CN111934042B - Physical recycling method for retired power battery - Google Patents
Physical recycling method for retired power battery Download PDFInfo
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- CN111934042B CN111934042B CN202010768488.8A CN202010768488A CN111934042B CN 111934042 B CN111934042 B CN 111934042B CN 202010768488 A CN202010768488 A CN 202010768488A CN 111934042 B CN111934042 B CN 111934042B
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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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- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
Abstract
The invention relates to a physical recycling method of retired power batteries, which comprises the following steps: step S1: discharging the retired lithium ion battery and then shredding the retired lithium ion battery; step S2: performing diaphragm treatment on the mixture shredded in the step S1, performing pyrolysis treatment by using pyrolysis equipment, heating in a closed space for pyrolysis at the temperature ranging from 200 ℃ to 400 ℃, and fully pyrolyzing the organic matters at high temperature; and step S3: after the step S2 is finished, sequentially performing primary hammering, primary cyclone dust removal and primary vibrating screen treatment on the material to obtain finished anode and cathode powder; a mixture A consisting of a shell, copper foil, aluminum foil and anode and cathode powders; and step S4: selecting the steel shell in the material by a suspension flotation magnetic method of the material on a lower magnetic roller and an upper magnetic roller to obtain a finished product of the steel shell battery shell for recycling; the method has the advantages of improving economic benefits and high recovery rate of valuable metals.
Description
Technical Field
The invention belongs to the technical field of recycling of lithium ion batteries, and particularly relates to a physical recycling method of a retired power battery.
Background
With the explosive growth of new energy automobiles under the guidance of national policies, a power battery cannot be effectively recycled after being scrapped and becomes a serious social problem, the power battery consists of a positive electrode, a negative electrode, a diaphragm (polyethylene or polypropylene) and a shell, the positive electrode material consists of positive electrode powder (lithium cobaltate, lithium nickel manganese oxide, lithium iron phosphate and lithium titanate) and an aluminum foil, the negative electrode consists of graphite powder and a copper foil, and the shell generally consists of an aluminum shell, a steel shell, plastics, an aluminum plastic film and the like; the existing physical recovery process for the retired power battery in the field has the defects of low recovery rate of valuable metals, mainly reflects in diaphragm treatment, hardware recovery treatment, copper-aluminum separation of a large amount of doped noble metal (cobalt, nickel and lithium) powder contained in copper and aluminum and mixed copper-aluminum powder and control of dust amount, and the factors directly influence the economic benefit of the whole retired battery recovery industry.
The traditional process has the following four defects: 1. the traditional diaphragm is a sieving method, an air flow adsorption method, and the sieving method and the air flow adsorption method have the defects that: the production capacity is low, the diaphragm is difficult to treat (the diaphragm has no economic value, is generally buried or incinerated in the open air and has great environmental pollution), the separation effect of the positive and negative electrode powder, the copper-aluminum powder and the diaphragm is poor, and the recovery rate of valuable metals (cobalt, nickel and lithium) is low, because a part of the valuable metals (cobalt, nickel and lithium) can be taken away from the surface of the diaphragm while the decommissioned power battery mixture is treated by a screening method or an air flow adsorption method, the economic benefit is directly influenced; 2. the recovery of hardware (nickel-plated steel shell), the traditional process generally selects the crushed mixed material of the retired power battery in a way of putting the material under an upper magnetic roller, so that the anode and cathode powder and copper and aluminum can be selected while the hardware is selected, the recovery of the hardware can only reach within 70%, the rest 30% is valuable metal, and the recovery benefit can be directly influenced; 3. the recycling value is directly influenced due to the reasons that the recycling rate of the positive and negative electrode powder is low and the content of the copper and aluminum powder is low because a large amount of valuable metal (cobalt nickel lithium) is wrapped in the traditional crushed copper and aluminum material; 4. the copper-aluminum powder in the traditional process is directly sold, aluminum does not count the price but only counts the copper price, but only counts the copper price and is not high (because the content of copper in the copper-aluminum powder is between 30 and 60 percent); aiming at the defects, a physical recycling method for the retired power battery, which improves economic benefits and has high recovery rate of valuable metals, needs to be developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a physical recycling method for retired power batteries, which improves the economic benefit and has high recovery rate of valuable metals.
