CN113582171B - Method for recycling graphite negative electrode of lithium ion battery - Google Patents
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- C01B33/113—Silicon oxides; Hydrates thereof
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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- 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 recycling graphite cathodes of lithium ion batteries, which is characterized in that spent lithium ion batteries are collected, cathode materials are collected, the collected cathode materials are fully washed to obtain recycled cathode materials, the method solves the problem of recycling waste battery cathode materials, and capacity loss exists in the recycling process of the spent cathode materials. In order to alleviate the problem of poor cycling stability caused by volume expansion of the silicon material in the charge-discharge process, the silicon is subjected to carbon coating to serve as a buffer layer. The method has the advantages of simple preparation process, low preparation cost and stable performance, solves the problem of waste battery treatment, and has wide application prospect. The method solves the problem of recycling the waste battery cathode material.
Description
Technical Field
The invention relates to the treatment problem of waste lithium ion batteries, in particular to a method for recycling graphite cathodes of lithium ion batteries, and a method for recycling waste battery cathode materials.
Background
In recent years, with the widespread use of lithium ion batteries, the recovery treatment of waste batteries has become an important issue. The waste lithium ion batteries are recycled and disassembled, and the anode and cathode materials are reused after being treated, so that the method is an important direction for further promoting energy conservation and emission reduction.
At present, the commercial lithium ion battery cathode material is mainly graphite, and the graphite still has very good telephony performance after the battery cathode material is recovered after failure due to high stability, however, the specific capacity of the recovered cathode material is obviously reduced compared with the specific capacity of the commercial graphite material due to the introduction of materials such as conductive agents, binders and the like in the process of manufacturing pole pieces, and in order to improve the specific capacity of the recovered cathode material, the invention combines the recovered cathode material with the silicon material, fully utilizes the characteristic of high specific capacity of the silicon material, improves the specific capacity of the recovered cathode, and further promotes the recycling problem of the waste battery cathode material.
Disclosure of Invention
The invention aims to provide a method for recycling a graphite cathode of a lithium ion battery, which is simple and feasible and is used for preparing SiO x A modified graphite material.
Still another object of the present invention is: providing the SiO x Use of modified graphite materials.
The invention aims at realizing the following technical scheme: the method for recycling the graphite cathode of the lithium ion battery comprises the following steps of:
step one: collecting a negative electrode plate of a lithium ion battery after circulation failure, collecting a negative electrode material on the surface of a current collector, dispersing the negative electrode material in deionized water, carrying out suction filtration after ultrasonic treatment for 10min, dispersing in ethanol, carrying out ultrasonic treatment for 10min, carrying out suction filtration, respectively carrying out ultrasonic-suction filtration on the negative electrode material with deionized water and ethanol for 5-10 times, drying the negative electrode material, soaking the negative electrode material in 0.08-0.2M dilute hydrochloric acid (HCl) for 2-3 h, carrying out suction filtration, soaking and suction filtration with deionized water for multiple times, and drying the obtained negative electrode material in a blast drying oven; obtaining a recovered negative electrode material;
step two: 0 to 1g of silicon oxide (SiO) with a particle size distribution ranging from 3 to 4 mu m in D50 is taken x ,0<x<2) Grinding the silicon dioxide 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 oxide 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 anode material obtained in the first step, placing the mixed sample in a tube furnace, performing heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 650-750 ℃ for 2-4 h, keeping the heat treatment temperature at 900-950 ℃ for 2-3 h, keeping the temperature rising speed at 3-6 ℃/min, cooling to room temperature, and taking out to obtain SiO x A modified graphite material.
The method realizes the reutilization of the recovered anode material by compounding the recovered anode material with the silicon material.
The lithium ion battery after the failure in the first step is a lithium ion battery with the capacity of less than 80% of the initial capacity, and the method for taking the negative electrode plate comprises the steps of disassembling the lithium ion battery in an environment with the humidity lower than 10% to obtain the negative electrode plate.
The invention also provides the SiO obtained x The modified graphite material can be used for a lithium ion battery cathode. Test results show that the material can improve the specific capacity and the rate capability of the recovered negative electrode.
The invention provides a simple recovery and capacity expansion method for the waste battery cathode material, which can greatly improve the specific capacity of the recovered cathode, has simple preparation process and low preparation cost, and has practical application value for the recovery and reuse of the pushed waste battery. The method solves the problem of recycling of the waste battery anode material, and the capacity loss problem exists in the recycling process of the anode material after failure. In order to alleviate the problem of poor cycling stability caused by volume expansion of the silicon material in the charge-discharge process, the silicon is subjected to carbon coating to serve as a buffer layer. The preparation method disclosed by the invention is simple in preparation process, low in preparation cost and stable in performance of the obtained product, solves the problem of treatment of waste batteries, and has a wide application prospect.
