CN111600090A - Process for recycling waste lithium batteries - Google Patents
Process for recycling waste lithium batteries Download PDFInfo
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- CN111600090A CN111600090A CN202010491125.4A CN202010491125A CN111600090A CN 111600090 A CN111600090 A CN 111600090A CN 202010491125 A CN202010491125 A CN 202010491125A CN 111600090 A CN111600090 A CN 111600090A
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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 the technical field of battery recycling, in particular to a process for recycling waste lithium batteries. The method comprises the following steps: preparing a eutectic solvent, mixing and heating quaternary ammonium salt and an amine compound to prepare the eutectic solvent, wherein the quaternary ammonium salt is selected from one or a mixture of more of choline chloride, choline acetate or acetylcholine, and the amine compound is selected from one or a mixture of more of urea, ethanolamine and triethanolamine; and leaching, namely leaching the lithium cobaltate positive plate and the positive plate disassembled from the waste lithium battery by using the eutectic solvent to obtain a metal-containing solution and an aluminum foil current collector. The method has the advantages of wide raw material source, low cost, simple process method steps and the like.
Description
Technical Field
The invention relates to the technical field of battery recycling, in particular to a process for recycling waste lithium batteries.
Background
Lithium ion batteries have important applications in many fields due to their advantages of high energy density, long life cycle, low self-discharge energy, good safety performance, etc. Particularly, with the popularization and use of various intelligent electronic products and new energy automobiles, the application amount of lithium batteries in the products is larger.
At present, China has become the largest new energy automobile market in the world, and by the expectation of 2020, the demand of the lithium ion battery for the automobile in China will reach 125GWH, the scrappage will reach 32GWH, the scrappage battery is converted into the quality which will reach about 50 ten thousand tons, and the treatment of the waste battery with the huge quantity can become a troublesome problem. On the one hand, the conventional landfill treatment method causes pollution of soil and groundwater due to a large amount of heavy metals contained in the battery, so that the method is not feasible. On the other hand, the waste batteries contain valuable metal materials such as Co, Li, Ni, Cu, a1, etc., which are unfortunately not recycled. Therefore, the research on the recycling process of the waste lithium batteries has important economic significance and environmental protection significance.
In the prior art, the process for recovering valuable metals from waste lithium batteries mainly comprises a pyrogenic process, a hydrometallurgy and a combination of the pyrometallurgical process and the hydrometallurgy. The pyrogenic process is simple in treatment process, but high in energy consumption and generates a large amount of waste gas. The wet treatment mainly comprises the steps of leaching metals by inorganic acid or organic acid, wherein the inorganic acid has high leaching efficiency, but toxic and harmful gases (chlorine, sulfur dioxide, nitrogen dioxide and the like) can be generated, and the residual acidic waste liquid is difficult to treat and can bring secondary pollution; the organic acid leaching can lead to the complexity of the subsequent nickel, cobalt and manganese separation process and increase the recovery cost. It can be seen that there are many improvements in the existing processes for recovering valuable metals from spent lithium batteries.
Disclosure of Invention
The invention aims to provide a process for recovering waste lithium batteries, which aims to solve the problems that the existing process for recovering valuable metals from waste batteries has the defects of complex operation, high recovery cost, large amount of waste gas or waste liquid and the like, and further the recovery process is difficult to realize industrialization.
The invention provides a process for recycling waste lithium batteries, which comprises the following steps:
preparing a eutectic solvent: mixing and heating quaternary ammonium salt and amine compound to prepare the eutectic solvent, wherein the quaternary ammonium salt is selected from one or a mixture of more of choline chloride, choline acetate or acetylcholine, and the amine compound is selected from one or a mixture of more of urea, ethanolamine and triethanolamine;
leaching: and leaching the anode plate disassembled from the waste lithium battery by using the eutectic solvent to obtain a metal-containing solution and an aluminum foil current collector.
Further, the process further comprises, prior to the step of leaching, a battery pre-treatment: disassembling the waste lithium battery to obtain a positive plate of the lithium battery, and cleaning and drying the positive plate.
Further, in the step of battery pretreatment, the positive electrode sheet is washed and dried, and then coarsely pulverized to a particle size of 80 to 120 mesh.
