CN110444830B - Combined treatment method for negative electrode and diaphragm of waste lithium ion battery - Google Patents

Combined treatment method for negative electrode and diaphragm of waste lithium ion battery Download PDF

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CN110444830B
CN110444830B CN201910588579.0A CN201910588579A CN110444830B CN 110444830 B CN110444830 B CN 110444830B CN 201910588579 A CN201910588579 A CN 201910588579A CN 110444830 B CN110444830 B CN 110444830B
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diaphragm
lithium ion
ion battery
negative electrode
waste lithium
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CN110444830A (en
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田忠良
赖延清
李松贤
罗飞林
龚培育
张凯
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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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  • Organic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
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  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a combined treatment method of a cathode and a diaphragm of a waste lithium ion battery, which comprises the following steps: (1) crushing and mixing a waste lithium ion battery cathode and a diaphragm to obtain mixed fragments, wherein the mass ratio of the cathode to the diaphragm is 5-10: 1; (2) placing the mixed fragments in a mixed solvent, stirring for 3-6 h at 70-140 ℃, separating and recovering the copper foil from the solution, performing ultrasonic treatment on the residual solution at 0-70 ℃, separating to obtain a solid and a filtrate, and collecting the filtrate to return to the step (2) for reuse as the solvent; (3) and (3) putting the solid in an inert atmosphere for high-temperature carbonization to obtain the composite carbon material. The method can realize high added value utilization of the waste lithium ion battery carbon material and the diaphragm, and can also recover the copper foil in a simple substance form, and has the advantages of simple operation, low cost, environmental protection and the like.

