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CN109378542B - Method for recycling copper, aluminum and rubber in waste power lithium batteries - Google Patents

Method for recycling copper, aluminum and rubber in waste power lithium batteries Download PDF

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Publication number
CN109378542B
CN109378542B CN201811321397.9A CN201811321397A CN109378542B CN 109378542 B CN109378542 B CN 109378542B CN 201811321397 A CN201811321397 A CN 201811321397A CN 109378542 B CN109378542 B CN 109378542B
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aluminum
copper
rubber
particles
magnetite
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CN109378542A (en
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杨柳毅
万洪强
王奉刚
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03BSEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B7/00Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
    • 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
    • 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)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a method for recycling copper, aluminum and rubber in waste power lithium batteries, which is characterized by comprising the following steps of: 1) disassembling: disassembling the waste power battery pack to obtain a battery monomer; 2) crushing and granulating: carrying out first-stage crushing and second-stage superfine grinding on the battery monomer to obtain a product A; 3) screening: screening the product A by using screening equipment to obtain minus sieve 100-plus 160-mesh positive and negative electrode powder and plus sieve 100-plus 160-mesh product B; 4) and (3) magnetite induced specific gravity separation: and carrying out primary magnetite induced specific gravity separation on the product B to obtain pure rubber particles and a copper-aluminum mixture, and carrying out secondary magnetite induced specific gravity separation on the copper-aluminum mixture to obtain pure copper particles and pure aluminum particles respectively. The invention adopts the induced specific gravity separation technology of the superfine high-purity magnetite, can better recover copper aluminum and rubber in the waste power lithium battery, and the obtained copper aluminum and rubber have low mutual content.

