CN110661055B - Method for efficiently stripping waste lithium ion battery material - Google Patents
Method for efficiently stripping waste lithium ion battery material Download PDFInfo
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- CN110661055B CN110661055B CN201910973131.0A CN201910973131A CN110661055B CN 110661055 B CN110661055 B CN 110661055B CN 201910973131 A CN201910973131 A CN 201910973131A CN 110661055 B CN110661055 B CN 110661055B
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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 the technical field of waste lithium ion battery treatment, and provides a method for efficiently stripping a waste lithium ion battery material, which comprises the following steps: carrying out microwave sintering on the pole piece obtained after the waste lithium ion battery is disassembled, and separating powder on the surface of the pole piece after cooling to respectively obtain a metal foil and an electrode material; wherein the temperature of the microwave sintering is 350-500 ℃, and the heat preservation time is 30-120 min. The invention utilizes the vibration of organic binder molecules in a high-frequency magnetic field (microwave), the molecules collide and rub with each other to generate heat energy, and the material absorbs the energy and then rapidly heats up from inside to outside, so that the organic binder is decomposed in a short time, and the purpose of separating the anode and cathode materials from the metal foil is achieved; the method provided by the invention has the advantages of short flow, simple operation, no pollution, high stripping speed and high efficiency, and can obtain complete metal foils and clean anode and cathode materials.
Description
Technical Field
The invention relates to the technical field of waste lithium ion battery treatment, in particular to a method for efficiently stripping a waste lithium ion battery material.
Background
With the development of mobile communication and electronic industry, lithium ion batteries have also been rapidly developed and widely used in the fields of mobile phones, notebook computers, tablet computers, digital cameras, electric vehicles, and the like. Statistically, the global consumption of lithium ion batteries rapidly increased from 5 hundred million in 2000 to 70 hundred million in 2015. In 2020, the quantity of waste lithium ion batteries in China only can reach 250 hundred million, and the total weight is 50 ten thousand tons. After the lithium ion battery is charged and discharged for hundreds of times to thousands of times, the electrode active material gradually loses activity due to the problems of structural change, dissolution loss and the like, so that the capacity of the lithium battery is reduced, and finally the lithium ion battery is scrapped. If the waste lithium ion battery is discarded at will, electrolyte salt and organic solvent in the battery can cause harm to the environment, and simultaneously, the waste of resources is also caused. With the rapid increase of the new energy automobile output, the retirement peak of the power battery is about to come, according to the measurement and calculation, the demand of the power lithium battery reaches 125Gwh in 2020, and the scrappage reaches 32.2Gwh, about 50 ten thousand tons; by 2023, the scrappage will reach 101Gwh, about 116 ten thousand tons. The lithium ion battery contains valuable metal elements such as lithium, cobalt, nickel, copper, aluminum and the like, and the content of the valuable metal elements is far higher than the mine grade, so that the recovery of the lithium ion battery is of great significance to the environmental protection and the resource saving.
The pole pieces (including the positive pole piece and the negative pole piece) of the electrode are composed of electrode materials (positive pole materials or negative pole materials), organic binders and current collectors (metal foils), wherein the powdery electrode materials are bound on the metal foils through the organic binders, and the electrode materials and the metal foils need to be peeled off to realize the recovery of valuable metals. At present, a plurality of methods for stripping pole pieces in the recovery process of waste lithium ion batteries are provided. CN200910304134.1 discloses an efficient leaching process for a waste lithium battery positive electrode active material, which adopts an acid leaching method, adopts a strong acid solution to carry out acid leaching on the positive electrode material and a current collector (aluminum foil), and then separates out valuable metal elements by extraction, precipitation and other methods. The method can not obtain metal aluminum, and the aluminum and other elements need to be separated by hydrometallurgy in the later period, so the process is long. CN201610832665.8 discloses a method for recycling a strong alkaline solution in the waste lithium battery recycling industry, which is characterized in that a current collector (aluminum foil) is dissolved by using strong alkaline to separate a positive electrode material from the aluminum foil, and then the solution is filtered to obtain the positive electrode material. This method also fails to obtain metallic aluminum. CN201610314509.2 discloses a separation and collection device and a method for all-component materials of waste lithium batteries, which are characterized in that a mechanical crushing method is adopted to crack the waste batteries into particles, in the process of rolling and crushing, a positive electrode material and a current