The purpose of the invention is realized by the following steps: the physical recycling method of the retired power battery comprises the following steps:
step S1: discharging the retired lithium ion battery and then shredding the retired lithium ion battery;
step S2: performing diaphragm treatment on the mixture shredded in the step S1, performing pyrolysis treatment by using pyrolysis equipment, heating in a closed space to perform pyrolysis, wherein the temperature range is 200-400 ℃, and fully pyrolyzing and disappearing the organic matters at high temperature;
and step S3: after the step S2 is finished, sequentially performing primary hammering, primary cyclone dust removal and primary vibrating screen treatment on the material to obtain finished anode and cathode powder; the shell, the copper foil, the aluminum foil and the anode and cathode powders form a mixture A;
and step S4: selecting and treating the steel shells in the mixture A obtained in the step S3 by a suspension flotation magnetic method of the material on a lower magnetic roller and an upper magnetic roller to obtain a finished product of the steel shell battery shell for recycling, and then sequentially carrying out secondary flail knife crushing, secondary cyclone dust removal and a secondary vibrating screen on the mixture A without the steel shells to obtain a finished product of anode and cathode powder and a finished product of the aluminum shell battery shell for recycling; copper powder, aluminum powder and a positive and negative electrode powder combined mixture B;
step S5: sequentially carrying out three-stage high-speed fine crushing, three-stage cyclone dust removal and three-stage ultrasonic screening on the mixture B obtained in the step S4 to obtain finished anode and cathode powder and copper-aluminum mixture particles, and recovering the finished anode and cathode powder;
step S6: and (5) sequentially carrying out four-stage cyclone dust removal and specific gravity screening on the copper-aluminum mixture particles in the step S5 to obtain finished copper particles and finished aluminum particles, and then respectively packaging.
And in the steps S1 to S6, dust removal is carried out in a negative pressure mode.
And screening and packaging the screened finished product of the anode and cathode powder, the screened finished product of the copper, the screened finished product of the aluminum and the screened finished product of the steel shell in a negative pressure mode.
The diaphragm treatment is heating pyrolysis treatment on the retired power battery material in a rotary furnace.
And in the step S3 to the step S6, the feeding and discharging of the materials between the devices are carried out in a negative pressure mode.
And in the step S1-the step S2, waste gas treatment equipment is adopted, and the waste gas treatment equipment comprises water spraying, activated carbon adsorption and RCO catalytic oxidation.
The invention has the beneficial effects that: the invention has the advantages that the traditional method for treating the diaphragm is changed, the method has the characteristics of high recovery rate of valuable metals, small pollution and the like, particularly, the diaphragm is subjected to pyrolysis treatment, no valuable metals are lost without the production of the diaphragm, and conditions are created for the subsequent smelting recovery; in addition, the traditional method for processing the hardware (nickel-plated iron shell) is changed, the method disclosed by the invention is used for selecting the hardware by a suspension flotation magnetic method of materials on a lower magnetic roller and an upper magnetic roller, valuable metals including cobalt, nickel, lithium, copper and aluminum cannot be brought away in the selection process, the suspension magnetic selection has the characteristic that the recovery rate of the selected hardware is up to 99%, the problem of valuable metal loss in the selection process is reduced, and other beneficial effects are detailed in specific embodiments.
Drawings
Fig. 1 is a process flow diagram of the physical recycling method of the retired power battery of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without making creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the terms used herein are for the purpose of describing particular embodiments only and are not intended to be limiting of the invention, and terms such as "and/or" as used herein include any and all combinations of one or more of the associated listed items; in addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Examples
The physical recycling method of the retired power battery comprises the following steps: step S1: discharging the retired lithium ion battery and then shredding the retired lithium ion battery; step S2: performing diaphragm treatment on the mixture shredded in the step S1, performing pyrolysis treatment by using pyrolysis equipment, heating in a closed space to perform pyrolysis, wherein the temperature range is 200-400 ℃, and fully pyrolyzing the organic matters at high temperature; and step S3: after the step S2 is finished, sequentially performing primary hammering, primary cyclone dust removal and primary vibrating screen treatment on the material to obtain finished anode and cathode powder; . The shell, the copper foil, the aluminum foil and the anode and cathode powders form a mixture A; and step S4: selecting and treating the steel shells in the mixture A obtained in the step S3 by a suspension flotation magnetic method of the material on a lower magnetic roller and an upper magnetic roller to obtain a finished product of the steel shell battery shell for recycling, and then sequentially carrying out secondary flail knife crushing, secondary cyclone dust removal and a secondary vibrating screen on the mixture A without the steel shells to obtain a finished product of anode and cathode powder and a finished product of the aluminum shell battery shell for recycling; copper powder, aluminum powder and a positive and negative electrode powder combined mixture B; step S5: sequentially carrying out three-stage high-speed fine crushing, three-stage cyclone dust removal and three-stage ultrasonic screening on the mixture B obtained in the step S4 to obtain finished anode and cathode powder and copper-aluminum mixture particles, and recovering the finished anode and cathode powder; step S6: and (2) sequentially performing four-stage cyclone dust removal and specific gravity screening on the copper-aluminum mixture particles in the step S5 to obtain finished copper particles and finished aluminum particles, and then respectively packaging the finished copper particles and the finished aluminum particles, wherein dust removal is performed in the step S1-step S6 in a negative pressure mode, screened finished anode and cathode powder, finished copper, finished aluminum and finished steel shells are screened and packaged in a negative pressure mode, the diaphragm treatment is to perform heating pyrolysis treatment on retired power battery materials in a rotary furnace, feeding and discharging of the materials between equipment in the step S3-step S6 are transmitted and processed in a negative pressure mode, waste gas treatment equipment is adopted in the step S1-step S2, and the waste gas treatment equipment is water spraying, activated carbon adsorption and RCO catalytic oxidation.
