CN109256597B - Method and system for recovering lithium and cobalt from waste lithium cobalt oxide battery - Google Patents
Method and system for recovering lithium and cobalt from waste lithium cobalt oxide battery Download PDFInfo
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Abstract
The invention discloses a method and a system for recovering lithium and cobalt from waste lithium cobaltate batteries. The method comprises the following steps: disassembling a positive plate from a waste lithium cobalt oxide battery; removing the binder in the positive plate, leaching valuable metal elements in the positive plate through acid dissolution to obtain an acidified leaching solution; carrying out ultrafiltration treatment on the acidified leaching solution by using an ultrafiltration membrane; separating lithium ions from other cations different from the lithium ions in the acidified leachate by using a nanofiltration membrane technology to obtain a lithium-containing solution and a solution containing other cations, and concentrating and enriching the lithium-containing solution and the solution containing other cations by using a reverse osmosis technology respectively, wherein the other cations comprise cobalt ions; and precipitating lithium ions in the lithium-containing solution by using a lithium precipitator, and precipitating cobalt ions in the solution containing other cations by using an alkaline substance, thereby realizing the recovery of lithium and cobalt. The invention adopts the combined technology of ultrafiltration-nanofiltration-reverse osmosis, and has the characteristics of simple and environment-friendly process, small acid and alkali consumption, good and stable membrane separation effect and the like.
Description
Technical Field
The invention relates to a method and a corresponding system for recovering lithium and cobalt from waste lithium cobaltate batteries, and belongs to the technical field of lithium battery recovery.
Background
Lithium and its compounds are strategic materials with important significance in national economy and national defense construction, and are novel green energy materials closely related to people's life. As a new chemical power source, lithium ion batteries have become the main energy source of 3C electronic products, and account for over 80% of the consumer electronics market. In recent years, the lithium battery technology is continuously improved, the energy density is improved, the demand in the fields of new energy automobiles and energy storage power supplies is greatly increased, and the production and marketing of lithium ion batteries are greatly increased. Pure electric vehicles represented by Tesla adopt a lithium battery of a lithium cobaltate anode material of a high-voltage platform produced under the pine to provide power. In addition, in the field of 3C consumer electronics, lithium batteries using a large amount of lithium cobaltate positive electrode materials are expected to be a very important field for recycling waste batteries, particularly lithium cobaltate positive electrode materials.
However, in the practical use of the lithium ion battery, the charge-discharge cycle is about 500-1000 times, and the service life is 3-5 years. The scrapping peak of the waste lithium battery is expected to come around 2020 in China. Although the discarded lithium ion battery does not contain heavy metals such as lead, cadmium, mercury and the like and has relatively small environmental pollution, the discarded lithium ion battery contains valuable metals such as cobalt, nickel, manganese, lithium and the like and toxic and harmful substances such as lithium hexafluorophosphate and the like, and serious pollution and resource waste are easily caused due to improper disposal. The waste lithium ion battery contains a large amount of rare and precious metals such as cobalt, nickel, lithium and the like, and has remarkable economic benefit. Therefore, how to scientifically, environmentally and efficiently recover valuable metals such as cobalt, lithium and the like from waste lithium batteries becomes a technical hotspot in the current recovery field.
