CN108011146B - Recycling method of waste lithium battery - Google Patents
Recycling method of waste lithium battery Download PDFInfo
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- CN108011146B CN108011146B CN201711146734.0A CN201711146734A CN108011146B CN 108011146 B CN108011146 B CN 108011146B CN 201711146734 A CN201711146734 A CN 201711146734A CN 108011146 B CN108011146 B CN 108011146B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
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- 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
- C22B7/001—Dry processes
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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
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Abstract
The invention belongs to the field of battery recovery, and particularly discloses a green and environment-friendly method for recycling waste lithium batteries. The method for recycling the waste lithium batteries comprises the steps of lithium battery pretreatment, crushing and drying, battery fragment separation and separator treatment. Electrolyte is recovered by filtering the crushed lithium battery, and the electrolyte is collected by condensing the exhaust gas of the drying equipment, so that the recovery rate of the electrolyte is improved, and the treatment capacity of sewage and waste gas is reduced; meanwhile, the drying of the drying equipment is favorable for fully separating the electrolyte on the battery fragments; the dried battery fragments are sequentially subjected to stirring and screening treatment, so that resources such as a battery pole piece current collector and precious and scarce metals in the lithium battery can be respectively recovered, the recovery rate is high, and the pollution in the whole recovery process is small.
Description
Technical Field
The invention belongs to the field of battery recovery, and particularly relates to a method for recycling waste lithium batteries.
Background
With the development of technology, electronic products have penetrated into every corner of people's lives. Compared with cadmium-nickel batteries and hydrogen-nickel batteries, lithium ion batteries have the advantages of small volume, light weight, high working voltage, high specific energy of volume and mass, no memory effect, small self-discharge, wide working temperature range, long service life and the like, which already dominate the market of small portable electronic products, for example: application to portable telephones, video cameras, portable notebooks, etc. With the continuous development of society and the emergence of climate, energy and environmental problems, lithium ion batteries have also been widely used in the field of electric vehicles.
In 2010, the output of lithium ion batteries in China is about 26.87 hundred million; in 2013, the output of the lithium ion battery in China reaches 47.68 hundred million; in 2016, the lithium battery yield reaches 78.42 hundred million in China. The production and consumption of lithium batteries in China show a rapid growth trend, the yield of the lithium batteries is expected to continue to increase rapidly along with the development of electric automobiles in the future, the service life of the lithium batteries is generally 3-5 years, and therefore more waste lithium batteries can appear in the future under the condition that a large number of scrapped lithium batteries are kept in the market.
LiPF contained in lithium ion battery6、LiBF4、LiClO4And the electrolytes and organic solvents such as EC, EMC, DMC and the like have great harm to the environment and human bodies, and are determined as hazardous waste by the nation. On the other hand, most of the lithium ion battery anode materials are transition metal oxides, such as LiFePO4、LiCoO2、Li[NixCo1－2xMnx]O2Etc., containing precious and rare metals such as cobalt, nickel, lithium, etc.; and the current collector of the lithium ion battery pole piece, such as copper and aluminum foil material resources. Therefore, the method has great significance for carrying out harmless treatment on the waste lithium ion battery and carrying out resource recycling on the metal in the waste lithium ion battery.
With the rapid development of the lithium ion battery technology, the yield and the scrap quantity of the lithium ion battery show a rapid increasing trend, and more patents and reports for researching the recycling of the waste lithium ion battery are provided, and the wet recovery and the dry recovery are mainly provided. For example, patent application No. 201610314509.2 discloses a device and a method for separating and collecting all-component materials of waste lithium batteries, which mainly adopt simple dry methods such as mechanical crushing, vacuum separation, vibration screening, specific gravity separation, air flow separation and the like to separate and collect electrode materials, current collector metals, plastic diaphragms and battery shells in the waste lithium batteries; the electrolyte adopts a vacuum recovery method, the recovery efficiency is low, and the equipment investment is large. Also, for example, the patent application No. 201010262198.2 discloses a method for recovering valuable metals from waste lithium batteries, which comprises mechanically crushing discharged waste lithium batteries, calcining at 350-400 ℃ to obtain a material containing cobalt, copper and aluminum, and performing wet treatment; its advantages are simple pre-treatment, difficult treatment of waste gas after sintering and high cost.