Description

Combined treatment method for negative electrode and diaphragm of waste lithium ion battery
Technical Field
The invention belongs to the technical field of waste battery recovery, and particularly relates to a combined treatment method of a negative electrode and a diaphragm of a waste lithium ion battery.
Background
Lithium Ion Batteries (LIBs) have been widely used in the fields of 3C digital products and new energy vehicles due to their advantages of high specific energy, wide operating temperature range, no memory effect, etc. Taking a power lithium ion battery as an example, as the service life of the power lithium ion battery is limited (3-5 years), with the rapid development of new energy industry, about 12-17 million tons of waste power batteries need to be recycled in 2020, otherwise harmful substances in the waste power batteries can cause serious pollution to the atmosphere, water and soil.
At present, the recovery method of the waste lithium ion battery negative electrode mainly comprises pyrogenic recovery and wet recovery. The pyrogenic process recovery requires a high-temperature roasting method to remove the binder, so that the active substance is separated from the current collector, the requirement on equipment is high, the energy consumption is high, the recovered graphite contains metal oxide impurities, and the copper foil cannot be recovered in a simple substance form. Therefore, in order to avoid the above problems, the recovery of the cathode of the waste lithium ion battery is mainly based on wet recovery. Patent CN201710386043 discloses a method for recycling copper foil and graphite, in which a waste lithium battery negative electrode is soaked in a 1-3 mol/L sulfuric acid solution to completely separate the graphite from the copper foil; then taking out the copper foil, washing with water, and drying to obtain a copper foil product; filtering, drying and recovering the graphite-containing solution to obtain a graphite product. Compared with commercial negative electrode graphite, the edge and the surface of the layer of the recycled graphite become unstable along with the circulation in the battery circulation process, and the phenomena of graphite layer expansion and edge peeling occur, so that the recycled graphite product cannot be compared with commercial carbonaceous materials, and the competitive advantage is not obvious.
With the increasing number of scrapped lithium ion batteries, the number of waste diaphragm materials is increased year by year, and the treatment of waste diaphragms has not been paid attention by people and is still a subject with potential and challenge. The novel carbon material prepared by using the waste diaphragm material has the natural advantage of low cost, and can reduce the pollution to the atmosphere, water and soil.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a combined treatment method of a waste lithium ion battery cathode and a diaphragm, which realizes high value-added utilization of a waste lithium ion battery cathode carbon material and the diaphragm, and can recover copper foil in a simple substance form, and has the advantages of simple operation, low cost, environmental friendliness and the like.
The negative electrode of the invention refers to a battery negative electrode formed by loading a carbon material on a copper foil through a binder; wherein, the carbon material is a material mixed by graphite and conductive carbon black according to a certain proportion; the binder is one or a mixture of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA) and Styrene Butadiene Rubber (SBR).
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a combined treatment method for a negative electrode and a diaphragm of a waste lithium ion battery comprises the following steps:
(1) crushing and mixing a waste lithium ion battery cathode and a diaphragm to obtain mixed fragments, wherein the mass ratio of the cathode to the diaphragm is 5-10: 1;
(2) placing the mixed fragments in a mixed solvent, stirring for 3-6 h at 70-140 ℃, separating and recovering the copper foil from the solution, performing ultrasonic treatment on the residual solution at 0-70 ℃, separating to obtain a solid and a filtrate, and collecting the filtrate to return to the step (2) for reuse as the solvent;
(3) and (3) putting the solid in an inert atmosphere for high-temperature carbonization to obtain the composite carbon material.
Preferably, in the step (1), the separator is selected from any one of a Polyethylene (PE) separator, a polypropylene (PP) separator, a PE-PP double-layer separator, and a PE-PP-PE triple-layer separator.
Preferably, in the step (1), the negative electrode and the diaphragm are crushed into 0.5-3 cm2Of the chip (a).
Preferably, in the step (2), the liquid-solid mass ratio of the mixed fragments to the mixed solvent is 5-10: 1.
Preferably, in the step (2), the mixed solvent is water (H)2O), N-methylpyrrolidone (NMP), N-Dimethylacetamide (DMA), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), Tetrahydrofuran (THF) and at least one of toluene, p-xylene, amyl acetate and trichloroethylene, wherein the volume ratio of the N, N-Dimethylformamide (DMSO) to the Tetrahydrofuran (THF) is 2-5: 1.
Preferably, in the step (2), the stirring manner is at least one selected from mechanical stirring, gas flow stirring and jet stirring.
Preferably, in the step (2), the ultrasonic conditions are as follows: the ultrasonic power is 400-800W, the ultrasonic frequency is 20-300 kHz, and the ultrasonic time is 1-3 h.
Preferably, in the step (3), the inert gas is at least one selected from nitrogen and argon, and the gas flow rate is 30-100 mL/min.
Preferably, in the step (3), the high-temperature carbonization conditions are as follows: the heating rate is 1-10 ℃/min, the carbonization temperature is 600-1000 ℃, and the carbonization time is 3-7 h.
Preferably, the composite carbon material has the core-shell structural characteristic of the amorphous carbon coated graphite, the coating thickness of the amorphous carbon is 5-20 nm, and the composite carbon material is used as a lithium ion battery negative electrode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the traditional lithium ion battery recovery process, the negative carbon and the diaphragm are generally treated in modes of combustion, stockpiling and the like, but the treatment method disclosed by the invention prepares the composite carbon material with a core-shell structure by using waste negative carbon and diaphragm raw materials and adopting an impregnation-carbonization method, so that the utilization added value is increased; and the copper current collector in the negative electrode can be recovered in a simple substance form, so that resources are saved.
