CN113782858A - By SiOxMethod for increasing and recycling negative electrode capacity of lithium ion battery at @ C - Google Patents

By SiOxMethod for increasing and recycling negative electrode capacity of lithium ion battery at @ C Download PDF

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Publication number
CN113782858A
CN113782858A CN202111006266.3A CN202111006266A CN113782858A CN 113782858 A CN113782858 A CN 113782858A CN 202111006266 A CN202111006266 A CN 202111006266A CN 113782858 A CN113782858 A CN 113782858A
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China
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negative electrode
electrode material
sio
lithium ion
ion battery
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CN202111006266.3A
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Chinese (zh)
Inventor
崔大祥
葛美英
颜雪冬
刘鹏飞
张芳
卢玉英
王亚坤
王金
张放为
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Ningbo Veken Battery Co ltd
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Ningbo Polytechnic
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Ningbo Veken Battery Co ltd
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Ningbo Polytechnic
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Priority to CN202111006266.3A priority Critical patent/CN113782858A/en
Publication of CN113782858A publication Critical patent/CN113782858A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a method for preparing SiOxThe method for increasing and recovering the negative electrode capacity of the lithium ion battery by using the @ C mainly aims at the problem of recovering and reprocessing the negative electrode material of the waste battery, and the specific capacity loss of the graphite negative electrode material of the battery after failure existsxThe characteristic of high specific capacity modifies and recovers the cathode material, and adopts a one-step method to realize the carbon coating of SiOxThe material and the recycled cathode material are compounded to increase the capacity and solve the problem of SiOxThe problem of cycle performance attenuation caused by volume expansion in the charge-discharge cycle process is continuously used for manufacturing the lithium ion battery cathode material. 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.

Description

By SiOxMethod for increasing and recycling negative electrode capacity of lithium ion battery at @ C
Technical Field
The invention relates to a treatment problem of waste lithium ion batteries, in particular to a method for using SiOxA method for increasing and recycling negative electrode capacity of a lithium ion battery at @ C, belonging to the field of recycling of lithium ion battery materials.
Background
In recent years, with the wide application of lithium ion batteries, the demand for positive and negative electrode materials is increasing, and the recycling of waste batteries is a key problem.
The failure reasons of the lithium ion battery based on the graphite cathode system are often failure of electrolyte and a positive electrode, and the cathode graphite material has high stability, so that the lithium ion battery has a recycling value. However, the conductive agent, the binder and the like introduced in the pole piece manufacturing process are difficult to remove, and the direct recycling affects the electrochemical performance of the pole piece, especially the capacity exertion of the pole piece. Using high specific capacity SiOxThe material can increase the capacity of recycling the cathode material, and the invention uses SiOxThe @ C composite material is compounded with the recycled negative electrode, so that the gram capacity of the recycled negative electrode material can be increased, and simultaneously SiO can be overcomexThe problem of poor cycle performance caused by volume expansion during the cycle. The method has practical application value in promoting the recycling of the waste batteries.
Disclosure of Invention
The invention aims to provide a simple and feasible method for increasing gram capacity of a failed lithium ion battery cathode material.
The invention aims to provide a method for preparing SiOxThe method for increasing and recovering the negative electrode capacity of the lithium ion battery by @ C comprises the following steps:
taking the lithium ion battery after the cycle failure, discharging the battery to the state of charge of 10% SOC, disassembling, soaking the negative electrode material in deionized water for 2h, and collecting the negative electrode material; washing the collected negative electrode material with nitric acid with the concentration of 10%, taking the precipitate, then placing the precipitate in absolute ethyl alcohol, performing ultrasonic treatment for 1 hour, and performing spray drying to obtain a recovered negative electrode material;
the failed lithium ion battery is a lithium ion battery with the capacity reduced to below 60 percent of the initial capacity;
40-60 g of SiOxUniformly mixing 1-4 g of carbon source, uniformly mixing the powder and the carbon source in a mixer, uniformly mixing the mixture with 500g of recovered negative electrode material, performing heat treatment in an inert gas atmosphere at the heat treatment temperature of 650-750 ℃ for 2-3 h and at the heat treatment temperature of 850-950 ℃ for 3h, wherein the heating rate is 3-7 ℃/min, cooling the powder to room temperature, and taking out the powder to obtain carbon-coated SiOxA composite material with a recovered anode material;
said SiOxThe particle size distribution of the powder is D50 and is 3.2-3.8 microns; the carbon source is at least one of glucose, asphalt and nano-cellulose; the inert gas atmosphere is high-purity argon or high-purity nitrogen.