In this embodiment, 1, by changing the conventional diaphragm removing and processing method, the method has the characteristics of high recovery rate of valuable metals, low pollution and the like, specifically, the diaphragm is subjected to pyrolysis processing, no valuable metals are lost due to no diaphragm, conditions are created for downstream hydrometallurgy recovery of the users, and the pyrolysis equipment and the process have two types: the utility model provides a pyrolysis equipment technology is fixed quantitative horizontal pyrolysis machine (feed bin size determines the productivity size) material and heats in airtight space and carry out the pyrolysis process, lets the burning of organic matter (diaphragm and organic matter) through high temperature, the advantage: the temperature is controllable, generally between 200 ℃ to 400 ℃, so that the copper-aluminum metal in the pyrolyzed decommissioned power battery can not be oxidized at high temperature, and subsequent copper-aluminum recovery is not affected, and the defects are as follows: the capacity is relatively low, and the other pyrolysis heat preparation process is that the rotary furnace heats and pyrolyzes the decommissioned power battery materials, and has the advantages that: the productivity is large, because the material is thrown in the circulation, the circulation ejection of compact, the shortcoming: the temperature is not easy to control, high-temperature oxidation can be caused to copper and aluminum in the power battery when the temperature is too high, the shape of the oxidized copper and aluminum is changed into powder, and the subsequent recovery of the copper and aluminum is influenced. The waste gas generated by the process is recycled by water spraying, activated carbon adsorption and RCO catalytic oxidation waste gas treatment equipment, so that secondary pollution to the environment is avoided;
2. the invention changes the traditional method for selecting the treated hardware (nickel-plated steel shell), the process is to select the hardware by a suspension flotation magnetic method with materials on a lower magnetic roller and an upper magnetic roller, valuable metals including cobalt, nickel, lithium, copper and aluminum cannot be taken away in the selection process, the recovery rate of the selected hardware is up to 99% by suspension magnetic selection, and the problem of loss in the valuable metal selection process is reduced;
3. after the positive and negative electrode powder mixture wrapped in the copper-aluminum powder is subjected to high-speed fine crushing, the positive and negative electrode powder (valuable metal) wrapped in the copper-aluminum powder is fully separated from copper and aluminum, and then the copper-aluminum powder and the positive and negative electrode powder are separated through a high-mesh ultrasonic sieve.
4. The clean copper-aluminum powder mixture is screened by a gravity screen to separate copper and aluminum respectively, the copper content is about 97 percent, the aluminum content is about 90 percent, and the separated 97 percent copper powder and 90 percent aluminum powder can be sold respectively.
