CN110611137A - Dry recovery method for waste power lithium battery - Google Patents
Dry recovery method for waste power lithium battery Download PDFInfo
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- CN110611137A CN110611137A CN201910859050.8A CN201910859050A CN110611137A CN 110611137 A CN110611137 A CN 110611137A CN 201910859050 A CN201910859050 A CN 201910859050A CN 110611137 A CN110611137 A CN 110611137A
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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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- 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 relates to a dry recovery method of waste power lithium batteries, which comprises S1, crushing the battery cores of the waste power lithium batteries by adopting a shearing and crushing mode to obtain electrode crushed materials and diaphragms; s2, performing high-temperature treatment on the electrode crushed aggregates, removing the binder, and grinding the electrode crushed aggregates by using a stirring mill to obtain electrode powder and a copper-aluminum mixture; s3, carrying out primary air flow separation on the electrode powder, the copper-aluminum mixture and the diaphragm to respectively obtain the electrode powder, the diaphragm mixture and the copper-aluminum mixture; s4, grading the electrode powder and diaphragm mixture to obtain electrode powder and diaphragm; and S5, carrying out secondary sorting on the copper-aluminum mixture to obtain a copper foil and an aluminum foil. The invention provides a complete pretreatment route for waste power lithium batteries, carries out classified recovery on copper foils, aluminum foils, diaphragms and electrode powder, and adopts a dry method means to effectively reduce environmental pollution and reduce subsequent treatment pressure while recovering resources, thereby being a resource and harmless pretreatment process.
Description
Technical Field
The invention relates to the field of solid waste recovery and treatment, in particular to a dry recovery method for waste power lithium batteries.
Background
The lithium battery has the characteristics of high working voltage, high energy density, long cycle life, good safety performance, cleanness, no pollution and the like, and is widely applied to important fields of traffic, electric power, mobile communication, new energy storage, aerospace military industry and the like. Along with the popularization and the promotion of new energy automobiles, the lithium battery is more colorful in the field of new energy automobile energy storage. The power lithium battery has large energy consumption and short service life, so that the scrappage is increased rapidly, the environment is seriously polluted, and meanwhile, the waste power lithium battery contains a large amount of resources such as copper, aluminum, graphite and the like, so that the resources are not effectively recycled, and the resource waste is also caused. Therefore, the recycling of waste power lithium batteries is urgent.
However, the recovery of the waste power lithium battery in China is currently in a laboratory stage, and is mainly divided into two parts, namely pretreatment and subsequent treatment, the pressure of the subsequent treatment can be relieved by optimizing the pretreatment, and a complete recycling and harmless pretreatment process is not formed at home at present.
Disclosure of Invention
The invention designs a dry recovery method of waste power lithium batteries, which solves the problems of low recovery rate, environmental pollution and high energy consumption of the waste power lithium batteries in the prior pretreatment technology.
In order to solve the technical problems, the invention adopts the following scheme:
a dry recovery method of waste power lithium batteries comprises the following steps:
s1, crushing the battery cell of the waste power lithium battery in a shearing and crushing mode to obtain electrode crushed materials and a diaphragm;
s2, performing high-temperature treatment on the electrode crushed aggregates, removing the binder, and grinding the electrode crushed aggregates by using a stirring mill to obtain electrode powder and a copper-aluminum mixture;
s3, carrying out primary air flow separation on the electrode powder, the copper-aluminum mixture and the diaphragm obtained in the S1 to respectively obtain the electrode powder, the diaphragm mixture and the copper-aluminum mixture;
s4, carrying out classification treatment on the electrode powder and diaphragm mixture to obtain electrode powder and a diaphragm;
and S5, carrying out secondary sorting on the copper-aluminum mixture to obtain a copper foil and an aluminum foil.
There is no precedence between step S4 and step S5.
Preferably, in the step S1, the crushing mode is shear crushing to ensure the shape of the crushed material.
Preferably, in step S2, the binder is removed by the high-temperature treatment under ventilation conditions to ensure that the organic binder undergoes a cracking reaction, so as to obtain the cracked gas and the electrode powder.
In step S2, the step of removing the binder from the electrode scrap at a high temperature includes: and spreading the electrode crushed aggregates in the container, volatilizing and removing the binder at high temperature under the ventilation condition to obtain the electrode powder and copper-aluminum mixture.