The recovery technology of the waste lithium batteries is more, the early recovery technology only focuses on the purification of certain metal elements with the highest economic value, the method is single, the cobalt in the waste lithium cobaltate is typically recovered, and the lithium is not comprehensively recovered. The prior recovery technology of valuable metals of waste batteries mainly focuses on two aspects of hydrometallurgy and pyrometallurgy, and the methods realize the recovery of valuable metal elements or the synthesis of precursors from the waste lithium batteries. The most used method is pyrogenic process-acid leaching or alkali solution-acid leaching, and then valuable metal elements are recovered by combining precipitation, electrochemistry, extraction and other modes. The pyrometallurgy mainly uses high-temperature calcination to remove organic matters and binders, and then the target product is obtained through screening, magnetic separation, impurity removal, leaching and purification. In the process technology of alkali dissolution, acid leaching and nickel-cobalt-manganese extraction by a hydrometallurgy method, the alkali dissolution and acid leaching are mainly adopted, and then valuable metal elements are recycled by adopting a fractional precipitation or extraction method, wherein the used alkali mainly comprises sodium hydroxide and potassium hydroxide; the acid is divided into inorganic acid and organic acid, such as common inorganic acid hydrochloric acid, sulfuric acid, nitric acid and even phosphoric acid, the organic acid includes citric acid, malic acid and the like, the used extractant includes organic solvents such as P204, P507 and the like, and most recovered products are sulfate. Although the solvent extraction method has high extraction efficiency and high purity of the obtained product, the organic solvent is more or less dissolved and damaged and is volatile to pollute the environment, so that secondary pollution is caused, in addition, the extraction method has high cost and has limitation in industrial production. If the equipotential of nickel and cobalt is close, nickel and cobalt can be synchronously deposited in the electrodeposition technology to form cobalt-nickel alloy, which affects subsequent purification and restricts the application of the enlargement. Furthermore, the prior art precipitates or extracts nickel cobalt manganese and then purifies the lithium-containing solution. The process is particularly complicated, the pH value needs to be adjusted in 4-5 stages, a large amount of acid and alkali is consumed, the process is long, and accurate control is not easy.
For example, in chinese patent CN106395784A, positive and negative electrode materials are obtained by detachment and peeling, then lithium cobaltate positive electrode active material is obtained by calcination, and lithium-containing solution and cobalt phosphate precipitate are obtained by combined leaching with phosphoric acid and hydrogen peroxide and solid-liquid separation. The method adopts roasting combined leaching process to directly obtain cobalt phosphate and lithium-containing solution, thereby realizing the separation and recovery of cobalt and lithium. In the Chinese patent CN106505270A, ammonium sulfate is adopted for roasting to obtain reduction roasting slag, aluminum foil is screened and separated to obtain cobalt-lithium-containing reduction slag, dilute sulfuric acid is adopted for leaching, the pH value is adjusted for precipitating cobalt, and cobalt hydroxide is subjected to high-temperature roasting to obtain cobalt powder; precipitating lithium by using a lithium precipitating agent. The method recovers cobalt and lithium, but uses high-temperature sintering twice, and has larger energy consumption. In addition, in the chinese patent CN108336442A, an organic solvent is used to strip the anode material and the aluminum foil, and sulfuric acid acidification recovery and multi-step precipitation impurity removal are adopted to recover and obtain cobalt powder and lithium carbonate products. The method uses the organic solvent for stripping, although the stripping effect is good, the stripping cost of the organic solvent is high, the efficiency is low, and the organic matters are volatile, so that the environmental pollution is easily caused, and the large-scale application is restricted.
Other methods such as an ion exchange method, sulfide bacteria leaching and the like can successfully recover valuable metal elements, but the methods have certain limitations, such as complex operation and complex steps of the ion exchange method, and are only suitable for separation and purification of a small amount of ions; the culture and use conditions of the bacteria in the sulfide bacteria leaching technology are harsh, and the application and popularization of the technology are restricted by factors such as difficult industrialization.
Disclosure of Invention
The invention mainly aims to provide a method and a system for recovering lithium and cobalt from waste lithium cobaltate batteries, thereby overcoming the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a method for recovering lithium and cobalt from waste lithium cobaltate batteries, which comprises the following steps:
disassembling a positive plate from a waste lithium cobalt oxide battery;
removing the binder in the positive plate, and leaching valuable metal elements in the positive plate through acid dissolution to obtain an acidified leaching solution;
carrying out ultrafiltration treatment on the acidified leaching solution by using an ultrafiltration membrane;
separating lithium ions from other cations different from the lithium ions in the acidified leachate by using a nanofiltration membrane technology to obtain a lithium-containing solution and a solution containing other cations, and concentrating and enriching the lithium-containing solution and the solution containing other cations by using a reverse osmosis technology, wherein the other cations comprise cobalt ions;
and precipitating lithium ions in the lithium-containing solution by using a lithium precipitator, and precipitating cobalt ions in the solution containing other cations by using an alkaline substance, thereby realizing the recovery of lithium and cobalt.