collector are separated under the combined action of shearing of a crushing blade and mutual friction between the particles and fragments, and then the positive electrode material and the current collector are separated and collected through subsequent separation steps of air separation, sieving and the like. Although metal aluminum powder can be obtained by this method, the aluminum powder in the positive electrode material and the positive electrode material in the aluminum powder cannot be efficiently separated. CN103985920B discloses a method for separating lithium cobaltate and aluminum foil on a waste lithium ion positive plate, which comprises the steps of roasting the waste positive plate by using a box-type resistance furnace at 500-600 ℃, then soaking in water under the stirring condition, finally obtaining a mixed solution of the aluminum foil and a positive active material by a screening method, and obtaining the lithium cobaltate after the mixed solution is subjected to high-temperature treatment. The method has high requirement on equipment, and the anode plate is difficult to avoid embrittlement during roasting, so that the anode plate and the active material are not completely separated. CN102703706B discloses a method for separating lithium cobaltate and aluminum foil on a waste lithium ion positive electrode sheet, which comprises the steps of soaking cell fragments of a waste lithium cobaltate cell in N, N-dimethylformamide and/or N-methylpyrrolidone for 0.5-3 h under stirring and ultrasonic oscillation, and then filtering to obtain filtrate and filter residue, wherein the lithium cobaltate is positioned in the filter residue; and screening the filter residue, wherein oversize products are aluminum, copper foil and a diaphragm, and undersize products are mixed powder of lithium cobaltate and graphite. The method adopts the organic solvent to treat the waste lithium cobaltate battery, has long flow, complex operation, large organic solvent consumption and high cost, and the filtered filter residue carries the organic solvent which is volatilized during drying to cause environmental pollution.
Disclosure of Invention
In view of the above, the present invention provides a method for efficiently peeling off waste lithium ion battery materials. The method provided by the invention has the advantages of short flow, simple operation, no pollution and good stripping effect, and can obtain complete metal foils and clean anode and cathode materials.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for efficiently stripping waste lithium ion battery materials comprises the following steps: carrying out microwave sintering on the pole piece obtained after the waste lithium ion battery is disassembled, and separating powder on the surface of the pole piece after cooling to respectively obtain a metal foil and an electrode material;
wherein the temperature of the microwave sintering is 350-500 ℃, and the heat preservation time is 30-120 min.
Preferably, the heating rate of heating to the microwave sintering temperature is 10-30 ℃/min.
Preferably, the microwave sintering is performed in an air, nitrogen, argon or vacuum environment.
Preferably, when the microwave sintering is performed in a nitrogen or argon environment, the flow rate of the nitrogen or argon is independently 5-10L/min.
Preferably, when the microwave sintering is performed in a vacuum environment, the pressure of the vacuum environment is 10-100 kPa.
Preferably, the microwave power of the microwave sintering is 1-2.8 kw.
Preferably, in the microwave sintering process, the organic binder in the pole piece is cracked, and the generated volatile matter enters a tail gas treatment system for treatment.
Preferably, the separation method is sieving, the oversize is metal foil, and the undersize is electrode material.
The invention provides a method for efficiently stripping waste lithium ion battery materials, which comprises the following steps: carrying out microwave sintering on the pole piece obtained after the waste lithium ion battery is disassembled, and separating powder on the surface of the pole piece after cooling to respectively obtain a metal foil and an electrode material; wherein the temperature of the microwave sintering is 350-500 ℃, and the heat preservation time is 30-120 min. The invention utilizes the vibration of organic binder molecules in a high-frequency magnetic field (microwave), the molecules collide and rub with each other to generate heat energy, and the material absorbs the energy and then rapidly heats up from inside to outside, so that the organic binder is decomposed in a short time, and the purpose of separating the electrode material from the metal foil is achieved; the method provided by the invention has the advantages of short flow, simple operation, no pollution, high stripping speed and high efficiency, and can obtain complete metal foils and clean electrode materials. The results of the examples show that the positive/negative electrode material remaining on the metal foil after peeling using the method of the present invention was less than 1.0 wt.% of the total amount of the positive/negative electrode material.
Detailed Description
The invention provides a method for efficiently stripping waste lithium ion battery materials, which comprises the following steps: and (3) performing microwave sintering on the pole piece obtained after the waste lithium ion battery is disassembled, and separating powder on the surface of the pole piece after cooling to respectively obtain the metal foil and the electrode material.