Preferably, in the step S2, the temperature of the high-temperature treatment is 400-500 ℃; the high-temperature treatment time is 1-2 h.
Preferably, in the step S2, the stirring mill uses quartz sand with a particle size of 3-6mm as the grinding medium, and the medium filling rate is greater than 50%.
Preferably, the step S2 further includes a flue gas purification treatment process, where the flue gas purification treatment process treats the flue gas generated by the high-temperature treatment.
Preferably, in step S3, a variable diameter pulsating air flow separator is used to perform primary air flow separation on the electrode powder, the copper-aluminum mixture and the diaphragm;
preferably, the air volume of the variable diameter pulsating air flow separator is 40-50m3/h；
Preferably, the taper ratio of the variable-diameter section of the variable-diameter pulsating airflow separator is 1/25-4/25;
preferably, the height of the straight cylinder section of the variable diameter pulsating airflow separator is 0.5-1 m;
preferably, the inner diameter of a discharge opening of the gas distributor of the variable-diameter pulsating gas flow separator accounts for 15-20% of the cross-sectional area of the separation column.
Specifically, in step S3, the step of performing primary air flow separation on the electrode powder, the copper-aluminum mixture and the diaphragm by using the variable-diameter pulsating air flow separation device includes: putting the materials into a feeder, and adjusting the air volume of an air flow separator to 40-50m3And h, uniformly feeding by using a feeder to obtain the electrode powder, the diaphragm mixture and the copper-aluminum mixture.
In step S3, the primary air stream sorting process further includes a step of performing dust removal processing on the sorting device.
Preferably, in step S4, the mixture of the electrode powder and the separator is classified by using a cyclone separator. When the mixture of the electrode powder and the diaphragm is graded, the graded air volume is constant, and a dust removal device is adopted.
Preferably, in step S5, a variable diameter pulsating air flow separator is used for secondary air flow separation of the copper-aluminum mixture;
preferably, the air volume of the variable-diameter pulsating airflow sorting machine is 150m3/h；
Preferably, the taper ratio of the variable-diameter section of the variable-diameter pulsating airflow separator is 1/25-4/25;
preferably, the height of the straight cylinder section of the variable diameter pulsating airflow separator is 0.5-1 m;
preferably, the inner diameter of a discharge opening of the gas distributor of the variable-diameter pulsating gas flow separator accounts for 15-20% of the cross-sectional area of the separation column.
Specifically, in step S5, the step of performing secondary air flow separation on the copper-aluminum mixture by using the variable-diameter pulsating air flow separation device includes: the heavy product of the primary air flow separation is a copper-aluminum mixture, and enters secondary air flow separation equipment, and the air volume of the separator is adjusted to 120-150m3And h, obtaining the copper foil and the aluminum foil.
Preferably, in step S1, before the cutting and crushing of the battery cells, a deep discharge process is further performed on the waste power lithium batteries.
The dry recovery method of the waste power lithium battery has the following beneficial effects:
(1) the invention provides a complete pretreatment route for the waste power lithium battery, effectively classifies and recovers metal resources (copper and aluminum), diaphragms and electrode powder in the waste power lithium battery, does not produce any pollution in the treatment process, and is a resource and environment-friendly pretreatment process for the waste power lithium battery. In addition, the pretreatment process has the characteristics of simple structure, easy operation and the like, is easy to realize industrialization and large-scale production, and is very suitable for large-scale industrial application.
(2) The method recovers the waste power lithium battery, generates some volatile organic compounds when the battery core is crushed, volatilizes the electrode crushed aggregates when the temperature reaches 400-.
(3) The electrode crushed aggregates are treated at high temperature, and the rest solid matters mainly comprise a mixture of copper foil, aluminum foil, electrode powder and a diaphragm and enter main separation equipment. In addition, the crushing mode adopted by the invention is shear type crushing, so that the shape after crushing is ensured, and meanwhile, the particle size is larger, thereby being beneficial to subsequent sorting. Secondly, sorting according to density and grading according to granularity according to density difference and granularity difference of copper foil, aluminum foil, diaphragm and electrode powder, and realizing a sorting-grading integrated process for sorting 4 products by feeding materials once, wherein the sorted copper foil and aluminum foil can be reused after further treatment.