In some embodiments, the method for recovering lithium and cobalt from waste lithium cobalt oxide batteries specifically comprises:
(1) discharging, disassembling and classifying the waste lithium cobalt oxide battery to obtain a positive plate;
(2) carrying out high-temperature treatment on the positive plate, wherein the high-temperature treatment is at least used for removing the binder in the positive plate;
(3) continuously contacting the high-temperature treated positive plate with an acidic substance to leach valuable metal elements in the positive plate to obtain an acidified leaching solution;
(4) respectively passing the acidified leachate through an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane to obtain a concentrated lithium-containing solution and a solution containing other cations;
(5) adding a lithium precipitator into the lithium-containing solution, and reacting to obtain a lithium precipitate;
(6) and (3) removing impurities from the solution containing other cations, adding an alkaline substance, and reacting to obtain a cobalt precipitate.
The embodiment of the invention also provides a system for recovering lithium and cobalt from the waste lithium cobaltate battery, which comprises the following steps:
the disassembling mechanism can disassemble and classify the waste lithium cobalt oxide batteries to obtain positive plates;
the acidification leaching mechanism can leach valuable metal elements in the positive plate to obtain an acidification leaching solution;
the combined system of ultrafiltration-nanofiltration-reverse osmosis comprises an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane, and is at least used for separating and concentrating lithium ions in acidified leachate from other cations;
a lithium precipitation mechanism for precipitating lithium ions at least;
a cobalt precipitation mechanism for at least precipitating out cobalt ions in the other cations.
Compared with the prior art, the invention has the beneficial effects that:
1) the method for recovering lithium and cobalt from waste lithium cobalt oxide batteries has the advantages that the valuable metal separation technology is advanced, the separation effect is good, lithium ions are preferentially separated from other divalent cations by adopting an ultrafiltration-nanofiltration-reverse osmosis combined mode, the process flow is simplified, the process is a physical process, organic matters or impurity ions cannot be introduced, and the single-stage interception effect of cobalt ions reaches more than 95%;
2) the method for recovering lithium and cobalt from waste lithium cobaltate batteries has a novel separation and purification concept, and is characterized in that ultrafiltration pretreatment is preferentially adopted to acidify the leachate to remove residual organic macromolecules, so that the pollution and blockage to a nanofiltration membrane are reduced, lithium and other divalent metal ions are separated from the acidified leachate, then lithium-containing and cobalt-containing solutions are respectively treated, impurities are removed and concentrated to obtain a product, the process flow is greatly shortened, the entrainment loss of lithium ions in a complicated impurity removal process is reduced, and the recovery rate of lithium is greatly improved;
3) the method adopts a physical separation process, has low energy consumption, is carried out at normal temperature in a concentration and purification process, has no phase change, no chemical reaction and no other impurities, greatly reduces the use amount of acid and alkali in the separation and purification process, adopts common inorganic acid for acidification leaching, reduces the cost, avoids the use of an organic extractant, and is green and environment-friendly;
4) the lithium carbonate product recovered by the method has high purity and high recovery rate of valuable metal ions. The nanofiltration membrane process technology improves the product purity, thoroughly removes impurity ions, and has high comprehensive recovery rate of lithium ions;
5) the invention is provided with digital display and on-line detection facilities, has advanced whole process equipment, easy control of process conditions, simple and convenient operation, high automation degree and easy amplification, and is suitable for industrial production application.
6) The mother liquor in the process can be recycled without discharging, thereby reducing secondary pollution to the environment.
Drawings
Fig. 1 is a schematic flow diagram of a process for recovering lithium and cobalt from spent lithium cobalt oxide batteries in an exemplary embodiment of the invention.