The invention has no special requirements on the disassembling method, and the pole piece can be obtained after disassembling by using the disassembling method well known by the technical personnel in the field; the pole piece comprises a positive pole piece and a negative pole piece; the positive/negative electrode sheet consists of a metal foil (current collector) and a positive/negative electrode material adhered to the surface of the metal foil, and the adhesive is an organic adhesive; the invention has no special requirements on the types of the metal foils, and in the field, the current collector of the positive plate of the lithium ion battery is usually an aluminum foil, and the current collector of the negative plate is usually a copper foil.
In the invention, the temperature of the microwave sintering is 350-500 ℃, preferably 400-450 ℃, the heat preservation time is 30-120 min, preferably 40-100 min, and the heating rate of heating to the microwave sintering temperature is preferably 10-30 ℃/min, more preferably 15-25 ℃/min; the microwave power of the microwave sintering is preferably 1-2.8 kw, and more preferably 1.4-2.5 kw.
In the present invention, the microwave sintering is preferably performed in an air, nitrogen, argon or vacuum environment; when the microwave sintering is carried out in a nitrogen or argon environment, the flow rate of the nitrogen or argon is preferably 5-10L/min independently, and more preferably 6-8L/min independently; when the microwave sintering is performed in a vacuum environment, the pressure of the vacuum environment is preferably 10 to 100kPa, and more preferably 40 to 80 kPa.
The invention uses a microwave sintering method to lead the organic binder to self-heat after absorbing the microwave, thereby leading the organic binder to be cracked and removed and achieving the purpose of stripping the electrode material and the metal foil (specifically, the anode material and the aluminum foil are stripped, and the cathode material and the copper foil are stripped); the invention can reduce the sintering temperature and shorten the sintering time through microwave sintering, and can realize the rapid cracking and volatilization of the organic binder at the temperature of below 500 ℃.
In the invention, in the microwave sintering process, the organic binder in the pole piece is cracked, and the generated volatile matters preferably enter a tail gas treatment system for treatment, and particularly preferably are pumped to a cooling system for cooling and then recovered.
After microwave sintering is finished, the sintered pole piece is cooled, and then powder on the surface of the pole piece is separated to respectively obtain the metal foil and the electrode material. In the invention, after the organic binder is decomposed, the electrode material is attached to the metal foil in a powder form, and the powder is separated to obtain a complete metal foil (specifically an aluminum foil or a copper foil) and a clean electrode material (a positive electrode material or a negative electrode material).
In the present invention, the cooling is preferably furnace-cooled to room temperature.
In the invention, the separation method is preferably sieving, wherein the oversize is a metal foil, and the undersize is an electrode material; the invention has no special requirement on the mesh number of the sieved screen, and the powdery electrode material can pass through the sieve.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
The current collectors of the positive plates in the waste lithium ion batteries used in the following examples are all aluminum foils, the current collectors of the negative plates are all copper foils, and the residual amounts of the positive/negative electrode materials in the following examples are the percentages of the mass of the residual positive/negative electrode materials on the aluminum foils/copper foils and the total mass of the positive/negative electrode materials.
Example 1
And (3) placing the positive/negative plate obtained after the lithium ion battery is disassembled into a microwave sintering furnace, wherein the microwave power is 1.4kw, heating to 350 ℃ at the heating rate of 10 ℃/min under the air condition, and keeping the temperature for 120 min. And cooling the pole piece along with the furnace, taking out and sieving, wherein the oversize product is aluminum foil/copper foil, and the undersize product is a positive/negative electrode material. The remaining amount of the positive/negative electrode material on the aluminum/copper foil was 1.0 wt.%.
Example 2
And (3) placing the positive and negative pole pieces obtained after the lithium ion battery is disassembled into a microwave sintering furnace, vacuumizing to 50kPa with the microwave power of 2.0kw, heating to 400 ℃ at the heating rate of 20 ℃/min, and keeping the temperature for 60 min. And cooling the pole piece along with the furnace, taking out and sieving, wherein the oversize product is aluminum foil/copper foil, and the undersize product is a positive/negative electrode material. The remaining amount of the positive/negative electrode material on the aluminum/copper foil was 0.8 wt.%.
Example 3
And (3) placing the positive and negative pole pieces obtained after the lithium ion battery is disassembled into a microwave sintering furnace, wherein the microwave power is 2.5kw, heating to 500 ℃ at the temperature rise rate of 30 ℃/min under the air condition, and keeping the temperature for 30 min. And cooling the pole piece along with the furnace, taking out and sieving, wherein the oversize product is aluminum foil/copper foil, and the undersize product is a positive/negative electrode material. The remaining amount of the positive/negative electrode material on the aluminum/copper foil was 0.3 wt.%.