The method mainly aims at the problem of recycling and reprocessing the waste battery cathode material, and the specific capacity loss of the failed battery graphite cathode material existsxThe characteristic of high specific capacity modifies and recovers the cathode material, and adopts a one-step method to realize the carbon coating of SiOxThe material and the recycled cathode material are compounded to increase the capacity and solve the problem of SiOxThe problem of cycle performance attenuation caused by volume expansion in the charge-discharge cycle process is continuously used for manufacturing the lithium ion battery cathode material. The method has the advantages of capability of recycling the failed cathode material, simple preparation process, low preparation cost, stable performance and capability ofHas wide application prospect.
Drawings
FIG. 1 is a schematic view of a carbon-coated SiO filmxAnd a charge-discharge curve of the recovered negative electrode material.
Detailed Description
Example 1:
by SiOxThe method for increasing and recovering the negative electrode capacity of the lithium ion battery at @ C comprises the following steps:
step one, recycling a negative electrode material: taking a failure lithium ion battery with the capacity reduced to 50% of the initial capacity after circulation, discharging the battery to the state of charge of 10% SOC, disassembling, soaking a negative electrode material in deionized water for 2 hours, and collecting the negative electrode material; washing the collected negative electrode material with nitric acid with the concentration of 10%, taking the precipitate, then placing the precipitate in absolute ethyl alcohol, performing ultrasonic treatment for 1 hour, and performing spray drying to obtain a recovered negative electrode material;
step two: 60g of SiO with a particle size distribution D50 of 3.2 μmxAnd (2) mixing 4g of carbon source in a mass ratio of 1:1 of glucose and nanocellulose uniformly in a mixer, uniformly mixing the carbon source with 500g of the recycled negative electrode material obtained in the first step, performing heat treatment in a high-purity argon atmosphere at a heating rate of 7 ℃/min until the temperature reaches 750 ℃ for 2h, performing heat treatment at 950 ℃ for 3h, and cooling the powder to room temperature and taking out the powder to obtain the composite material of the carbon-coated SiOx and the recycled negative electrode material.
In this example, the prepared carbon-coated SiOxThe composite material of the recycled negative electrode material, a binder (CMC), a conductive agent (SP) and SBR are mixed according to 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, performing charge and discharge test at the ambient temperature of 25 ℃, wherein the gram capacity is 426.4mAh/g, charging and discharging are performed by 0.8mA/g, the cycle is 200 weeks, and the capacity retention rate is 83.5%.
Example 2
By SiOxThe method for increasing and recovering the negative electrode capacity of the lithium ion battery with @ C is similar to the method of the embodiment 1, and comprises the following steps:
step one, recycling a negative electrode material: taking a failure lithium ion battery with the capacity reduced to 50% of the initial capacity after circulation, discharging the battery to the state of charge of 10% SOC, disassembling, soaking a negative electrode material in deionized water for 2 hours, and collecting the negative electrode material; washing the collected negative electrode material with nitric acid with the concentration of 10%, taking the precipitate, then placing the precipitate in absolute ethyl alcohol, performing ultrasonic treatment for 1 hour, and performing spray drying to obtain a recovered negative electrode material;
step two: 50g of SiO having a particle size distribution D50 of 3.5 μm were takenxPowder, taking 4g of carbon source according to the mass ratio of 1:4 of glucose and nano-cellulose, uniformly mixing the carbon source and 500g of recycled negative electrode material obtained in the first step after uniformly mixing the carbon source and the recycled negative electrode material in a mixer, carrying out heat treatment in the atmosphere of high-purity argon gas at the temperature rise speed of 7 ℃/min and the heat treatment temperature of 700 ℃ for 2h and at the temperature of 950 ℃ for 3h, taking out the powder after the temperature of the powder is reduced to room temperature, and obtaining carbon-coated SiOxA composite material with a recovered anode material;
in this example, the prepared carbon-coated SiOxThe composite material of the recycled negative electrode material, a binder (CMC), a conductive agent (SP) and SBR are mixed according to 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, performing charge and discharge test at the ambient temperature of 25 ℃, wherein the gram capacity is 417mAh/g, charging and discharging are performed by 0.8mA/g, the cycle is 200 weeks, and the capacity retention rate is 89.6%.