Detailed Description
In view of the defects of low recovery efficiency, long process and secondary pollution to the environment of the existing lithium cobaltate waste lithium battery, the inventor of the present invention provides the technical scheme of the invention through long-term research and a large amount of practices, and the technical scheme mainly comprises the process steps of battery disassembly, classification, positive plate crushing, heat treatment, acid leaching, ultrafiltration membrane-nanofiltration membrane-reverse osmosis separation enrichment of valuable metal ions, impurity removal, precipitation and the like. The technical solution, its implementation and principles, etc. will be further explained as follows.
The nanofiltration membrane-reverse osmosis combined process technology has wide application in the fields of seawater desalination treatment and biomedicine. The nanofiltration membrane is a composite membrane, the surface and the separation layer of the nanofiltration membrane are composed of polyelectrolyte, and the nanofiltration membrane has the effect of trapping inorganic salts. The relevant membrane permeation theories mainly include a solution diffusion theory, a hydrogen bond theory, a diffusion pore flow theory and a selective adsorption pore flow theory. The filtration performance of the nanofiltration membrane is also related to the charge property of the membrane, the process of membrane manufacture and the like. According to the characteristics that the nanofiltration membrane has different selective permeability on solutes and has higher rejection rate on divalent ions than monovalent ions, the nanofiltration membrane technology is utilized to separate monovalent cations and divalent cations in the leachate, and then solutions of the monovalent ions and the divalent ions are respectively concentrated by reverse osmosis to realize the separation and concentration of lithium elements and cobalt elements. The process greatly reduces the using amount of acid and alkali, avoids the technical processes of extracting cobalt and the like by using an organic solvent, simultaneously combines a reverse osmosis concentration technology, reduces the energy consumption of solution concentration and evaporation, can quickly realize separation and purification of valuable metal ion pairs, has the characteristics of environmental protection, low energy consumption and high recovery efficiency, is simple in process operation, and is easy to amplify to realize industrialization.
As one aspect of the technical scheme of the invention, the invention relates to a method for recovering lithium and cobalt from waste lithium cobalt oxide batteries, which comprises the following steps:
disassembling a positive plate from a waste lithium cobalt oxide battery;
removing the binder in the positive plate, and leaching valuable metal elements in the positive plate through acid dissolution to obtain an acidified leaching solution;
carrying out ultrafiltration treatment on the acidified leachate by using an ultrafiltration membrane to remove residual organic matters and other macromolecules and reduce the blockage and pollution to a subsequent membrane;
separating lithium ions from other cations different from the lithium ions in the acidified leachate by using a nanofiltration membrane technology to obtain a lithium-containing solution and a solution containing other cations, and concentrating and enriching the lithium-containing solution and the solution containing other cations by using a reverse osmosis technology, wherein the other cations comprise cobalt ions;
and precipitating lithium ions in the lithium-containing solution by using a lithium precipitator, and precipitating cobalt ions in the solution containing other cations by using an alkaline substance, thereby realizing the recovery of lithium and cobalt.
In some embodiments, the method for recovering lithium and cobalt from waste lithium cobalt oxide batteries specifically comprises:
(1) discharging, disassembling and classifying the waste lithium cobalt oxide battery to obtain a positive plate;
(2) carrying out high-temperature treatment on the positive plate, wherein the high-temperature treatment is at least used for removing the binder in the positive plate;
(3) continuously contacting the high-temperature treated positive plate with an acidic substance to leach valuable metal elements in the positive plate to obtain an acidified leaching solution;
(4) respectively passing the acidified leachate through an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane to obtain a concentrated lithium-containing solution and a solution containing other cations;
(5) adding a lithium precipitator into the lithium-containing solution, and reacting to obtain a lithium precipitate;
(6) and (3) removing impurities from the solution containing other cations, adding an alkaline substance, and reacting to obtain a cobalt precipitate.
In some embodiments, the waste lithium cobalt oxide battery mainly uses lithium cobalt oxide as a positive electrode material, and representative examples include, but are not limited to, a mobile phone battery, a notebook computer battery, a digital camera battery, and a part of a high voltage lithium cobalt oxide power battery.
In some embodiments, step (2) specifically comprises: and calcining the positive plate, and performing high-temperature treatment to remove the binder.