It can be understood that the process of the application does not need to carry out complicated pretreatment operation on the waste lithium battery, does not need to grind the waste lithium battery into very small particle size to improve the extraction efficiency of metal, and does not need to carry out harsh pretreatment operation such as high-temperature calcination and the like. According to the method, follow-up operation can be carried out only by cleaning and drying the battery positive plate obtained by disassembly. In addition, the positive plate after being cleaned and dried can be simply and coarsely crushed into 80-120 meshes, and the metal leaching efficiency in subsequent leaching can be good. Wherein the coarse grinding of the battery positive plate to 80-120 meshes comprises any point value in the particle size range, such as the coarse grinding of the battery positive plate to 80 meshes, 90 meshes, 100 meshes, 110 meshes and 120 meshes.
Further, in the step of preparing the eutectic solvent, the molar ratio of the quaternary ammonium salt to the amine compound is 1:1-1:3, the heating temperature of the quaternary ammonium salt to the amine compound is 80-95 ℃, and the heating time is 5-10 hours.
Wherein the molar ratio of the quaternary ammonium salt to the amine compound is 1:1-1:3 inclusive, e.g., the molar ratio of the quaternary ammonium salt to the amine compound is 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:2.8, or 1: 3. The heating temperature of the quaternary ammonium salt and the amine compound is 80-95 ℃ inclusive of any value within this temperature range, for example, the heating temperature of the quaternary ammonium salt and the amine compound is 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃ or 95 ℃. Heating time of 5-10 hours includes any point within the time range, for example, heating time of 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours.
Preferably, in the step of preparing the eutectic solvent, the heating temperature is 90 ℃, the reaction time is 5-8 hours, the quaternary ammonium salt is choline chloride, and the amine compound is urea.
Further, in the leaching step, the leaching condition using the eutectic solvent is that the heating and stirring are carried out at 170-200 ℃ for 5-24 hours, and the ratio of the mass of the positive electrode plate to the volume of the eutectic solvent is 10-100 g/L.
Wherein the leaching temperature using the eutectic solvent is 170-200 ℃ includes any value within the leaching temperature, for example, the leaching temperature using the eutectic solvent is 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃. The heating time using the eutectic solvent is 5 to 24 hours including any point within the leaching time, for example, the heating time using the eutectic solvent is 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, or 24 hours. The ratio of the mass of the positive electrode plate to the volume of the eutectic solvent is 10-100g/L and includes any point value in the range of the solid-to-liquid ratio, for example, the ratio of the mass of the positive electrode plate to the liquid dosage of the eutectic solvent is 10g/L, 20g/L, 25g/L, 30g/L, 40g/L, 50g/L, 80g/L or 100 g/L.
Optionally, the waste lithium battery is a cobalt acid lithium battery, a lithium manganate battery or a ternary lithium battery, and the ternary lithium battery is a nickel cobalt lithium manganate battery or a nickel cobalt lithium aluminate battery.
Optionally, the waste lithium battery is a lithium nickel cobalt manganese oxide battery, and the process further includes, after the leaching step, precipitating: separating the solution containing the metal from the aluminum foil current collector, adding a precipitator with the same volume ratio into the solution containing the metal, precipitating for 5-10 hours at normal temperature, and filtering to obtain a solution containing the lithium and a solid precipitate containing cobalt, nickel and manganese respectively; wherein, the precipitant is selected from one of saturated carbonate, oxalate or sodium hydroxide.
Optionally, the process further comprises, after the step of precipitating, performing a purification: calcining the filtered solid precipitate at the temperature of 500-700 ℃ for 2-4 hours to obtain cobaltosic oxide; evaporating the filtered lithium-containing solution to obtain a lithium salt precipitate.
Preferably, in the step of purifying, the precipitate after filtration is calcined at 600 ℃ for 3 hours.
Optionally, the process further comprises, after the step of precipitating, performing a purification: and recrystallizing the lithium-containing solution to obtain lithium carbonate precipitate or lithium hydroxide precipitate.
Further, the process further comprises, after the step of recrystallizing, firing: and roasting the lithium carbonate precipitate or the lithium hydroxide precipitate obtained after recrystallization and the solid precipitate containing cobalt, nickel and manganese at the temperature of 800-900 ℃ for 3-5 hours to obtain the ternary active material.