Example 3:
by SiOxThe method for increasing and recovering the negative electrode capacity of the lithium ion battery with @ C is similar to the method of the embodiment 1, and comprises the following steps:
step one, recycling a negative electrode material: taking a failure lithium ion battery with the capacity reduced to 50% of the initial capacity after circulation, discharging the battery to the state of charge of 10% SOC, disassembling, soaking a negative electrode material in deionized water for 2 hours, and collecting the negative electrode material; washing the collected negative electrode material with nitric acid with the concentration of 10%, taking the precipitate, then placing the precipitate in absolute ethyl alcohol, performing ultrasonic treatment for 1 hour, and performing spray drying to obtain a recovered negative electrode material;
step two: 40g of SiO having a particle size distribution D50 of 3.2 μm were takenxMixing 4g of carbon source according to the mass ratio of 1:1 of asphalt to nano-cellulose in a mixer, uniformly mixing the carbon source with 500g of the recycled negative electrode material obtained in the step one, and performing heat treatment in a high-purity argon atmosphere at the temperature rise speed of 3 ℃/min and the heat treatment temperatureKeeping the temperature at 700 ℃ for 2h and at 850 ℃ for 3h, taking out the powder after the temperature of the powder is reduced to room temperature to obtain carbon-coated SiOxA composite material with a recovered anode material;
the carbon-coated SiO prepared in this examplexThe composite material of the recycled negative electrode material, a binder (CMC), a conductive agent (SP) and SBR are mixed according to 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, performing charge and discharge test at the ambient temperature of 25 ℃, wherein the gram capacity is 438mAh/g, charging and discharging are performed by 0.8mA/g, the cycle is 200 weeks, and the capacity retention rate is 88.9%.

Claims (6)

1. By SiOxThe method for increasing and recovering the negative electrode capacity of the lithium ion battery is characterized by comprising the following steps of:
step one, recycling a negative electrode material: discharging the lithium ion battery after the cycle failure until the electric quantity is 10% SOC, disassembling, soaking the negative electrode material in deionized water for 2 hours, and collecting the negative electrode material; washing the collected negative electrode material with nitric acid with the concentration of 10%, taking the precipitate, then placing the precipitate in absolute ethyl alcohol, performing ultrasonic treatment for 1 hour, and performing spray drying to obtain a recovered negative electrode material;
step two: 40-60 g of SiOxAnd uniformly mixing the powder and 1-4 g of carbon source, uniformly mixing the mixture in a mixer, uniformly mixing the mixture with 500g of the recycled negative electrode material obtained in the step one, performing heat treatment in an inert gas atmosphere at a heating rate of 3-7 ℃/min to 650-750 ℃ for 2-3 h, performing heat preservation at 850-950 ℃ for 3h, and taking out the powder after the temperature of the powder is reduced to room temperature to obtain the composite material of the carbon-coated SiOx and the recycled negative electrode material.
2. A method of using SiO as claimed in claim 1xThe method for increasing and recycling the negative electrode capacity of the lithium ion battery is characterized by comprising the following steps of: and step one, the failed lithium ion battery is the lithium ion battery with the capacity reduced to the initial capacity of below 60%.