Drawings
FIG. 1 is SiO x Cycle data for the modified graphite material.
Detailed Description
Example 1:
a method for recycling graphite cathode of lithium ion battery, which realizes recycling of the recycled cathode by attaching the recycled cathode material and a silicon material, comprises the following steps of x Modified graphite material:
step one: collecting a negative electrode plate of a lithium ion battery after circulation failure, collecting a negative electrode material on the surface of a current collector, dispersing the negative electrode material in deionized water, carrying out suction filtration after ultrasonic treatment for 10min, dispersing in ethanol, carrying out ultrasonic treatment for 10min, carrying out suction filtration, respectively carrying out ultrasonic-suction filtration on the negative electrode material with deionized water and ethanol for 5 times, drying the negative electrode material, then soaking the negative electrode material in dilute hydrochloric acid (HCl) with the concentration of 0.1M for 3h, carrying out suction filtration, soaking the negative electrode material in deionized water for multiple times, carrying out suction filtration, and drying the obtained negative electrode material in a blast drying box; obtaining a recovered negative electrode material;
step two: 1g of silicon oxide (SiO) having a particle size distribution in the range of 3 μm D50 was taken x ,0<x<2) Grinding the mixture and asphalt as carbon source in a ball mill, wherein the mass ratio of asphalt to silicon oxide is 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 anode material obtained in the first step, placing the mixed sample in a tube furnace, performing 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 rising speed at 5 ℃/min, cooling to room temperature, and taking out to obtain SiO x A modified graphite material.
SiO obtained in this example x Modified graphiteThe mass ratio of the material to the binder (CMC) to the conductive agent (SP) to the SBR is 8:0.5:1:0.5 is mixed into slurry to prepare a working electrode, the working electrode is stood for more than 10 hours after being assembled into a button cell, and a charge and discharge test is carried out at the ambient temperature of 25 ℃, wherein the gram capacity is 479.4mAh/g. Fig. 1 is cycle data of a coin cell, and it can be seen from the graph that the capacity retention rate of the cell after 300 cycles is 87.2%.
Example 2:
a method for recycling graphite cathode of lithium ion battery is similar to the step of example 1, and SiO is prepared according to the following steps x Modified graphite material:
step one: collecting a negative electrode plate of a lithium ion battery after circulation failure, collecting a negative electrode material on the surface of a current collector, dispersing the negative electrode material in deionized water, carrying out ultrasonic treatment for 10min, carrying out suction filtration, dispersing in ethanol, carrying out ultrasonic treatment for 10min, carrying out suction filtration, respectively carrying out ultrasonic-suction filtration treatment on the negative electrode material with deionized water and ethanol for 10 times, drying the negative electrode material, then soaking the negative electrode material in dilute hydrochloric acid (HCl) with the concentration of 0.2M for 3h, carrying out suction filtration, soaking the negative electrode material in deionized water for multiple times, carrying out suction filtration, and drying the obtained negative electrode material in a blast drying box; obtaining a recovered negative electrode material;
step two: 0.5g of silicon oxide (SiO) having a particle size distribution in the range of 4 μm D50 was taken x ,0<x<2) Grinding the mixture and asphalt as carbon source in a ball mill, wherein the mass ratio of asphalt to silicon oxide is 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 anode material obtained in the first step, placing the mixed sample in a tube furnace, performing 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 rising speed at 5 ℃/min, cooling to room temperature, and taking out to obtain SiO x A modified graphite material.
SiO obtained in this example x The modified graphite material, a binder (CMC) and a conductive agent (SP) and SBR are mixed according to a mass ratio of 8:0.5:1:0.5 is mixed into slurry to prepare a working electrode, the working electrode is stood for more than 10 hours after being assembled into a button cell, and a charge and discharge test is carried out at the ambient temperature of 25 ℃, wherein the gram capacity is 408.7mAh/g.
Example 3:
a method for recycling graphite cathode of lithium ion battery is similar to the step of example 1, and SiO is prepared according to the following steps x Modified graphite material:
step one: collecting a negative electrode plate of a lithium ion battery after circulation failure, collecting a negative electrode material on the surface of a current collector, dispersing the negative electrode material in deionized water, carrying out suction filtration after ultrasonic treatment for 10min, dispersing in ethanol, carrying out ultrasonic treatment for 10min, carrying out suction filtration, respectively carrying out ultrasonic-suction filtration on the negative electrode material with deionized water and ethanol for 5 times, drying the negative electrode material, then soaking the negative electrode material in dilute hydrochloric acid (HCl) with the concentration of 0.2M for 3h, carrying out suction filtration, soaking the negative electrode material in deionized water for multiple times, carrying out suction filtration, and drying the obtained negative electrode material in a blast drying box; obtaining a recovered negative electrode material;
step two: 0.1g of silicon oxide (SiO) having a particle size distribution in the range of 4 μm D50 was taken x ,0<x<2) Grinding the mixture with carbon source asphalt or sucrose in a ball mill, wherein the mass ratio of the asphalt to the silicon oxide is 4:100, so as to obtain a ground sample;
step three: premixing the ground sample in the second step with 10g of the recycled anode material obtained in the first step, placing the mixed sample in a tube furnace, performing heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 750 ℃ for 2h, keeping the heat treatment temperature at 950 ℃ for 3h, keeping the temperature rise speed at 5 ℃/min, cooling to room temperature, and taking out to obtain SiO x A modified graphite material.