Drawings
FIG. 1: the invention discloses a schematic diagram of a dry recovery pretreatment process of waste power lithium batteries;
FIG. 2: the invention discloses a schematic diagram of a waste power lithium battery dry-method recovery system;
description of reference numerals:
10-a shearing and crushing device; 20-high temperature roasting device; 30-a flue gas purification device; 40-a dry recovery system of waste power lithium batteries; 41-primary air flow separator; 42-secondary air flow sorter; 43-primary classifier; 50-discharge device.
Detailed Description
The invention is further illustrated below with reference to fig. 1 to 2:
as shown in figure 1, the social development is restricted by the reason that a large number of waste power lithium batteries in the market cannot obtain good benefits, and the current treatment technology has the problems of low recovery efficiency, high treatment pressure and serious environmental pollution. Aiming at the problem, the invention provides a dry recovery method of waste power lithium batteries, which comprises the following steps: s1, crushing the battery cell in a shearing and crushing mode to obtain crushed electrode materials and a diaphragm; s2, performing high-temperature treatment on the electrode crushed aggregates, removing the binder, and grinding the electrode crushed aggregates by using a stirring mill to obtain electrode powder and a copper-aluminum mixture; s3, performing primary air flow separation on the electrode powder, the copper-aluminum mixture and the diaphragm by using a variable-diameter pulsating air flow separation device to obtain the electrode powder, the diaphragm mixture and the copper-aluminum mixture; s4, grading the mixture of the electrode powder and the diaphragm to obtain the electrode powder and the diaphragm; and S5, carrying out secondary air flow separation on the copper-aluminum mixture by adopting a variable-diameter pulsating air flow separation device to obtain a copper foil and an aluminum foil.
The treatment system is used for recovering the waste power lithium battery, volatile organic matters can be generated when the battery core is crushed, when the crushed electrode materials are subjected to high-temperature binder removal, the binder is organic matters, and can be volatilized when the temperature reaches 400-plus-500 ℃ to generate flue gas, and the flue gas and the volatile organic matters generated in the crushing process are ignited and added with quick lime to convert acid gas containing fluorine and phosphorus into calcium fluoride and calcium phosphate so as to realize harmless treatment. The electrode crushed aggregates are treated at high temperature, and the rest solid matters mainly comprise a mixture of copper foil, aluminum foil, electrode powder and a diaphragm and enter main separation equipment. In addition, the crushing mode adopted by the invention is shear type crushing, so that the shape after crushing is ensured, and meanwhile, the particle size is larger, thereby being beneficial to subsequent sorting. Secondly, sorting according to density and grading according to granularity according to density difference and granularity difference of copper foil, aluminum foil, diaphragm and electrode powder, and realizing a sorting-grading integrated process for sorting 4 products by feeding materials once, wherein the sorted copper foil and aluminum foil can be reused after simple treatment. The invention provides a complete pretreatment route for the waste power lithium battery, effectively classifies and recovers metal resources (copper and aluminum), diaphragms and electrode powder in the waste power lithium battery, does not produce any pollution in the treatment process, and is a resource and environment-friendly pretreatment process for the waste power lithium battery. In addition, the pretreatment process has the characteristics of simple structure, easy operation and the like, is easy to realize industrialization and large-scale production, and is very suitable for large-scale industrial application.
The crushing process adopts a shearing crushing mode, and in order to ensure the safety of the crushing process, the crushing process is under the protection of inert gas, and the crushing temperature is kept below 20 ℃.
In order to improve the efficiency of removing the binder by high-temperature roasting and ensure that the electrode powder does not generate oxidation-reduction reaction in the heating process, the roasting temperature is 400-500 ℃, and the good ventilation condition is ensured, and the roasting time is 1-2 h. And (4) treating the roasted organic volatile matters by a flue gas purification device and then discharging.
After the process, the residual solid mixture enters a dry recovery system of the waste power lithium battery.
The mixture is separated into two parts of copper foil, aluminum foil mixture and electrode powder and diaphragm mixture by a primary sorting system. Preferably, the air volume in the process is controlled to be 40-50m3And h, arranging a cloth bag dust removal device at the discharge end of the light product.
After the separation process is finished, the light products (electrode powder and diaphragm mixture) enter a primary grading system and are divided into two parts, namely electrode powder and a diaphragm. The classification system is equipped with a complete dust removal system.
The heavy product (copper foil and aluminum foil mixture) enters a secondary sorting system and is divided into a light product aluminum foil and a heavy product copper foil.
Preferably, the air quantity in the process is controlled to be 120-150m3And h, arranging a cloth bag dust removal device at the discharge end of the light product.