3. A method of using SiO as claimed in claim 1xThe method for increasing and recycling the negative electrode capacity of the lithium ion battery is characterized by comprising the following steps of:SiO as described in step twoxThe particle size distribution of the powder is D50 and is 3.2-3.8 microns; the carbon source is at least one of glucose, asphalt or nano-cellulose; the inert gas atmosphere is high-purity argon or high-purity nitrogen.
4. A method of using SiO as claimed in any one of claims 1 to 3xThe method for increasing and recycling the negative electrode capacity of the lithium ion battery is characterized by comprising the following steps of: comprises the following steps:
step one, recycling a negative electrode material: taking a failure lithium ion battery with the capacity reduced to 50% of the initial capacity after circulation, discharging the battery to the state of charge of 10% SOC, disassembling, soaking a negative electrode material in deionized water for 2 hours, and collecting the negative electrode material; washing the collected negative electrode material with nitric acid with the concentration of 10%, taking the precipitate, then placing the precipitate in absolute ethyl alcohol, performing ultrasonic treatment for 1 hour, and performing spray drying to obtain a recovered negative electrode material;
step two: 60g of SiO with a particle size distribution D50 of 3.2 μmxAnd (2) mixing 4g of carbon source in a mass ratio of 1:1 of glucose and nanocellulose uniformly in a mixer, uniformly mixing the carbon source with 500g of the recycled negative electrode material obtained in the first step, performing heat treatment in a high-purity argon atmosphere at a heating rate of 7 ℃/min until the temperature reaches 750 ℃ for 2h, performing heat treatment at 950 ℃ for 3h, and cooling the powder to room temperature and taking out the powder to obtain the composite material of the carbon-coated SiOx and the recycled negative electrode material.
5. A method of using SiO as claimed in any one of claims 1 to 3xThe method for increasing and recycling the negative electrode capacity of the lithium ion battery is characterized by comprising the following steps of: comprises the following steps:
step one, recycling a negative electrode material: taking a failure lithium ion battery with the capacity reduced to 50% of the initial capacity after circulation, discharging the battery to the state of charge of 10% SOC, disassembling, soaking a negative electrode material in deionized water for 2 hours, and collecting the negative electrode material; washing the collected negative electrode material with nitric acid with the concentration of 10%, taking the precipitate, then placing the precipitate in absolute ethyl alcohol, performing ultrasonic treatment for 1 hour, and performing spray drying to obtain a recovered negative electrode material;
step two: 50g of SiO having a particle size distribution D50 of 3.5 μm were takenxThe powder is prepared by mixing the components of the powder,taking 4g of carbon source according to the mass ratio of 1:4 of glucose to nanocellulose, placing the carbon source in a mixer to be uniformly mixed, uniformly mixing the carbon source with 500g of the recycled negative electrode material obtained in the step one, placing the mixture in a high-purity argon atmosphere for heat treatment, keeping the temperature for 2h at the temperature rising speed of 7 ℃/min and the heat treatment temperature for 700 ℃, keeping the temperature for 3h at the temperature of 950 ℃, taking out the mixture after the powder is cooled to room temperature, and obtaining carbon-coated SiOxAnd recovering the negative electrode material.
6. A method of using SiO as claimed in any one of claims 1 to 3xThe method for increasing and recycling the negative electrode capacity of the lithium ion battery is characterized by comprising the following steps of: comprises the following steps:
step one, recycling a negative electrode material: taking a failure lithium ion battery with the capacity reduced to 50% of the initial capacity after circulation, discharging the battery to the state of charge of 10% SOC, disassembling, soaking a negative electrode material in deionized water for 2 hours, and collecting the negative electrode material; washing the collected negative electrode material with nitric acid with the concentration of 10%, taking the precipitate, then placing the precipitate in absolute ethyl alcohol, performing ultrasonic treatment for 1 hour, and performing spray drying to obtain a recovered negative electrode material;
step two: 40g of SiO having a particle size distribution D50 of 3.2 μm were takenxPowder, namely, taking 4g of carbon source according to the mass ratio of 1:1 of asphalt to nanocellulose, putting the carbon source into a mixer for uniform mixing, then uniformly mixing the carbon source with 500g of the recycled negative electrode material obtained in the step one, putting the mixture into a high-purity argon gas atmosphere for heat treatment, keeping the temperature for 2h at the temperature rising speed of 3 ℃/min and the heat treatment temperature of 700 ℃, keeping the temperature for 3h at the temperature of 850 ℃, taking the powder out after the temperature of the powder is reduced to room temperature, and obtaining carbon-coated SiOxAnd recovering the negative electrode material.