Disclosure of Invention
The invention aims to provide a method for recycling waste lithium batteries, which has high resource recovery rate and is environment-friendly.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for recycling the waste lithium batteries comprises the steps of lithium battery pretreatment, crushing and drying, battery fragment separation and separator treatment;
lithium battery pretreatment: putting the lithium battery into a discharge cell for discharging for more than 2 hours, and washing the discharged lithium battery with water and then draining the lithium battery to finish the pretreatment;
crushing and drying: crushing the filtered and dried lithium battery by using crushing equipment, and filtering to obtain battery fragments and electrolyte; sending the battery fragments into drying equipment for drying for 10-50 minutes, and collecting electrolyte after exhaust gas of the drying equipment is condensed;
and a battery fragment separation step: stirring the dried battery fragments to separate lithium cobaltate and carbon powder from the electrode foil; screening the stirred battery fragments to separate a mixture of lithium cobaltate and carbon powder;
and (3) treatment of the separated matter: and (3) winnowing the oversize material to obtain a metal block, a plastic block, a metal foil and diaphragm paper, sintering the mixture of lithium cobaltate and carbon powder, and refining to recover cobalt, lithium and nickel.
Furthermore, in the step of pretreating the lithium battery, a sodium chloride aqueous solution with the concentration of 5% -20% is placed in the battery to serve as a conductive solution.
Further, in the crushing and drying steps, the crushing equipment is a blade crusher, the drying equipment is a tunnel drying furnace with a conveying tray, and the drying temperature of the tunnel drying furnace is controlled to be 90-200 ℃ in the drying process; in the tunnel type drying furnace, the drying temperature gradually increases along the conveying direction of the conveying tray.
Further, in the step of separating the battery fragments, a stirring roller is adopted for stirring, and a vibrating screen is adopted for screening.
Further, in the step of separating the battery fragments, the stirring roller and the vibrating screen are respectively exhausted for dust removal.
Further, in the crushing and drying step, the crushing device and the drying device are placed in the housing means, and the inside of the housing means is placed in a negative pressure state.
Further, inert gas is introduced into the housing means.
Further, the inert gas is nitrogen.
The invention has the beneficial effects that: electrolyte is recovered by filtering the crushed lithium battery, and the electrolyte is collected by condensing the exhaust gas of the drying equipment, so that the recovery rate of the electrolyte is improved, and the treatment capacity of sewage and waste gas is reduced; meanwhile, the drying of the drying equipment is favorable for fully separating the electrolyte on the battery fragments; the dried battery fragments are sequentially subjected to stirring and screening treatment, so that resources such as a battery pole piece current collector and precious and scarce metals in the lithium battery can be respectively recovered, the recovery rate is high, and the pollution in the whole recovery process is small.
Drawings
FIG. 1 is a process flow diagram of the process of the present invention;
Detailed Description
The invention will be further explained with reference to the drawings.
Referring to fig. 1, the method for recycling waste lithium batteries includes a lithium battery pretreatment step, a crushing and drying step, a battery fragment separation step, and a separator treatment step;
lithium battery pretreatment: putting the lithium battery into a discharge cell for discharging for more than 2 hours, and washing the discharged lithium battery with water and then draining the lithium battery to finish the pretreatment; in the step, a conductive liquid for discharging the lithium battery is contained in the discharge cell; the conductive liquid can be various, and is preferably a sodium chloride aqueous solution with the concentration of 5 to 20 percent; generally, waste lithium batteries are put into batteries after being framed;
crushing and drying: crushing the filtered and dried lithium battery by using crushing equipment, and filtering to obtain battery fragments and electrolyte; sending the battery fragments into drying equipment for drying for 10-50 minutes, condensing exhaust gas of the drying equipment, collecting electrolyte, and treating and discharging residual tail gas after condensation; in the step, the adopted crushing equipment is generally a blade crusher, the adopted drying equipment is generally a tunnel drying furnace with a conveying tray, and the drying temperature of the tunnel drying furnace is controlled to be 90-200 ℃ in the drying process; the purpose of drying the battery fragments is mainly to evaporate and remove the electrolyte and water attached to the battery fragments by heating; in order to improve safety, in the tunnel type drying furnace, the drying temperature is gradually increased along the conveying direction of the conveying tray; therefore, under the conveying action of the conveying tray, the electrolyte on the battery fragments can be volatilized from low to high in sequence according to the volatilization points, and the electrolyte with a lower combustion point can be prevented from being heated and combusted;
and a battery fragment separation step: stirring the dried battery fragments to separate lithium cobaltate and carbon powder from the electrode foil; screening the stirred battery fragments to separate a mixture of lithium cobaltate and carbon powder; in this step, stirring is usually performed by using a stirring drum, and sieving is usually performed by using a vibrating screen; in order to reduce pollution, the stirring roller and the vibrating screen are generally required to be exhausted and dedusted respectively;
and (3) treatment of the separated matter: and (3) winnowing the oversize material to obtain a metal block, a plastic block, a metal foil and diaphragm paper, sintering the mixture of lithium cobaltate and carbon powder, and refining to recover cobalt, lithium and nickel.