Example 4
And (3) placing the positive and negative pole pieces obtained after the lithium ion battery is disassembled into a microwave sintering furnace, wherein the microwave power is 2..0kw, filling nitrogen/argon according to the rate of 5L/min, heating to 450 ℃ according to the rate of 20 ℃/min, and preserving the heat for 60 min. And cooling the pole piece along with the furnace, taking out and sieving, wherein the oversize product is aluminum foil/copper foil, and the undersize product is a positive/negative electrode material. The remaining amount of the positive/negative electrode material on the aluminum/copper foil was 0.5 wt.%.
Comparative example 1
Other conditions were the same as in example 1, and sintering was carried out in a normal sintering furnace without using only a microwave sintering furnace. The remaining amount of the positive/negative electrode material on the aluminum/copper foil was 50 wt.%.
According to the embodiments, the method provided by the invention can decompose and remove the organic binder, so that the purpose of peeling the anode and cathode materials from the metal foil is achieved, the method is suitable for separating the anode and cathode materials of the lithium ion battery from the aluminum foil/copper foil, the flow is short, the operation is simple, no pollution is caused, the peeling effect is good, and the complete aluminum foil/copper foil and the clean anode and cathode materials can be obtained.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A method for efficiently stripping waste lithium ion battery materials is characterized by comprising the following steps: carrying out microwave sintering on the pole piece obtained after the waste lithium ion battery is disassembled, and separating powder on the surface of the pole piece after cooling to respectively obtain a metal foil and an electrode material;
wherein the temperature of the microwave sintering is 350 ℃, and the heat preservation time is 30-120 min; the microwave sintering is carried out in a vacuum environment; the pressure of the vacuum environment is 10-100 kPa; the heating rate of heating to the microwave sintering temperature is 10-30 ℃/min; the microwave power of the microwave sintering is 1-2.8 kw; in the microwave sintering process, the organic binder in the pole piece is cracked, and the generated volatile matter enters a tail gas treatment system for treatment; the separation method comprises the steps of sieving, wherein the oversize is made of metal foil, and the undersize is made of electrode materials.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111342163A (en) * | 2020-04-08 | 2020-06-26 | 江西省科学院应用物理研究所 | Method for recovering positive active material of waste lithium battery |
| CN111733326A (en) * | 2020-07-03 | 2020-10-02 | 昆明理工大学 | Method for efficiently recycling ternary cathode material of waste lithium ion battery |
| CN112593085A (en) * | 2020-12-14 | 2021-04-02 | 中国矿业大学 | Device and method for recycling electrode material of retired lithium ion battery through segmented heat treatment |
| CN114361637B (en) * | 2022-01-14 | 2023-05-19 | 中南大学 | Method for separating electrode material and foil of lithium battery |
| CN114744319A (en) * | 2022-04-18 | 2022-07-12 | 南方科技大学 | Method for separating waste anode and cathode materials of waste lithium ion batteries |
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| CN103247837A (en) * | 2013-05-08 | 2013-08-14 | 国家电网公司 | Method for treating waste lithium battery by microwave pyrolysis |
| CN108110358A (en) * | 2017-12-16 | 2018-06-01 | 淄博国利新电源科技有限公司 | The recovery method of waste and old lithium ion battery binding agent |
| CN108336442A (en) * | 2018-03-01 | 2018-07-27 | 中国科学院过程工程研究所 | A method of detaching aluminium foil and anode waste from lithium ion battery positive plate |
| CN109103537A (en) * | 2018-09-27 | 2018-12-28 | 四川理工学院 | A kind of waste lithium cell microwave cracking processing method |
| CN109860753A (en) * | 2019-02-18 | 2019-06-07 | 银隆新能源股份有限公司 | A method of roasting waste and old lithium ion battery positive and negative pole material |
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| CN103247837A (en) * | 2013-05-08 | 2013-08-14 | 国家电网公司 | Method for treating waste lithium battery by microwave pyrolysis |
| CN108110358A (en) * | 2017-12-16 | 2018-06-01 | 淄博国利新电源科技有限公司 | The recovery method of waste and old lithium ion battery binding agent |
| CN108336442A (en) * | 2018-03-01 | 2018-07-27 | 中国科学院过程工程研究所 | A method of detaching aluminium foil and anode waste from lithium ion battery positive plate |
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