The method for recovering the graphite negative electrode of the lithium ion battery as claimed in claim 1, wherein the method comprises the following steps: and step one, the lithium ion battery after failure is the lithium ion battery with the capacity reduced to below 80% of the initial capacity, and the method for taking the negative pole piece is to disassemble the lithium ion battery in the environment with the humidity lower than 10% to obtain the negative pole piece.
3. The method for recycling graphite negative electrodes of lithium ion batteries according to claim 1 or 2, characterized in that: SiO was prepared as followsxModified graphite material:
the method comprises the following steps: taking a lithium ion battery negative pole piece which is subjected to cyclic failure, collecting a negative pole material on the surface of a current collector, dispersing the negative pole material in deionized water, performing ultrasonic treatment for 10min, performing suction filtration, then dispersing in ethanol, performing ultrasonic treatment for 10min, performing suction filtration, performing ultrasonic-suction filtration treatment for 5 times respectively by using the deionized water and the ethanol, drying the negative pole material, then soaking the negative pole material for 3 hours by using dilute hydrochloric acid (HCl) with the concentration of 0.1M, performing suction filtration, repeatedly soaking and suction filtration by using the deionized water, and drying the obtained negative pole material in a blast drying box; obtaining a recovered negative electrode material;
step two: 1g of Silica (SiO) having a particle size distribution in the range D50 of 3 μm was takenx，0<x<2) Grinding the carbon source pitch and the pitch in a ball mill, wherein the mass ratio of the pitch to the silicon monoxide is 5:100, and obtaining a ground sample;
step three: premixing the sample ground in the step two with 10g of the recycled negative electrode material obtained in the step one, placing the mixed sample in a tube furnace, carrying out heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 650 ℃ for 2h, keeping the heat treatment temperature at 900 ℃ for 3h, keeping the temperature at the temperature rising speed of 5 ℃/min, cooling to room temperature, taking out, and obtaining SiOxA modified graphite material.
4. The method for recycling graphite negative electrodes of lithium ion batteries according to claim 1 or 2, characterized in that: SiO was prepared as followsxModified graphite material:
the method comprises the following steps: taking a lithium ion battery negative pole piece which is subjected to cyclic failure, collecting a negative pole material on the surface of a current collector, dispersing the negative pole material in deionized water, performing ultrasonic treatment for 10min, performing suction filtration, then dispersing in ethanol, performing ultrasonic treatment for 10min, performing suction filtration, performing ultrasonic-suction filtration treatment for 10 times respectively by using deionized water and ethanol, drying the negative pole material, then soaking the negative pole material for 3 hours by using dilute hydrochloric acid (HCl) with the concentration of 0.2M, performing suction filtration, repeatedly soaking and suction filtration by using deionized water, and drying the obtained negative pole material in a blast drying box; obtaining a recovered negative electrode material;
step two: 0.5g of Silica (SiO) having a particle size distribution in the range D50 of 4 μm was takenx，0<x<2) Grinding the carbon source pitch and the pitch in a ball mill, wherein the mass ratio of the pitch to the silicon monoxide is 5:100, and obtaining a ground sample;
step three: premixing the sample ground in the step two with 10g of the recycled negative electrode material obtained in the step one, placing the mixed sample in a tube furnace, carrying out heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 650 ℃ for 2h and 900 ℃ for 3h, keeping the temperature at the temperature rising speed of 5 ℃/min, cooling to room temperature, taking out, and obtaining SiOxA modified graphite material.
5. According to the rightThe method for recycling the graphite cathode of the lithium ion battery according to claim 1 or 2, characterized by comprising the following steps: SiO was prepared as followsxModified graphite material:
the method comprises the following steps: taking a lithium ion battery negative pole piece which is subjected to cyclic failure, collecting a negative pole material on the surface of a current collector, dispersing the negative pole material in deionized water, performing ultrasonic treatment for 10min, performing suction filtration, then dispersing in ethanol, performing ultrasonic treatment for 10min, performing suction filtration, performing ultrasonic-suction filtration treatment for 5 times respectively by using deionized water and ethanol, drying the negative pole material, then soaking the negative pole material for 3 hours by using dilute hydrochloric acid (HCl) with the concentration of 0.2M, performing suction filtration, repeatedly soaking and suction filtration by using deionized water, and drying the obtained negative pole material in a blast drying box; obtaining a recovered negative electrode material;
step two: 0.1g of Silica (SiO) having a particle size distribution in the range D50 of 4 μm was takenx，0<x<2) Grinding the carbon source asphalt or sucrose in a ball mill with the mass ratio of asphalt to silicon monoxide being 4:100 to obtain a ground sample;
step three: premixing the sample ground in the step two with 10g of the recycled negative electrode material obtained in the step one, placing the mixed sample in a tube furnace, carrying out heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 750 ℃ for 2h and at 950 ℃ for 3h, keeping the temperature at the temperature rising speed of 5 ℃/min, cooling to room temperature, taking out, and obtaining SiOxA modified graphite material.
6. The method for recycling graphite negative electrodes of lithium ion batteries according to claim 1 or 2, characterized in that: SiO was prepared as followsxModified graphite material:
the method comprises the following steps: taking a lithium ion battery negative pole piece which is subjected to cyclic failure, collecting a negative pole material on the surface of a current collector, dispersing the negative pole material in deionized water, performing ultrasonic treatment for 10min, performing suction filtration, then dispersing in ethanol, performing ultrasonic treatment for 10min, performing suction filtration, performing ultrasonic-suction filtration treatment for 5 times respectively by using the deionized water and the ethanol, drying the negative pole material, then soaking the negative pole material for 3 hours by using dilute hydrochloric acid (HCl) with the concentration of 0.1M, performing suction filtration, repeatedly soaking and suction filtration by using the deionized water, and drying the obtained negative pole material in a blast drying box; obtaining a recovered negative electrode material;
step two: putting the recycled negative electrode material obtained in the step one into a tubular furnace, carrying out heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 650 ℃ for 2h and 900 ℃ for 3h, raising the temperature at 5 ℃/min, cooling to room temperature, taking out to obtain SiOxA modified graphite material.
7. SiO (silicon dioxide)xA modified graphitic material prepared according to the method of any one of claims 1 to 6.
8. SiO according to claim 7xThe modified graphite material is applied to the graphite cathode of the lithium ion battery.
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