Description

Method for recycling copper, aluminum and rubber in waste power lithium batteries
Technical Field
The invention relates to a method for recycling lithium batteries, in particular to a method for recycling copper, aluminum and rubber in waste power lithium batteries.
Background
In recent years, with the guidance of new energy automobile policies in China, the new energy automobile sales volume in China is greatly increased, and the total annual total sales of new energy automobiles in China in 2017 is 77.7 thousands, which is 53% higher. Wherein, the annual accumulated sales volume of pure electric is 65.2 thousands, and the annual accumulated sales volume of plug-in hybrid is 12.5 thousands. The sales volume of domestic new energy automobiles is expected to exceed 200 million in 2020, and annual year-on-year acceleration of sales volume in the future is expected to exceed 40%. At present, ternary lithium batteries, lithium iron phosphate and the like are mostly adopted as power batteries in new energy automobiles in China, and the battery capacity is slowly attenuated due to cyclic charge and discharge, so that a large number of power lithium batteries are expected to enter the retirement period within two or three years, and are recycled to recycle materials such as copper-aluminum rubber and the like and valuable metal elements such as nickel-cobalt-manganese-lithium and the like in the power lithium batteries, so that good economic benefit can be realized, and the environmental pollution caused by discarding the power lithium batteries can be avoided. At present, anode and cathode powder of a lithium battery is recycled and collected mainly by screening and dust collection and then leached. Copper foils and aluminum foils in positive and negative pole pieces of waste power lithium batteries and rubber particles for packaging are mostly sorted by adopting a method of air separation and electric separation after crushing at present, and the sorting method has the defects that the obtained copper and aluminum products have large mutual content, the purity of the products is reduced, and the sales value of the products is also reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for recycling copper, aluminum and rubber in waste power lithium batteries.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for recycling copper, aluminum and rubber in waste power lithium batteries comprises the following steps:
1) disassembling: disassembling the waste power battery pack to obtain a battery monomer;
2) crushing and granulating: carrying out first-stage crushing and second-stage superfine grinding on the battery monomer to obtain a product A;
3) screening: screening the product A by using screening equipment to obtain minus sieve 100-plus 160-mesh positive and negative electrode powder and plus sieve 100-plus 160-mesh product B;
4) and (3) magnetite induced specific gravity separation: and carrying out primary magnetite induced specific gravity separation on the product B to obtain pure rubber particles and a copper-aluminum mixture, and carrying out secondary magnetite induced specific gravity separation on the copper-aluminum mixture to obtain pure copper particles and pure aluminum particles respectively.
Furthermore, the disassembly process in the step 1) is performed in a closed protective atmosphere, so that the environment pollution caused by the disassembly process can be effectively avoided, and the monomer material loss in the disassembly process can be avoided.
Further, in the step 2), the ultra-fine grinding granulator performs friction granulation on the copper foil and the aluminum foil in the single battery, the current collector and the single battery packaging aluminum shell to enable the product A to be produced in a spherical particle shape, and the positive and negative battery powder is rubbed off from the aluminum foil and the copper foil, and if the copper and aluminum sheets are produced in a sheet-shaped broken product, the copper and aluminum sheets are difficult to separate by gravity separation.
Further, the positive and negative electrode powder obtained by the first-stage crushing and second-stage ultrafine grinding granulator in the step 2) through ventilation and dust removal and the minus sieve 100-mesh 160-mesh positive and negative electrode powder obtained in the step 3) are all sent into a cracking furnace for roasting, and valuable elements are extracted through leaching after roasting, so that the high-efficiency utilization and recovery of the waste lithium ion batteries can be realized.
Further, in the step 4), the product B is firstly prepared by adopting superfine high-purity magnetite and water to have the density of 1.5-2.5t/m3The slurry is prepared by separating rubber particles and copper aluminum particles, recovering superfine high-purity magnetite by adopting low-intensity magnetic separation, and preparing the obtained copper aluminum particles into the slurry with the density of 3-7t/m by adopting the superfine high-purity magnetite and water3The slurry separates copper and aluminum particles to obtain pure copper particles and pure aluminum particles respectively, because the specific gravity of the copper, the aluminum and the rubber is respectively 8.95t/m3The specific gravity of the aluminum is 2.7t/m3The specific gravity of the rubber is 1.2t/m3Therefore, copper and aluminum particles can be separated by adopting weak magnetic separation recovery.
Further, the fineness of the superfine high-purity magnetite is 0.01-0.038mmmm, wherein Fe3O4The content is more than 95 percent, the specific gravity of the slurry is controlled by adjusting the concentration of the ultra-fine ultra-pure iron concentrate prepared by the ultra-fine ultra-pure iron concentrate and water, and the ultra-fine ultra-pure iron concentrate, copper, aluminum and rubber can be recycled and reused by a screening or magnetic separation scheme without bringing new impurities into copper-aluminum rubber particles.
Further, the aperture of the screen mesh of the screening device in the step 3) is 140 meshes.
Compared with the prior art, the invention has the advantages that:
1. compared with the electric separation-shaking table process disclosed in patent CN106972215A, the process is simple, the purity of copper-aluminum powder products is high, the mutual content of copper-aluminum products is low, and higher sales economic income can be realized;
2. compared with the existing dry method separation process of rubber particles and copper aluminum powder, the invention adopts the ultrafine high-purity iron concentrate to induce specific gravity separation, strengthens the buoyancy of the separation medium to the copper aluminum particles, has high purity of the copper and aluminum powder products, low mutual content of the copper and aluminum products, simple process flow, greatly reduced dust in workshops and greatly reduced equipment investment and workshop investment.
Drawings
FIG. 1 is a process flow diagram of an embodiment 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
As shown in the attached figure 1, the method for recycling copper, aluminum and rubber in waste power lithium batteries comprises the following steps:
1) disassembling: 200kg of waste power battery pack is subjected to discharging and disassembling procedures to obtain 150kg of battery monomer;
2) crushing and granulating: 150kg of single battery is crushed in one section, and a dust removal device connected with the crushing device absorbs and collects a plastic diaphragm with light density and fine-grained battery powder and then screens the plastic diaphragm and the battery powder to obtain a plastic diaphragm product and a battery powder product;
3) screening: sieving the products of the first-stage crushing heavier products after the two-stage ultrafine grinding granulator process to obtain 140-mesh anode and cathode powder of undersize, and 140-mesh copper, aluminum and rubber granules of oversize;
4) and (3) magnetite induced specific gravity separation: the fineness of the mixture is 0.02mm and Fe3O4The superfine magnetite with the content of more than 95 percent is prepared into the superfine magnetite with the specific gravity of 2.0t/m3The slurry is mixed with copper powder, aluminum powder and rubber particles with 140 meshes of oversize materials, stirred for 5 minutes and settled for 5 seconds, the rubber particles suspended on the surface of the slurry are separated from the copper and aluminum particles settled on the bottom layer, and the ultra-fine ultrapure magnetite and water are recovered by screening (or low-intensity magnetic separation) through a 300-mesh screen; the specific gravity of the bottom layer copper aluminum particles and the mixture is 5t/m3The superfine ultrapure magnetite slurry is mixed and stirred for 5 minutes and then settled for 5 seconds, and aluminum particles suspended on the surface of the slurry are separated from copper particles settled on the bottom layer; and (3) recovering the superfine ultrapure magnetite and water by adopting screening or low-intensity magnetic separation, wherein the water and the magnetite can be recycled by 100 percent.
In this embodiment, the minus sieve 140-mesh positive and negative electrode powders obtained in step 2) and step 3) and the dust-removing material obtained in the first and second stage crushing and grinding processes are combined, calcined at 700 ℃ for 3 hours, volatilized to remove the binder, and then used as the raw material for acid leaching extraction.