Compared with the prior art, the technical scheme of the application has the following beneficial effects:
the application discloses a process for recycling waste lithium batteries, which has the advantages of wide raw material source, low cost, simple process method steps and the like. Compared with the traditional pyrometallurgical and hydrometallurgical processes, the hydrogen is not generated in the process, so that the hydrogen-free high-pressure metal oxide fuel is not easy to burn and explode and has high safety; because a large amount of acid agent is not needed, a large amount of waste acid is not generated and needs secondary treatment, and the method is environment-friendly; because the high-purity metal oxides or active materials such as lithium, cobalt and the like can be obtained, the recycling of resources is realized, and the method is a hydrogen-precipitation-free, green and environment-friendly waste battery recycling process and has a high industrial application prospect.
Drawings
FIG. 1 is the XRD pattern of cobaltosic oxide obtained in example nine;
FIG. 2 is an SEM photograph of cobaltosic oxide obtained in example nine.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terms "comprises" and "comprising," and any variations thereof, of embodiments of the present invention are intended to cover non-exclusive inclusions.
Example one
The embodiment provides a process for recycling waste lithium batteries, which comprises the following steps:
preparing a eutectic solvent: mixing and heating quaternary ammonium salt and amine compound to prepare the eutectic solvent, wherein the quaternary ammonium salt is selected from one or a mixture of more of choline chloride, choline acetate or acetylcholine, and the amine compound is selected from one or a mixture of more of urea, ethanolamine and triethanolamine;
leaching: and leaching the anode plate disassembled from the waste lithium battery by using the eutectic solvent to obtain a metal-containing solution and an aluminum foil current collector.
In the embodiment, the high-value metal in the battery positive plate disassembled from the waste lithium battery is recycled by the method of leaching the eutectic solvent. It should be noted that the waste lithium battery in this embodiment refers to a lithium battery in which the positive electrode sheet uses a nickel cobalt lithium manganate or nickel cobalt lithium aluminate ternary positive electrode material, or refers to a lithium battery in which the positive electrode sheet uses a lithium cobaltate or lithium manganate or other positive electrode materials, and after the lithium battery is scrapped after reaching the service life, lithium, cobalt, nickel, and manganese therein all have metals with recycling values. In the embodiment, the eutectic solvent technology is applied to the recovery of the waste lithium batteries, and the battery positive plates in the waste lithium batteries are leached by the eutectic solvent to obtain a solution containing metal lithium, cobalt, nickel and manganese or a solution containing metal lithium and cobalt, so that high-value metals in the waste lithium batteries can be effectively recovered and recycled.
Example two
The embodiment provides a process for recycling waste ternary lithium batteries, wherein the waste ternary lithium batteries are nickel cobalt lithium manganate batteries, and the process comprises the following steps of:
battery pretreatment: disassembling the waste ternary lithium battery to obtain a positive plate, cleaning and drying the positive plate, and coarsely crushing the positive plate to 80 meshes;
preparing a eutectic solvent: mixing choline chloride and urea according to a molar ratio of 1:1, heating at 90 ℃ for 5-8 hours to obtain a eutectic solvent;
leaching: leaching the ternary battery positive plate subjected to battery pretreatment by using the prepared eutectic solvent to obtain a metal-containing solution and an aluminum foil current collector; the solid-liquid ratio between the mass of the ternary battery positive plate and the volume of the eutectic solvent is 10g/L, the leaching condition is that the solution is heated and stirred for 15 hours at 170 ℃, and the obtained solution containing metal contains metal lithium, cobalt, nickel and manganese.
In the embodiment, in the battery pretreatment step, a waste battery pretreatment mode in the prior art is not adopted, the ternary battery positive plate of the waste lithium battery is not ground to a small particle size, harsh processing conditions such as high-temperature calcination and the like are not adopted, and the step of subsequently recovering high-value metals can be performed only by simply disassembling the positive plate, cleaning and drying the positive plate. The whole process step is simpler to operate and is more beneficial to industrial application. The key point of the method is that the eutectic solvent is used for leaching the ternary battery positive plate in the waste lithium battery, lithium, cobalt, nickel and manganese metals in the ternary battery positive plate are smoothly leached through the specific eutectic solvent, and the leaching can be performed smoothly without complex battery pretreatment.
Further, in order to recycle high-value metals in the waste ternary lithium battery, the embodiment further includes the following steps:
and (3) precipitation: separating the metal-containing solution from an aluminum foil current collector by filtering, adding saturated sodium carbonate in an equal volume ratio into the filtered metal-containing solution, precipitating for 5-8 hours at normal temperature, and filtering to obtain a lithium-containing solution and a solid precipitate containing cobalt, nickel and manganese respectively;
and (3) purification: recrystallizing the lithium-containing solution for multiple times, for example, recrystallizing for two or three times to obtain lithium carbonate precipitate;
roasting: and roasting the lithium carbonate precipitate obtained by recrystallization and the solid precipitate containing cobalt, nickel and manganese at the temperature of 800-900 ℃ for 3-5 hours to obtain the ternary active material. The ternary active material can be used for preparing a novel ternary lithium battery anode material.