5. The process is completely negative pressure operation, firstly, no dust (valuable metal) is generated, the recovery rate is higher if no dust is generated, the traditional process is not completely negative pressure operation, the process is specifically experienced in a feeding mechanism and a discharging mechanism, 1, the feeding mechanism and the discharging mechanism are generally belt transmission and spiral transmission, and the feeding mechanism and the discharging mechanism can generate dust in the working process; 2. the discharging mechanism generally adopts a mode that a high-pressure fan blows materials into a cyclone dust collector in a positive pressure mode and then the materials are discharged through a wind shield, so that the problems of service life reduction and frequent maintenance of the high-pressure fan can be caused, dust can be generated as long as positive-pressure feeding is carried out, and the recovery rate is low if the dust is generated. The improved process includes that the materials after hammer crushing are sucked into a cyclone dust collector in a negative pressure mode and then are discharged through an air damper, so that the problems that the materials after hammer crushing are simultaneously fed into the cyclone dust collector through the air damper and then are discharged into a first-stage vibrating screen, the materials discharged from the first-stage vibrating screen and fed into a flail knife crusher, the materials discharged from the flail knife crusher and fed into the cyclone dust collector through the air damper and then are discharged into a second-stage vibrating screen, the materials discharged from the second-stage vibrating screen and fed into a high-speed fine crushing machine, the materials discharged from the high-speed fine crushing machine and fed into an ultrasonic screen through the air damper and then are discharged into the cyclone dust collector through the air damper and then are discharged into a specific gravity separation screen are solved.
6. And all the screened finished product anode and cathode powder, finished product copper powder, finished product aluminum powder and finished product hardware respectively enter a cyclone dust collector of each material in a negative pressure mode to be collected, and the materials are discharged by a wind shield to respectively package various finished products.
The present invention is further described in the detailed description, rather than by limitation, and it will be apparent to those skilled in the art that numerous changes in structure may be made without departing from the spirit and scope of the invention, all of which are intended to be covered by the appended claims.
Claims (3)
1. The physical recycling method of the retired power battery is characterized by comprising the following steps:
step S1: discharging the retired lithium ion battery and then shredding the retired lithium ion battery;
step S2: performing diaphragm treatment on the mixture shredded in the step S1, performing pyrolysis treatment by using pyrolysis equipment, heating in a closed space for pyrolysis at the temperature ranging from 200 ℃ to 400 ℃, and fully pyrolyzing the organic matters at high temperature;
and step S3: after the step S2 is finished, sequentially performing primary hammering, primary cyclone dust removal and primary vibrating screen treatment on the material to obtain finished anode and cathode powder; a mixture A consisting of a shell, copper foil, aluminum foil and anode and cathode powders;
and step S4: selecting and treating the steel shells in the mixture A obtained in the step S3 by a suspension flotation magnetic method of the material on a lower magnetic roller and an upper magnetic roller to obtain a finished product of the steel shell battery shell for recycling, and then sequentially carrying out secondary flail knife crushing, secondary cyclone dust removal and a secondary vibrating screen on the mixture A without the steel shells to obtain a finished product of anode and cathode powder and a finished product of the aluminum shell battery shell for recycling; copper powder, aluminum powder and a positive and negative electrode powder combined mixture B;
step S5: sequentially carrying out three-stage high-speed fine crushing, three-stage cyclone dust removal and three-stage ultrasonic screening on the mixture B obtained in the step S4 to obtain finished anode and cathode powder and copper-aluminum mixture particles, and recovering the finished anode and cathode powder;
step S6: sequentially carrying out four-stage cyclone dust removal and specific gravity screening on the copper-aluminum mixture particles in the step S5 to obtain finished copper particles and finished aluminum particles, and then respectively packaging;
the steps S1 to S6 are all dust removal in a negative pressure mode;
screening and packaging the screened finished anode and cathode powder, the screened finished copper, the screened finished aluminum and the screened finished steel shell in a negative pressure mode;
and in the step S3 to the step S6, the feeding and discharging of the materials between the devices are carried out in a negative pressure mode.
2. The physical recycling method of retired power battery according to claim 1, characterized in that: the diaphragm treatment is heating pyrolysis treatment on the retired power battery material in a rotary furnace.
3. The physical recycling method of retired power battery according to claim 1, characterized in that: and in the step S1-the step S2, waste gas treatment equipment is adopted, and the waste gas treatment equipment comprises water spraying, activated carbon adsorption and RCO catalytic oxidation.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN113953312A (en) * | 2021-11-16 | 2022-01-21 | 张金庆 | Automatic production line and process for extracting and repairing negative electrode material |
| CN115084703B (en) * | 2022-08-18 | 2022-12-06 | 深圳市杰成镍钴新能源科技有限公司 | Retired power battery recycling method, device and system |
| CN115784192B (en) * | 2023-02-02 | 2023-04-28 | 中国科学院过程工程研究所 | Method for recycling positive electrode powder of lithium iron phosphate battery |
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| KR101718422B1 (en) * | 2015-02-11 | 2017-04-04 | 한국지질자원연구원 | Continuous Heat treatment apparatus and Method of Recovering Valuable Metals from Lithium Battery using the same |
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