CN202111006266.3A 2021-08-30 2021-08-30 By SiOxMethod for increasing and recycling negative electrode capacity of lithium ion battery at @ C Pending CN113782858A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104466185A (en) * 2014-11-12 2015-03-25 中国科学院深圳先进技术研究院 Silicon/carbon negative electrode composite material and preparation method thereof as well as lithium ion battery and negative electrode thereof
CN105356001A (en) * 2015-12-14 2016-02-24 天津理工大学 Repairing modifying method of cathode waste material of waste lithium ion battery
CN106935836A (en) * 2017-04-26 2017-07-07 宁夏博尔特科技有限公司 Lithium ion battery Si oxide and carbon compound cathode materials and preparation method thereof
US20180205074A1 (en) * 2017-01-19 2018-07-19 Optimum Battery Co., Ltd. Method for preparing silicon-carbon composite, negative electrode, and lithium ion battery
CN108493438A (en) * 2018-04-27 2018-09-04 天津巴莫科技股份有限公司 A kind of lithium ion battery SiOxBase composite negative pole material and preparation method thereof
CN110828786A (en) * 2019-10-09 2020-02-21 兰溪致德新能源材料有限公司 Preparation method of long-cycle silicon oxide/carbon composite negative electrode material
CN111362269A (en) * 2020-03-09 2020-07-03 上海电气集团股份有限公司 Preparation method of SEI (solid electrolyte interphase) film of lithium ion battery cathode, lithium ion battery cathode material and application of lithium ion battery cathode material
CN112421008A (en) * 2020-11-23 2021-02-26 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of carbon-coated silicon monoxide material for lithium ion battery cathode, product and application thereof
CN113036255A (en) * 2021-02-26 2021-06-25 广东邦普循环科技有限公司 Method for preparing silicon-carbon composite material by using waste lithium ion battery cathode and application

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104466185A (en) * 2014-11-12 2015-03-25 中国科学院深圳先进技术研究院 Silicon/carbon negative electrode composite material and preparation method thereof as well as lithium ion battery and negative electrode thereof
CN105356001A (en) * 2015-12-14 2016-02-24 天津理工大学 Repairing modifying method of cathode waste material of waste lithium ion battery
US20180205074A1 (en) * 2017-01-19 2018-07-19 Optimum Battery Co., Ltd. Method for preparing silicon-carbon composite, negative electrode, and lithium ion battery
CN106935836A (en) * 2017-04-26 2017-07-07 宁夏博尔特科技有限公司 Lithium ion battery Si oxide and carbon compound cathode materials and preparation method thereof
CN108493438A (en) * 2018-04-27 2018-09-04 天津巴莫科技股份有限公司 A kind of lithium ion battery SiOxBase composite negative pole material and preparation method thereof
CN110828786A (en) * 2019-10-09 2020-02-21 兰溪致德新能源材料有限公司 Preparation method of long-cycle silicon oxide/carbon composite negative electrode material
CN111362269A (en) * 2020-03-09 2020-07-03 上海电气集团股份有限公司 Preparation method of SEI (solid electrolyte interphase) film of lithium ion battery cathode, lithium ion battery cathode material and application of lithium ion battery cathode material
CN112421008A (en) * 2020-11-23 2021-02-26 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of carbon-coated silicon monoxide material for lithium ion battery cathode, product and application thereof
CN113036255A (en) * 2021-02-26 2021-06-25 广东邦普循环科技有限公司 Method for preparing silicon-carbon composite material by using waste lithium ion battery cathode and application

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