Further, the calcining time is 0.5-6 h, and the calcining temperature is 300-800 ℃.
In some embodiments, step (3) specifically comprises: immersing the high-temperature treated positive plate in an acidic substance, adding hydrogen peroxide, controlling the solid-to-liquid ratio to be 40-120 g/L, and stirring at 30-90 ℃ to leach valuable metal elements in the positive plate to obtain an acidified leaching solution.
Further, the acidic substance includes any one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydrofluoric acid, and the like, but is not limited thereto. The invention has wide application range, is suitable for common inorganic acid acidification leaching and reduces the cost.
Further, the concentration of the acidic substance is 1-10 mol/L.
In some embodiments, step (4) specifically comprises: respectively inputting the acidified leachate obtained in the step (3) into an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane, wherein the pore diameter of the ultrafiltration membrane is
Preferably, it is
The working pressure of the nanofiltration membrane is 0.1-1.5 MPa, the working pressure of the nanofiltration membrane is 0.1-6 MPa, the flow rate of a single membrane is 0.1-5L/min, and the working pH value is 2-10, so that the concentrated lithium-containing solution and the solution containing other cations are finally obtained. The ultrafiltration-nanofiltration-reverse osmosis technology adopts ultrafiltration pretreatment to acidify leachate to remove residual organic macromolecules, reduces pollution and blockage to a nanofiltration membrane, adopts the nanofiltration membrane to separate lithium and other metal ions, is mainly used for monovalent and divalent ion separation, namely separation of lithium, cobalt, nickel and manganese, adopts a reverse osmosis membrane method to concentrate and enrich lithium-containing solution, reduces concentration evaporation capacity and improves lithium ion concentration.
The nanofiltration membrane may be made of a combination of two or more of Polyamide (PA), Polysulfone (PS), polyvinyl alcohol (PVA), Sulfonated Polysulfone (SPS), Sulfonated Polyethersulfone (SPES), and Cellulose Acetate (CA), and particularly preferably a polyamide/polysulfone composite membrane.
Further, the nanofiltration membrane comprises a plate type nanofiltration membrane or a roll type nanofiltration membrane. The invention adopts two or more than two membranes to be polymerized and compounded to assemble a plate type membrane group, a roll type membrane group and other types of membrane groups.
Furthermore, the molecular weight of the nanofiltration membrane is 50-1000 daltons, the nanofiltration membrane has good ion selectivity, and the rejection rate of divalent ions reaches over 95%.
Further, the concentration of the lithium-containing solution after concentration is 15g/L or more.
The invention adopts the combined technology of ultrafiltration-nanofiltration-reverse osmosis to realize the separation, enrichment and concentration of lithium ions and reduce the use amount of acid and alkali. The method comprises the steps of pretreating acidified leachate in an ultrafiltration process to remove residual organic macromolecules, reducing pollution and blockage to a nanofiltration membrane, enabling lithium ions to enter fresh water in the nanofiltration process, intercepting other divalent ions and more ions in concentrated water, enabling the single-stage interception rate to reach more than 95%, and then concentrating a lithium-containing solution again by combining with reverse osmosis to enable the lithium concentration to reach 3-10%. The combination process is carried out in a mode of combining series connection or parallel connection, and the separation and concentration effects are improved.
In some embodiments, the lithium precipitating agent in step (5) includes sodium carbonate, sodium bicarbonate, sodium fluoride, or the like, but is not limited thereto.
Further, the lithium precipitate includes lithium carbonate and lithium fluoride, and may be intermediate products such as lithium chloride and lithium sulfate products besides lithium carbonate and lithium fluoride, and may be concentrated and converted according to actual conditions.
Further, the content of lithium carbonate or lithium fluoride in the recovered lithium precipitate is more than 99.5wt%, the content of aluminum is less than 0.001wt%, the content of iron is less than 0.001wt%, the content of sodium is less than 0.025wt%, and the content of magnesium is less than 0.008 wt%.