(2) The mixed solvent used in the process can be recycled, the discharge amount of wastewater is greatly reduced, the energy consumption and the cost of the treatment process are reduced, and the process is green and environment-friendly.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be noted that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention.
Example 1
(1) Crushing the cathode of the waste lithium ion battery and the PE diaphragm into 3cm2Uniformly mixing the two to obtain mixed fragments, wherein the mass ratio of the negative electrode to the diaphragm is 10: 1;
(2) the mixed fragments were added to a solvent A having a volume ratio of NMP to toluene of 3:1, a liquid-solid mass ratio of 10:1, and mechanically stirred at 140 ℃ for 6 hours. Separating the copper foil from the solution by using a screen, washing the copper foil with alcohol, drying and recovering the copper foil. The remaining solution was designated as solution B;
(3) and (3) carrying out ultrasonic treatment on the solution B at the temperature of 50 ℃, wherein the power is 800W, the frequency is 300kHz, and the ultrasonic time is 3 h. Then respectively obtaining solid C and filtrate through filtration, and returning the collected filtrate to the step (2) to be used as a solvent for repeated use;
(4) and (3) putting the solid C in a nitrogen atmosphere for high-temperature carbonization, wherein the gas flow is 100mL/min, the heating rate is 10 ℃/min, and the temperature is kept at 1000 ℃ for 7h to obtain the composite carbon material.
The composite material with the core-shell structure characteristic and graphite coated by amorphous carbon is prepared by the embodiment, the thickness of the outer amorphous carbon is 5nm, and the purity of the recovered simple substance copper foil is 100%.
Example 2
(1) Crushing the negative electrode of the waste lithium ion battery and the PP diaphragm into 1.5cm2Uniformly mixing the two to obtain mixed fragments, wherein the mass ratio of the negative electrode to the diaphragm is 7: 1;
(2) adding the mixed fragments into a solvent A with a volume ratio of DMA to p-xylene of 5:1, wherein the liquid-solid mass ratio is 7:1, and stirring for 5 hours at a temperature of 100 ℃ by air flow. Separating the copper foil from the solution by using a screen, washing the copper foil with alcohol, drying and recovering the copper foil. The remaining solution was designated as solution B;
(3) performing ultrasonic treatment on the solution B at 40 ℃, wherein the power is 500W, the frequency is 150kHz, and the ultrasonic time is 2h, then respectively obtaining a solid C and a filtrate through filtration, and returning the collected filtrate to the step (2) to be used as a solvent for repeated use;
(4) and (3) putting the solid C in an argon atmosphere for high-temperature carbonization, wherein the gas flow is 50mL/min, the heating rate is 5 ℃/min, and the temperature is kept at 700 ℃ for 5h to obtain the composite carbon material.
The composite material with the core-shell structure characteristic and graphite coated by amorphous carbon is prepared by the embodiment, the thickness of the outer amorphous carbon is 12nm, and the purity of the recovered simple substance copper foil is 100%.
Example 3
(1) Crushing the negative electrode of the waste lithium ion battery and the PE-PP-PE three-layer diaphragm into 0.5cm2Uniformly mixing the two to obtain mixed fragments, wherein the mass ratio of the negative electrode to the diaphragm is 5: 1;
(2) adding the mixed fragments into a solvent A with the volume ratio of THF to trichloroethylene being 2:1, wherein the liquid-solid mass ratio is 5:1, and carrying out jet stirring for 3h at the temperature of 70 ℃. Separating the copper foil from the solution by using a screen, washing the copper foil with alcohol, drying and recovering the copper foil. The remaining solution was designated as solution B;
(3) performing ultrasonic treatment on the solution B at 0 ℃, wherein the power is 400W, the frequency is 20kHz, and the ultrasonic time is 1h, then respectively obtaining a solid C and a filtrate through filtration, and returning the collected filtrate to the step (2) to be used as a solvent for repeated use;
(4) and (3) putting the solid C in a nitrogen atmosphere for high-temperature carbonization, wherein the gas flow is 30mL/min, the heating rate is 1 ℃/min, and the temperature is kept at 600 ℃ for 3h to obtain the composite carbon material.
The composite material with the core-shell structure characteristic and graphite coated by amorphous carbon is prepared by the embodiment, the thickness of the outer amorphous carbon is 20nm, and the purity of the recovered simple substance copper foil is 100%.
Comparative example 1
The difference from example 1 is that the mass ratio of the negative electrode and the separator in step (1) was 1: 1. The composite material which has the structural characteristic of 'core-shell' and is prepared by the comparative example and is prepared by coating the graphite with the amorphous carbon, but the thickness of the outer amorphous carbon is more than 50nm, and the purity of the recovered simple substance copper foil is 100%.
Comparative example 2
The difference from example 1 is that the solvent in step (2) consists of water and ethanol in a volume ratio of 1: 1. The comparative example prepared a mechanically mixed powder of negative carbon and amorphous carbon, rather than a composite material with a "core-shell" structure, and the purity of the elemental copper foil recovered was 85%.
Comparative example 3
The same as example 1, except that the temperature of the ultrasonic treatment in the step (3) was 100 ℃. The comparative example prepared a mechanically mixed powder of negative carbon and amorphous carbon, rather than a composite material with a "core-shell" structure, and the purity of the elemental copper foil recovered was 85%.
Comparative example 4
The same as example 1 except that the volume ratio of NMP to toluene in step (2) was 10: 1. The composite material which has the structural characteristic of 'core-shell' and is prepared by the comparative example and is formed by coating the graphite with the amorphous carbon is obtained, but the thickness of the amorphous carbon on the outer layer is less than 1nm, and the purity of the simple substance copper foil obtained by recycling is 88%.
Comparative example 5
The same as example 1 except that the mixed chips were manually stirred in the solvent at 20 ℃ for 1 hour in step (2). The comparative example prepared a mechanically mixed powder of negative carbon and amorphous carbon, instead of a composite material with a "core-shell" structure, and the purity of the elemental copper foil recovered was 79%.