SiO obtained in this example x The modified graphite material, a binder (CMC) and a conductive agent (SP) and SBR are mixed according to a mass ratio of 8:0.5:1:0.5 is mixed into slurry to prepare a working electrode, the working electrode is stood for more than 10 hours after being assembled into a button cell, and a charge and discharge test is carried out at the ambient temperature of 25 ℃, wherein the gram capacity is 338.7mAh/g.
Example 4:
a method for recycling graphite cathode of lithium ion battery is similar to the step of example 1, except that silicon oxide is 0, namely the original step II is omitted, and SiO is prepared according to the following steps x Modified graphite material:
step one: collecting a negative electrode plate of a lithium ion battery after circulation failure, collecting a negative electrode material on the surface of a current collector, dispersing the negative electrode material in deionized water, carrying out suction filtration after ultrasonic treatment for 10min, dispersing in ethanol, carrying out ultrasonic treatment for 10min, carrying out suction filtration, respectively carrying out ultrasonic-suction filtration on the negative electrode material with deionized water and ethanol for 5 times, drying the negative electrode material, then soaking the negative electrode material in dilute hydrochloric acid (HCl) with the concentration of 0.1M for 3h, carrying out suction filtration, soaking the negative electrode material in deionized water for multiple times, carrying out suction filtration, and drying the obtained negative electrode material in a blast drying box; obtaining a recovered negative electrode material;
step two: placing the recovered cathode material obtained in the step one into a tube furnace, performing heat treatment under 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 a heating speed of 5 ℃/min, cooling to room temperature, and taking out to obtain SiO x A modified graphite material.
The material prepared in this example is not SiO-free x Modified recycled anode material, mixing the obtained material with a binder (CMC) and a conductive agent (SP) and SBR according to a mass ratio of 8:0.5:1:0.5 is mixed into slurry to prepare a working electrode, the working electrode is stood for more than 10 hours after being assembled into a button cell, and charge and discharge tests are carried out at the ambient temperature of 25 ℃, wherein the gram capacity is 293.4mAh/g.
Claims (7)
1. The method for recycling the graphite cathode of the lithium ion battery is characterized in that the method for recycling the graphite cathode of the lithium ion battery is characterized by comprising the following steps of:
step one: collecting a negative electrode plate of a lithium ion battery after circulation failure, collecting a negative electrode material on the surface of a current collector, dispersing the negative electrode material in deionized water, carrying out suction filtration after ultrasonic treatment for 10min, dispersing in ethanol, carrying out ultrasonic treatment for 10min, carrying out suction filtration, respectively carrying out ultrasonic-suction filtration on the negative electrode material with deionized water and ethanol for 5-10 times, drying the negative electrode material, soaking the negative electrode material in 0.08-0.2M dilute hydrochloric acid (HCl) for 2-3 h, carrying out suction filtration, soaking and suction filtration with deionized water for multiple times, and drying the obtained negative electrode material in a blast drying oven; obtaining a recovered negative electrode material;
step two: 0-1 g of silicon oxide SiO with the particle size distribution range of 3-4 mu m in D50 is taken x ,0<x<2, placing the mixture and the carbon source in a ball millGrinding, wherein the carbon source is at least one of asphalt or sucrose, and the mass ratio of the carbon source to the silicon oxide 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 anode material obtained in the first step, placing the mixed sample in a tube furnace, performing heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 650-750 ℃ for 2-4 h, keeping the heat treatment temperature at 900-950 ℃ for 2-3 h, keeping the temperature rising speed at 3-6 ℃/min, cooling to room temperature, and taking out to obtain SiO x A modified graphite material.
2. The method for recycling graphite negative electrode of lithium ion battery according to claim 1, wherein: the lithium ion battery after the failure is a lithium ion battery with the capacity reduced to less than 80% of the initial capacity, and the method for taking the negative electrode plate comprises the steps of disassembling the lithium ion battery in an environment with the humidity lower than 10% to obtain the negative electrode plate.