In steps S3 and S5, the primary and secondary sorting apparatuses employ a variable diameter pulsating air flow sorter. Preferably, the taper ratio of the variable-diameter section of the variable-diameter pulsating airflow separator is 1/25-4/25.
In steps S3 and S5, the primary and secondary sorting apparatuses employ a variable diameter pulsating air flow sorter. Preferably, the height of the straight cylinder section of the variable diameter pulsating gas flow separator is 0.5-1 m.
In steps S3 and S5, the primary and secondary sorting apparatuses employ a variable diameter pulsating air flow sorter. Preferably, the inner diameter of the discharge opening of the gas distributor of the variable-diameter pulsating gas flow separator accounts for 15-20% of the cross-sectional area of the separation column.
In step S4, the classifying means employs a cyclone.
As shown in fig. 2, a dry recovery system 40 for waste power lithium batteries comprises a primary air flow separator 41, a secondary air flow separator 42 and a primary classifier 43; the primary air flow separator 41 performs primary air flow separation on the electrode powder, the copper-aluminum mixture and the diaphragm to respectively obtain the electrode powder, the diaphragm mixture and the copper-aluminum mixture; the secondary airflow separator 42 performs secondary separation on the copper-aluminum mixture to obtain a copper foil and an aluminum foil; the primary classifier 43 performs classification processing on the electrode powder and separator mixture to obtain electrode powder and a separator.
And the high-temperature roasting device 20 is used for carrying out high-temperature treatment on the electrode crushed aggregates, removing the binder and grinding the electrode crushed aggregates by using a stirring mill to obtain the electrode powder and copper-aluminum mixture.
The device also comprises a flue gas purification device 30, wherein the flue gas purification device 30 is used for treating the flue gas generated by the high-temperature roasting device 20.
The battery cell cutting and crushing device further comprises a cutting and crushing device 10, wherein the cutting and crushing device is used for crushing the battery cells of the waste power lithium batteries to obtain electrode crushed materials and diaphragms.
The battery cell shearing and crushing device further comprises a discharging device 50, and before the battery cell is sheared and crushed, the discharging device 50 carries out a deep discharging process on the waste power lithium battery.
The invention is described above with reference to the accompanying drawings, it is obvious that the implementation of the invention is not limited in the above manner, and it is within the scope of the invention to adopt various modifications of the inventive method concept and solution, or to apply the inventive concept and solution directly to other applications without modification.
Claims (10)
1. A dry recovery method of waste power lithium batteries comprises the following steps:
s1, crushing the battery cell of the waste power lithium battery in a shearing and crushing mode to obtain electrode crushed materials and a diaphragm;
s2, performing high-temperature treatment on the electrode crushed aggregates, removing the binder, and grinding the electrode crushed aggregates by using a stirring mill to obtain electrode powder and a copper-aluminum mixture;
s3, carrying out primary air flow separation on the electrode powder, the copper-aluminum mixture and the diaphragm obtained in the S1 to respectively obtain the electrode powder, the diaphragm mixture and the copper-aluminum mixture;
s4, carrying out classification treatment on the electrode powder and diaphragm mixture to obtain electrode powder and a diaphragm;
and S5, carrying out secondary sorting on the copper-aluminum mixture to obtain a copper foil and an aluminum foil.
2. The dry recovery method of waste power lithium batteries according to claim 1, characterized in that: in the step S1, the crushing mode is shearing crushing to ensure the shape of the crushed material.
3. The dry recovery method of waste power lithium batteries according to claim 1, characterized in that: in the step S2, the binder is removed by the high-temperature treatment under ventilation conditions to ensure that the organic binder undergoes a cracking reaction, so as to obtain the cracked gas and the electrode powder.
4. The dry recovery method of waste power lithium batteries according to claim 2, characterized in that: in the step S2, the temperature of the high-temperature treatment is 400-; the high-temperature treatment time is 1-2 h.
5. The dry recovery method of waste power lithium batteries according to claim 3 or 4, characterized in that: in the step S2, the grinding medium used by the stirring mill adopts quartz sand with the granularity of 3-6mm, and the filling rate of the medium is more than 50%.
6. The dry recovery method of waste power lithium batteries according to claim 3, 4 or 5, characterized in that: the step S2 further includes a flue gas purification treatment process, where the flue gas purification treatment process treats the flue gas generated by the high-temperature treatment.