In some embodiments, step (6) specifically comprises: and (4) adding a copper removing agent into the solution containing other cations obtained in the step (4), adjusting the pH value to 3-5, adding an alkaline substance, and reacting to obtain a cobalt precipitate.
Further, the copper removing agent includes any one or a combination of two or more of sodium sulfide, nickel sulfide, iron powder, and the like, but is not limited thereto.
Further, the alkaline substance includes any one or a combination of two or more of sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, calcium hydroxide, and the like, but is not limited thereto.
Further, the concentration of the alkaline substance is 0.5-8 mol/L.
Further, the cobalt precipitate includes cobalt hydroxide and cobalt carbonate, and may also be cobalt oxide or cobaltosic oxide powder, and may be calcined and converted at high temperature according to actual conditions.
Further, the divalent cations include a mixture of cobalt ions, nickel ions, manganese ions, and the like.
Further, the cobalt precipitate includes a nickel cobalt manganese coprecipitate, which is a hydroxide or carbonate of nickel cobalt manganese, but is not limited thereto.
As one of more specific embodiments of the present invention, referring to fig. 1, the method for recovering lithium and cobalt from a waste lithium cobalt oxide battery may specifically include the following steps:
the method comprises the steps of taking waste lithium cobaltate batteries (including lithium cobaltate 3C products and waste positive plates generated in the production process of the lithium cobaltate batteries) as raw materials, discharging, breaking, dismantling and screening to obtain the positive plates, removing binders through high-temperature treatment, leaching valuable metal elements through acid dissolution, and performing ultrafiltration membrane-nanofiltration membrane-reverse osmosis treatment on filtrate to respectively obtain a mixed solution containing lithium solution and other ions. The lithium-containing solution is concentrated to more than 15g/L, and saturated lithium precipitator is added to precipitate lithium carbonate. Adding a copper removing agent to remove copper ions in the mixed solution containing nickel, cobalt and manganese separated by a nanofiltration membrane, adjusting the pH value to 3-5, precipitating to remove impurities such as aluminum, iron and the like, and then adding alkali to precipitate cobalt, thereby realizing the separation and recovery of lithium and cobalt. The concentrated mother liquor can be recycled without discharge, deionized water is properly added in the cycle for dilution, and a lithium product obtained by recrystallizing, washing and drying the lithium carbonate product meets the requirements of a battery grade and can be directly recycled.
In another aspect of the embodiments of the present invention, there is provided a system for recovering lithium and cobalt from a waste lithium cobalt oxide battery, including:
the disassembling mechanism can disassemble and classify the waste lithium cobalt oxide batteries to obtain positive plates;
the acidification leaching mechanism can leach valuable metal elements in the positive plate to obtain an acidification leaching solution;
the combined system of ultrafiltration-nanofiltration-reverse osmosis comprises an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane, and is at least used for separating and concentrating lithium ions in acidified leachate from other cations;
a lithium precipitation mechanism for precipitating lithium ions at least;
a cobalt precipitation mechanism for at least precipitating out cobalt ions in the other cations.
Further, the system further comprises: and the high-temperature treatment mechanism is at least used for carrying out high-temperature treatment on the positive plate so as to remove the binder in the positive plate.
Further, the system further comprises: and the impurity removal mechanism is at least used for removing impurities of the solution containing other cations.
Further, the system may specifically include, but is not limited to, a pulverizer, an acidification tank, an ultrafiltration-nanofiltration-reverse osmosis combination, a muffle furnace, a crystallizer, a high-speed centrifuge, a screen, a magnetic separator, a drying oven, and the like.