3. A method for recovering graphite negative electrode of lithium ion battery according to claim 1 or 2, characterized in that: siO was prepared as follows x Modified graphite material:
step one: collecting a negative electrode plate of a lithium ion battery after circulation failure, collecting a negative electrode material on the surface of a current collector, dispersing the negative electrode material in deionized water, carrying out suction filtration after ultrasonic treatment for 10min, dispersing in ethanol, carrying out ultrasonic treatment for 10min, carrying out suction filtration, respectively carrying out ultrasonic-suction filtration on the negative electrode material with deionized water and ethanol for 5 times, drying the negative electrode material, then soaking the negative electrode material in dilute hydrochloric acid (HCl) with the concentration of 0.1M for 3h, carrying out suction filtration, soaking the negative electrode material in deionized water for multiple times, carrying out suction filtration, and drying the obtained negative electrode material in a blast drying box; obtaining a recovered negative electrode material;
step two: 1g of silicon oxide SiO with a particle size distribution in the range of 3 μm D50 was taken x ,0<x<2, grinding the mixture and asphalt as a carbon source in a ball mill, wherein the mass ratio of the asphalt to the silicon oxide is 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 anode material obtained in the first step, and placing the mixed sampleHeat treatment is carried out in a tube furnace under the high-purity argon atmosphere, the heat treatment temperature is kept at 650 ℃ for 2h, the heat treatment temperature is kept at 900 ℃ for 3h, the heating speed is 5 ℃/min, the temperature is reduced to the room temperature, and the SiO is obtained after the temperature is taken out x A modified graphite material.
4. A method for recovering graphite negative electrode of lithium ion battery according to claim 1 or 2, characterized in that: siO was prepared as follows x Modified graphite material:
step one: collecting a negative electrode plate of a lithium ion battery after circulation failure, collecting a negative electrode material on the surface of a current collector, dispersing the negative electrode material in deionized water, carrying out ultrasonic treatment for 10min, carrying out suction filtration, dispersing in ethanol, carrying out ultrasonic treatment for 10min, carrying out suction filtration, respectively carrying out ultrasonic-suction filtration treatment on the negative electrode material with deionized water and ethanol for 10 times, drying the negative electrode material, then soaking the negative electrode material in dilute hydrochloric acid (HCl) with the concentration of 0.2M for 3h, carrying out suction filtration, soaking the negative electrode material in deionized water for multiple times, carrying out suction filtration, and drying the obtained negative electrode material in a blast drying box; obtaining a recovered negative electrode material;
step two: 0.5g of silicon oxide SiO with a particle size distribution in the range of 4 μm D50 was taken x ,0<x<2, grinding the mixture and asphalt as a carbon source in a ball mill, wherein the mass ratio of the asphalt to the silicon oxide is 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 anode material obtained in the first step, placing the mixed sample in a tube furnace, performing 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 rising speed at 5 ℃/min, cooling to room temperature, and taking out to obtain SiO x A modified graphite material.
5. A method for recovering graphite negative electrode of lithium ion battery according to claim 1 or 2, characterized in that: siO was prepared as follows x Modified graphite material:
step one: collecting a negative electrode plate of a lithium ion battery after circulation failure, collecting a negative electrode material on the surface of a current collector, dispersing the negative electrode material in deionized water, carrying out suction filtration after ultrasonic treatment for 10min, dispersing in ethanol, carrying out ultrasonic treatment for 10min, carrying out suction filtration, respectively carrying out ultrasonic-suction filtration on the negative electrode material with deionized water and ethanol for 5 times, drying the negative electrode material, then soaking the negative electrode material in dilute hydrochloric acid (HCl) with the concentration of 0.2M for 3h, carrying out suction filtration, soaking the negative electrode material in deionized water for multiple times, carrying out suction filtration, and drying the obtained negative electrode material in a blast drying box; obtaining a recovered negative electrode material;
step two: 0.1g of silicon oxide SiO with a particle size distribution in the range of 4 μm D50 was taken x ,0<x<2, grinding the mixture with carbon source asphalt or sucrose in a ball mill, wherein the mass ratio of the asphalt to the silicon oxide is 4:100, so as to obtain a ground sample;
step three: premixing the ground sample in the second step with 10g of the recycled anode material obtained in the first step, placing the mixed sample in a tube furnace, performing heat treatment in a high-purity argon atmosphere, keeping the heat treatment temperature at 750 ℃ for 2h, keeping the heat treatment temperature at 950 ℃ for 3h, keeping the temperature rise speed at 5 ℃/min, cooling to room temperature, and taking out to obtain SiO x A modified graphite material.
6. SiO (silicon dioxide) x A modified graphite material prepared according to any of the methods of claims 1 to 5.
7. A SiO according to claim 6 x The modified graphite material is applied to a graphite cathode of a lithium ion battery.
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