Through the steps of precipitation, purification and roasting, the high-value metal recovered from the waste lithium battery can be reused in a higher-purity substance form and with higher value.
EXAMPLE III
The embodiment provides a process for recycling waste ternary lithium batteries, wherein the waste ternary lithium batteries are nickel cobalt lithium manganate batteries, and the process comprises the following steps of:
battery pretreatment: disassembling the waste ternary lithium battery to obtain a positive plate, cleaning and drying the positive plate, and coarsely crushing the positive plate to 120 meshes;
preparing a eutectic solvent: mixing choline chloride and urea according to a molar ratio of 1:2, heating at 93 ℃ for 6-8 hours to obtain a eutectic solvent;
leaching: leaching the ternary battery positive plate subjected to battery pretreatment by using the prepared eutectic solvent to obtain a metal-containing solution and an aluminum foil current collector; the solid-liquid ratio between the mass of the ternary battery positive plate and the volume of the eutectic solvent is 80g/L, the leaching condition is that the solution is heated and stirred for 5 hours at the temperature of 200 ℃, and the obtained solution containing metal contains metal lithium, cobalt, nickel and manganese;
and (3) precipitation: separating the metal-containing solution from an aluminum foil current collector by filtering, adding sodium hydroxide with the same volume ratio into the filtered metal-containing solution, precipitating for 8-10 hours at normal temperature, and filtering to respectively obtain a lithium-containing solution and a solid precipitate containing cobalt, nickel and manganese;
and (3) purification: subjecting the lithium-containing solution to multiple recrystallizations, for example, two or three recrystallizations, to obtain a lithium hydroxide precipitate;
roasting: and roasting the lithium carbonate precipitate obtained by recrystallization and the solid precipitate containing cobalt, nickel and manganese at the temperature of 850-880 ℃ for 4-5 hours to obtain the ternary active material. The ternary active material can be used for preparing a novel ternary lithium battery anode material.
Example four
The embodiment provides a process for recycling waste ternary lithium batteries, wherein the waste ternary lithium batteries are nickel cobalt manganese acid lithium batteries, the mass ratio of nickel cobalt manganese is 8:1:1, and the process comprises the following steps:
battery pretreatment: disassembling the waste ternary lithium battery to obtain a positive plate, cleaning and drying the positive plate, and coarsely crushing the positive plate to 100 meshes;
preparing a eutectic solvent: mixing choline chloride and urea according to a molar ratio of 1:2, heating at 93 ℃ for 6-8 hours to obtain a eutectic solvent;
leaching: leaching the ternary battery positive plate subjected to battery pretreatment by using the prepared eutectic solvent to obtain a metal-containing solution and an aluminum foil current collector; the solid-liquid ratio between the mass of the ternary battery positive plate and the volume of the eutectic solvent is 24g/L, the leaching condition is that the solution is heated and stirred for 12 hours at 180 ℃, and the obtained solution containing metal contains metal lithium, cobalt, nickel and manganese;
and (3) precipitation: separating the metal-containing solution from an aluminum foil current collector by filtering, adding sodium hydroxide with the same volume ratio into the filtered metal-containing solution, precipitating for 8-10 hours at normal temperature, and filtering to respectively obtain a lithium-containing solution and a solid precipitate containing cobalt, nickel and manganese;
and (3) purification: subjecting the lithium-containing solution to multiple recrystallizations, for example, two or three recrystallizations, to obtain a lithium hydroxide precipitate;
roasting: and roasting the lithium carbonate precipitate obtained by recrystallization and the solid precipitate containing cobalt, nickel and manganese at the temperature of 850-880 ℃ for 4-5 hours to obtain the ternary active material. The ternary active material can be used for preparing a novel ternary lithium battery anode material.
As can be seen from the measurement of the metal leaching efficiency by the process of this example, the leaching efficiency of metal lithium is 94%, the leaching efficiency of metal nickel is 96%, the leaching efficiency of metal cobalt is 98%, and the leaching efficiency of metal manganese is 90%.