Claims (5)

1. A method for recycling copper, aluminum and rubber in waste power lithium batteries is characterized by comprising the following steps:
1) disassembling: disassembling the waste power battery pack to obtain a battery monomer;
2) crushing and granulating: carrying out first-stage crushing and second-stage superfine grinding on the battery monomer to obtain a product A; wherein, the ultra-fine grinding granulator rubs and granulates the copper foil and the aluminum foil in the single battery, the current collector and the single battery packaging aluminum shell to make the product A in a spherical particle shape and rub the positive and negative battery powder from the aluminum foil and the copper foil;
3) screening: screening the product A by using screening equipment to obtain minus sieve 100-plus 160-mesh positive and negative electrode powder and plus sieve 100-plus 160-mesh product B;
4) and (3) magnetite induced specific gravity separation: performing primary magnetite induced specific gravity separation on the product B to obtain pure rubber particles and a copper-aluminum mixture, and performing secondary magnetite induced specific gravity separation on the copper-aluminum mixture to obtain pure copper particles and pure aluminum particles respectively, wherein the specific process comprises the step of preparing the product B by adopting superfine high-purity magnetite and water to obtain the product B with the density of 1.5-2.5t/m3The slurry is prepared by separating rubber particles from copper-aluminum particles, and then recovering superfine high-purity magnetite by adopting low-intensity magnetic separation; the obtained copper-aluminum particles are prepared into the copper-aluminum alloy with the density of 3-7t/m by adopting superfine high-purity magnetite and water3The slurry separates copper and aluminum particles to respectively obtain pure copper particles and pure aluminum particles.
2. The method for recycling the copper, the aluminum and the rubber in the waste power lithium batteries as recited in claim 1, wherein the disassembling process in the step 1) is performed in a closed protective atmosphere.
3. The method for recycling copper, aluminum and rubber in waste power lithium batteries as claimed in claim 1, wherein the positive and negative electrode powders obtained by the primary crushing and secondary ultrafine grinding granulator in the step 2) through ventilation and dust removal and the minus sieve 100-mesh 160-mesh positive and negative electrode powders obtained in the step 3) are all sent into a cracking furnace for roasting, and then leaching is performed to extract valuable elements after roasting.
4. The method for recycling copper aluminum and rubber in waste power lithium batteries as claimed in claim 1, wherein the fineness of the ultra-fine high-purity magnetite is 0.01-0.038mm, wherein Fe3O4The content is more than 95 percent, and the specific gravity of the slurry is controlled by adjusting the concentration of the slurry prepared by the content and water.
5. The method for recycling the copper, the aluminum and the rubber in the waste power lithium batteries as recited in any one of claims 1-3, characterized in that the screen mesh of the screening equipment in the step 3) is 140 meshes.
CN201811321397.9A 2018-11-07 2018-11-07 Method for recycling copper, aluminum and rubber in waste power lithium batteries Active CN109378542B (en)

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CN109830773B (en) * 2019-03-19 2020-11-27 泰顺永庆电力技术有限公司 Waste lithium battery recovery processing method
CN111940125B (en) * 2020-07-30 2022-04-12 中陕核工业集团综合分析测试有限公司 Method and system for recovering precious metals in low-grade gold tailings
CN113908977A (en) * 2021-11-08 2022-01-11 湖南江冶机电科技股份有限公司 Recovery process of waste lithium battery

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Publication number Priority date Publication date Assignee Title
CN1071353A (en) * 1991-10-10 1993-04-28 峰安金属工业股份有限公司 By the method for separating of selecting special metal in the old metal material
CN107293814A (en) * 2016-04-11 2017-10-24 上海奇谋能源技术开发有限公司 A kind of electrode current collecting body of ultrasonic Separation lithium ion battery and the method for electrode material
CN107282285A (en) * 2016-04-11 2017-10-24 上海奇谋能源技术开发有限公司 A kind of method for the positive pole and negative pole for separating lithium ion battery
CN108615956A (en) * 2018-06-14 2018-10-02 河南巨峰环保科技有限公司 A kind of electric discharge dynamic lithium battery recovery process

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JP6238070B2 (en) * 2014-03-31 2017-11-29 三菱マテリアル株式会社 Disposal of used lithium ion batteries
CN106140796B (en) * 2016-08-25 2018-07-03 巩义市城区润达机械厂 Useless lithium battery processing system and treatment process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1071353A (en) * 1991-10-10 1993-04-28 峰安金属工业股份有限公司 By the method for separating of selecting special metal in the old metal material
CN107293814A (en) * 2016-04-11 2017-10-24 上海奇谋能源技术开发有限公司 A kind of electrode current collecting body of ultrasonic Separation lithium ion battery and the method for electrode material
CN107282285A (en) * 2016-04-11 2017-10-24 上海奇谋能源技术开发有限公司 A kind of method for the positive pole and negative pole for separating lithium ion battery
CN108615956A (en) * 2018-06-14 2018-10-02 河南巨峰环保科技有限公司 A kind of electric discharge dynamic lithium battery recovery process

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