In a preferred embodiment of the present invention, the crushing means and the drying means are placed in the housing means and the inside of the housing means is placed under negative pressure in the crushing and drying step. The housing means is typically provided with vent and solvent condensing recovery means. Inert gas can be introduced into the outer cover device according to the requirement to avoid the combustion of the volatilized heated electrolyte; the inert gas is preferably nitrogen.
The method is suitable for large-scale rapid treatment of the waste lithium batteries, has high recycling degree of the waste lithium batteries, avoids the problem of sewage treatment, and has small waste gas treatment amount.
Claims (8)
1. The method for recycling the waste lithium batteries is characterized by comprising the steps of lithium battery pretreatment, crushing and drying, battery fragment separation and separator treatment;
lithium battery pretreatment: putting the lithium battery into a discharge cell for discharging for more than 2 hours, and washing the discharged lithium battery with water and then draining the lithium battery to finish the pretreatment;
crushing and drying: crushing the filtered and dried lithium battery by using crushing equipment, and filtering to obtain battery fragments and electrolyte; sending the battery fragments into drying equipment for drying for 10-50 minutes, and collecting electrolyte after exhaust gas of the drying equipment is condensed; the drying equipment is a tunnel drying furnace with a conveying tray, and the drying temperature of the tunnel drying furnace is controlled to be 90-200 ℃ in the drying process; in the tunnel type drying furnace, the drying temperature is gradually increased along the conveying direction of the conveying tray;
and a battery fragment separation step: stirring the dried battery fragments to separate lithium cobaltate and carbon powder from the electrode foil; screening the stirred battery fragments to separate a mixture of lithium cobaltate and carbon powder;
and (3) treatment of the separated matter: and (3) winnowing the oversize material to obtain a metal block, a plastic block, a metal foil and diaphragm paper, sintering the mixture of lithium cobaltate and carbon powder, and refining to recover cobalt, lithium and nickel.
2. The method for recycling waste lithium batteries as claimed in claim 1, wherein: in the step of lithium battery pretreatment, a battery is placed in the battery and filled with a sodium chloride aqueous solution with the concentration of 5% -20% as a conductive solution.
3. The method for recycling waste lithium batteries as claimed in claim 2, wherein: in the crushing and drying steps, the crushing equipment adopted is a blade type crusher.
4. The method for recycling waste lithium batteries as claimed in claim 3, wherein: in the step of separating the battery fragments, a stirring roller is adopted for stirring, and a vibrating screen is adopted for screening.
5. The method for recycling waste lithium batteries as claimed in claim 4, wherein: and in the step of separating the battery fragments, exhausting and dedusting the stirring roller and the vibrating screen respectively.
6. The method for recycling waste lithium batteries as claimed in claim 1, 2, 3, 4 or 5, wherein: in the crushing and drying step, the crushing device and the drying device are arranged in the outer cover device, and the inner part of the outer cover device is in a negative pressure state.
7. The method for recycling waste lithium batteries as claimed in claim 6, wherein: and introducing inert gas into the outer cover device.
8. The method for recycling waste lithium batteries as claimed in claim 7, wherein: the inert gas is nitrogen.
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| CN108879010A (en) * | 2018-06-27 | 2018-11-23 | 深圳市恒创睿能环保科技有限公司 | A kind of technique of discarded soft-package battery electric discharge and component dissociation |
| CN108550947B (en) * | 2018-06-30 | 2021-06-29 | 贵州中伟资源循环产业发展有限公司 | Waste lithium battery electrolyte lithium hexafluorophosphate recycling device |
| CN108808156B (en) * | 2018-08-24 | 2020-10-16 | 广西师范大学 | Method for recovering electrolyte in waste lithium ion battery |
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| CN111430832B (en) * | 2020-03-11 | 2021-06-29 | 中南大学 | Full resource recovery method for waste ternary lithium ion battery without discharge pretreatment |
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| CN114583303B (en) * | 2022-01-12 | 2024-04-19 | 顺尔茨环保(北京)有限公司 | Crushing method and system for waste lithium ion batteries |
| CO2022006642A1 (en) * | 2022-05-19 | 2023-11-20 | Altero S A S | Dry process to recycle rechargeable lithium ion, lithium polymer and nickel metal hydride batteries and directly recover cobalt, nickel, lithium, manganese, base metals and electrolyte |
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