7. The dry recovery method for waste power lithium batteries as claimed in claim 1, wherein in step S3, a variable diameter pulsating air flow separator is used for primary air flow separation of the electrode powder, the copper-aluminum mixture and the diaphragm;
preferably, the air volume of the variable diameter pulsating air flow separator is 40-50m3/h；
Preferably, the taper ratio of the variable-diameter section of the variable-diameter pulsating airflow separator is 1/25-4/25;
preferably, the height of the straight cylinder section of the variable diameter pulsating airflow separator is 0.5-1 m;
preferably, the inner diameter of a discharge opening of the gas distributor of the variable-diameter pulsating gas flow separator accounts for 15-20% of the cross-sectional area of the separation column.
8. The dry recycling method for waste lithium power batteries as claimed in claim 1, wherein in step S4, the mixture of electrode powder and diaphragm is classified and treated by cyclone separator.
9. The dry recovery method for waste power lithium batteries as claimed in claim 1, characterized in that in step S5, a variable diameter pulsating air flow separator is used for secondary air flow separation of the copper-aluminum mixture;
preferably, the air volume of the variable-diameter pulsating airflow sorting machine is 150m3/h；
Preferably, the taper ratio of the variable-diameter section of the variable-diameter pulsating airflow separator is 1/25-4/25;
preferably, the height of the straight cylinder section of the variable diameter pulsating airflow separator is 0.5-1 m;
preferably, the inner diameter of a discharge opening of the gas distributor of the variable-diameter pulsating gas flow separator accounts for 15-20% of the cross-sectional area of the separation column.
10. The dry recycling method for waste lithium power batteries according to any one of claims 1 to 9, wherein in step S1, before the cutting and crushing of the battery cells, the dry recycling method further comprises a deep discharging process for the waste lithium power batteries.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111180820A (en) * | 2020-01-04 | 2020-05-19 | 浙江大学 | Method for recovering lithium ion battery original material and regenerating battery |
| CN111900506A (en) * | 2020-08-03 | 2020-11-06 | 韶山润泽新能源科技有限公司 | Battery positive plate regeneration treatment system and process |
| CN112974465A (en) * | 2020-12-28 | 2021-06-18 | 北京博萃循环科技有限公司 | Harmless recovery treatment method for waste lithium ion battery |
| CN113659225A (en) * | 2021-07-20 | 2021-11-16 | 河南巨峰环保科技有限公司 | Recycling method of lithium battery diaphragm waste material |
| CN114006070A (en) * | 2021-10-31 | 2022-02-01 | 湖南江冶机电科技股份有限公司 | Method for high-temperature pyrolysis and aerodynamic stripping and sorting of waste lithium batteries |
| CN114256527A (en) * | 2021-12-06 | 2022-03-29 | 中国矿业大学(北京) | Method for removing impurities and separating positive electrode and negative electrode of waste lithium ion battery mixed material |
| WO2022156070A1 (en) * | 2021-01-21 | 2022-07-28 | 惠州市特创电子科技股份有限公司 | Method for separation and recovery of circuit board drilling waste |
| WO2023070801A1 (en) * | 2021-10-31 | 2023-05-04 | 湖南江冶机电科技股份有限公司 | Recovery method for valuable components of waste lithium-ion batteries |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111180820A (en) * | 2020-01-04 | 2020-05-19 | 浙江大学 | Method for recovering lithium ion battery original material and regenerating battery |
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| CN112974465A (en) * | 2020-12-28 | 2021-06-18 | 北京博萃循环科技有限公司 | Harmless recovery treatment method for waste lithium ion battery |
| WO2022156070A1 (en) * | 2021-01-21 | 2022-07-28 | 惠州市特创电子科技股份有限公司 | Method for separation and recovery of circuit board drilling waste |
| CN113659225A (en) * | 2021-07-20 | 2021-11-16 | 河南巨峰环保科技有限公司 | Recycling method of lithium battery diaphragm waste material |
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| WO2023070801A1 (en) * | 2021-10-31 | 2023-05-04 | 湖南江冶机电科技股份有限公司 | Recovery method for valuable components of waste lithium-ion batteries |
| CN114256527A (en) * | 2021-12-06 | 2022-03-29 | 中国矿业大学(北京) | Method for removing impurities and separating positive electrode and negative electrode of waste lithium ion battery mixed material |
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