EXAMPLE five
The difference between the present embodiment and the fourth embodiment is only that the waste lithium ternary battery in the present embodiment is a nickel cobalt lithium manganate battery, and the mass ratio of nickel to cobalt is 5:3:2, and it can be known from the measurement of the metal leaching efficiency of the process in the present embodiment that the leaching efficiency of metal lithium is 96%, the leaching efficiency of metal nickel is 95%, the leaching efficiency of metal cobalt is 98%, and the leaching efficiency of metal manganese is 93%.
EXAMPLE six
The difference between the present embodiment and the fourth embodiment is only that the waste ternary lithium battery in the present embodiment is a nickel cobalt lithium manganate battery, and the mass ratio of nickel, cobalt and manganese is 1:1:1, and it can be known from the measurement of the metal leaching efficiency of the process in the present embodiment that the leaching efficiency of metal lithium is 92%, the leaching efficiency of metal nickel is 95%, the leaching efficiency of metal cobalt is 99%, and the leaching efficiency of metal manganese is 92%.
EXAMPLE seven
The embodiment provides a process for recycling waste lithium batteries, wherein the waste lithium batteries are lithium cobaltate batteries, and the process comprises the following steps:
battery pretreatment: disassembling the waste lithium battery to obtain a positive plate, cleaning and drying the positive plate, and then coarsely crushing the positive plate to 100 meshes;
preparing a eutectic solvent: mixing choline chloride and urea according to a molar ratio of 1:3, heating at 88 ℃ for 7-10 hours to obtain a eutectic solvent;
leaching: leaching the lithium cobaltate positive plate and the battery positive plate subjected to battery pretreatment by using the prepared eutectic solvent to obtain a metal-containing solution and an aluminum foil current collector; the solid-liquid ratio between the mass of the waste lithium cobaltate positive plate and the volume of the eutectic solvent is 24g/L, and the leaching condition is that the waste lithium cobaltate positive plate is heated and stirred for 12 hours at 180 ℃, so that the obtained metal-containing solution contains metal lithium and cobalt; among them, the leaching efficiency of metal lithium was 99%, the leaching efficiency of metal cobalt was 97%, aluminum was also contained in the metal-containing solution, and the leaching efficiency of metal aluminum was 3%, and it was found that metal lithium and cobalt were efficiently leached by the process of this example, and at the same time, aluminum was hardly leached, and even a small amount of aluminum was leached.
Example eight
The present embodiment is different from the fourth embodiment only in that, after the leaching step, the precipitation and purification steps adopted in the present embodiment are different from those of the fourth embodiment, specifically:
and (3) precipitation: separating the solution containing the metal from an aluminum foil current collector by filtration, adding saturated sodium carbonate with the same volume ratio into the solution containing the metal, precipitating for 3-5 hours at normal temperature, and then filtering to obtain filtrate and precipitate respectively;
and (3) purification: calcining the filtered precipitate at the temperature of 500-700 ℃ for 2-4 hours to obtain cobaltosic oxide; evaporating the filtered filtrate to obtain lithium salt precipitate.
Example nine
The present embodiment is different from the fourth embodiment only in that, after the leaching step, the precipitation and purification steps adopted in the present embodiment are different from those of the fourth embodiment, specifically:
and (3) precipitation: separating the solution containing the metal from the aluminum foil current collector by filtration, adding sodium hydroxide with the same volume ratio into the solution containing the metal, precipitating for 4-5 hours at normal temperature, and then filtering to respectively obtain filtrate and precipitate;
and (3) purification: calcining the filtered precipitate at 550-650 ℃ for 3-4 hours to obtain cobaltosic oxide; evaporating the filtered filtrate to obtain lithium salt precipitate.
As shown in fig. 1, the XRD pattern of the cobaltosic oxide obtained in this example is spinel type cobaltosic oxide; fig. 2 is a SEM image of cobaltosic oxide obtained in this example.
Example ten
The present embodiment is different from the fourth embodiment only in that, after the leaching step, the precipitation and purification steps adopted in the present embodiment are different from those of the fourth embodiment, specifically:
and (3) precipitation: separating the metal-containing solution from an aluminum foil current collector by filtration, adding sodium oxalate into the metal-containing solution in an equal volume ratio, precipitating at normal temperature for 3-4 hours, and filtering to obtain filtrate and precipitate respectively;
and (3) purification: calcining the filtered precipitate at 550-700 ℃ for 3-5 hours to obtain cobaltosic oxide; evaporating the filtered filtrate to obtain lithium salt precipitate.