Claims (9)

1. A joint treatment method for a negative electrode and a diaphragm of a waste lithium ion battery is characterized by comprising the following steps:
(1) crushing and mixing a waste lithium ion battery cathode and a diaphragm to obtain mixed fragments, wherein the mass ratio of the cathode to the diaphragm is 5-10: 1;
(2) placing the mixed fragments in a mixed solvent, stirring for 3-6 h at 70-140 ℃, separating and recovering the copper foil from the solution, performing ultrasonic treatment on the residual solution at 0-70 ℃, separating to obtain a solid and a filtrate, and collecting the filtrate to return to the step (2) for reuse as the solvent; the mixed solvent is at least one of water, N-methyl pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran, and at least one of toluene, p-xylene, amyl acetate and trichloroethylene, and the volume ratio of the mixed solvent to the mixed solvent is 2-5: 1;
(3) and (3) putting the solid in an inert atmosphere for high-temperature carbonization to obtain the composite carbon material.
2. The joint treatment method of the negative electrode and the diaphragm of the waste lithium ion battery according to claim 1, characterized in that: in the step (1), the diaphragm is selected from any one of a Polyethylene (PE) diaphragm, a polypropylene (PP) diaphragm, a PE-PP double-layer diaphragm and a PE-PP-PE three-layer diaphragm.
3. The joint treatment method of the negative electrode and the diaphragm of the waste lithium ion battery according to claim 1, characterized in that: in the step (1), the negative electrode and the diaphragm are crushed into fragments of 0.5-3 cm & lt 2 & gt.
4. The joint treatment method of the negative electrode and the diaphragm of the waste lithium ion battery according to claim 1, characterized in that: in the step (2), the liquid-solid mass ratio of the mixed fragments to the mixed solvent is 5-10: 1.
5. The joint treatment method of the negative electrode and the diaphragm of the waste lithium ion battery according to claim 1, characterized in that: in the step (2), the stirring manner is at least one selected from mechanical stirring, gas flow stirring and jet stirring.
6. The joint treatment method of the negative electrode and the diaphragm of the waste lithium ion battery according to claim 1, characterized in that: in the step (2), the ultrasonic conditions are as follows: the ultrasonic power is 400-800W, the ultrasonic frequency is 20-300 kHz, and the ultrasonic time is 1-3 h.
7. The joint treatment method of the negative electrode and the diaphragm of the waste lithium ion battery according to claim 1, characterized in that: in the step (3), the inert gas is at least one of nitrogen and argon, and the gas flow is 30-100 mL/min.
8. The joint treatment method of the negative electrode and the diaphragm of the waste lithium ion battery according to claim 1, characterized in that: in the step (3), the high-temperature carbonization conditions are as follows: the heating rate is 1-10 ℃/min, the carbonization temperature is 600-1000 ℃, and the carbonization time is 3-7 h.
9. The joint treatment method of the negative electrode and the diaphragm of the waste lithium ion battery according to claim 1, characterized in that: the composite carbon material has the core-shell structure characteristic of the amorphous carbon coated graphite, the coating thickness of the amorphous carbon is 5-20 nm, and the composite carbon material is used as a lithium ion battery negative electrode material.
CN201910588579.0A 2019-07-02 2019-07-02 Combined treatment method for negative electrode and diaphragm of waste lithium ion battery Expired - Fee Related CN110444830B (en)

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