EXAMPLE eleven
The present example is different from the seventh example only in that the positive electrode sheet is coarsely pulverized to 120 mesh in the battery pretreatment step of the present example. After the waste lithium cobaltate battery is leached, the leaching efficiency of the metal lithium is 98%, the leaching efficiency of the metal cobalt is 96%, and the metal-containing solution does not contain aluminum, which indicates that the aluminum is not leached.
The above detailed description is provided for the process for recycling waste ternary lithium batteries disclosed in the embodiments of the present invention, and the principle and the implementation manner of the present invention are explained by applying specific examples, and the description of the above embodiments is only used to help understanding the method and the core idea of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. A process for recycling waste lithium batteries is characterized by comprising the following steps:
preparing a eutectic solvent: mixing and heating quaternary ammonium salt and amine compound to prepare the eutectic solvent, wherein the quaternary ammonium salt is selected from one or a mixture of more of choline chloride, choline acetate or acetylcholine, and the amine compound is selected from one or a mixture of more of urea, ethanolamine and triethanolamine;
leaching: and leaching the lithium cobaltate positive plate and the positive plate disassembled from the waste lithium battery by using the eutectic solvent to obtain a metal-containing solution and an aluminum foil current collector.
2. The process of claim 1, further comprising, prior to the step of leaching, performing a pre-cell treatment: disassembling the waste lithium battery to obtain a positive plate of the lithium battery, and cleaning and drying the positive plate.
3. The process according to claim 2, wherein in the step of battery pretreatment, the positive electrode sheet is subjected to washing and drying, and then coarsely pulverized to a particle size of 80 to 120 mesh.
4. The process according to claim 1, wherein in the step of preparing the eutectic solvent, the molar ratio of the quaternary ammonium salt to the amine compound is 1:1-1:3, the heating temperature of the quaternary ammonium salt to the amine compound is 80-95 ℃, and the heating time is 5-10 hours.
5. The process according to claim 4, wherein in the step of preparing the eutectic solvent, the heating temperature is 90 ℃, the reaction time is 5-8 hours, the quaternary ammonium salt is choline chloride, and the amine compound is urea.
6. The process as claimed in claim 1, wherein in the leaching step, the leaching condition using the eutectic solvent is heating and stirring at 170-200 ℃ for 5-24 hours, and the ratio of the mass of the positive electrode sheet to the volume of the eutectic solvent is 10-100 g/L.
7. The process according to any one of claims 1 to 6, wherein the spent lithium batteries are lithium nickel cobalt manganese oxide batteries, the process further comprising, after the step of leaching, precipitation: separating the solution containing the metal from the aluminum foil current collector, adding a precipitator with the same volume ratio into the solution containing the metal, precipitating for 5-10 hours at normal temperature, and filtering to obtain a solution containing the lithium and a solid precipitate containing cobalt, nickel and manganese respectively; wherein, the precipitant is selected from one of saturated carbonate, oxalate or sodium hydroxide.
8. The process according to claim 7, further comprising, after the step of precipitating, a purification: calcining the filtered solid precipitate at the temperature of 500-700 ℃ for 2-4 hours to obtain cobaltosic oxide; evaporating the filtered lithium-containing solution to obtain a lithium salt precipitate.
9. The process according to claim 7, further comprising, after the step of precipitating, a purification: and recrystallizing the lithium-containing solution to obtain lithium carbonate precipitate or lithium hydroxide precipitate.
10. The process according to claim 9, further comprising, after the step of recrystallizing, performing a calcination: and roasting the lithium carbonate precipitate or the lithium hydroxide precipitate obtained after recrystallization and the solid precipitate containing cobalt, nickel and manganese at the temperature of 800-900 ℃ for 3-5 hours to obtain the ternary active material.
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| CN113078382A (en) * | 2021-03-25 | 2021-07-06 | 昆山慧封电子科技材料有限公司 | Lithium battery recovery processing method |
| CN113314777A (en) * | 2021-05-28 | 2021-08-27 | 中国科学院化学研究所 | Recovery method of solid battery material |
| CN113437379A (en) * | 2021-06-24 | 2021-09-24 | 齐鲁理工学院 | Method for recycling and regenerating waste ternary lithium battery |
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| CN115466842A (en) * | 2021-11-12 | 2022-12-13 | 金为环保科技(常州)有限公司 | Treatment method and application of waste lithium battery waste liquid |
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