In conclusion, the method adopts the ultrafiltration membrane to pretreat the acidified leachate to remove residual organic macromolecules and reduce the pollution and blockage to the nanofiltration membrane, utilizes the nanofiltration membrane technology to separate univalent cations and divalent cations in the leachate, and then uses reverse osmosis to respectively concentrate solutions of the univalent ions and the divalent ions to realize the separation and concentration of lithium elements and cobalt elements. The process greatly reduces the using amount of acid and alkali, avoids the technical processes of extracting cobalt and the like by using an organic solvent, simultaneously combines a reverse osmosis concentration technology, reduces the energy consumption of solution concentration and evaporation, can quickly realize separation and purification of valuable metal ion pairs, has the characteristics of environmental protection, low energy consumption and high recovery efficiency, is simple in process operation, and is easy to amplify to realize industrialization.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, 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 obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
Example 1
The method takes a certain type of waste lithium cobalt oxide battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 800g of lithium cobaltate positive electrode material, treating the lithium cobaltate positive electrode material in a muffle furnace at 450 ℃ for 2h, removing the binder, carrying out water quenching, and treating the lithium cobaltate positive electrode material in ultrasonic oscillation for 30min to strip the positive electrode material from the aluminum foil. The large-mesh sieve pores are adopted to remove and separate the aluminum foil, and the aluminum foil can be directly used for aluminum smelting after being washed. Treating the obtained black fine slag with 4mol/L sulfuric acid, simultaneously adding 30% hydrogen peroxide, controlling the solid-to-liquid ratio to be 80g/L, controlling the temperature to be 80 ℃, continuously stirring for 4h, and then filtering to obtain a leaching solution of valuable metals. The acid leaching residue is mainly carbon powder and other acid insoluble substances. The chemical components in the leachate were detected, and the results are shown in table 1 below:
TABLE 1 chemical composition in lixivium (unit: g/L)
| Categories | Aluminium | Cobalt | Lithium ion source | Iron | SO4 2- |
| Content (wt.) | 1.05 | 50.53 | 6.25 | 0.024 | 142.52 |
Adjusting the pH value of the acid leaching solution to about 3.5 by using alkali, diluting and adjusting the concentration of total anions and cations to 50g/L, performing ultrafiltration-nanofiltration-reverse osmosis treatment, controlling the pressure of an ultrafiltration membrane to be 1MPa, the pressure of a nanofiltration membrane to be 3.5MPa, the flow rate of concentrated water to be 3.0L/min, intercepting cobalt plasma by a membrane, enriching the cobalt plasma on the side of the concentrated water, and allowing lithium ions to enter fresh water, and respectively detecting to obtain a lithium-containing solution and other ion mixed solutions, wherein the cobalt ion single-stage interception rate reaches 95.5%. Lithium ions are enriched in fresh water, the enriched lithium-containing solution is further evaporated to enable the lithium concentration to reach 30g/L, saturated sodium carbonate is added at the temperature of 85 ℃ to precipitate lithium carbonate, and battery-grade lithium carbonate is obtained through processing such as washing, recrystallization, washing, drying and the like, wherein the detection results are shown in the following table 2:
TABLE 2 detection results of battery grade lithium carbonate
Removing impurities such as copper, iron and aluminum from the cobalt-containing solution by iron powder replacement and controlling the pH value to 5.0 with sodium hydroxide, filtering, and precipitating cobalt from the filtrate with 2.0mol/L sodium hydroxide to obtain Co (OH)2And (5) producing the product. The process has the advantages of short flow, environmental protection, preferential separation of lithium, simple operation and easy large-scale production, and the lithium carbonate and cobalt hydroxide products reach the levelThe quality requirement of the raw materials of the swimming battery enterprises.
Example 2
The method takes a certain type of waste lithium cobalt oxide battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 600g of lithium cobaltate positive electrode material, treating the lithium cobaltate positive electrode material in a muffle furnace at 650 ℃ for 2h, removing the binder, carrying out water quenching, and treating the lithium cobaltate positive electrode material in ultrasonic oscillation for 30min to strip the positive electrode material from the aluminum foil. The large-mesh sieve pores are adopted to remove and separate the aluminum foil, and the aluminum foil can be directly used for aluminum smelting after being washed. Treating the obtained black fine slag with 10mol/L sulfuric acid, simultaneously adding 30% hydrogen peroxide, controlling the solid-to-liquid ratio to be 80g/L, controlling the temperature to be 30 ℃, continuously stirring for 4h, and then filtering to obtain a leaching solution of valuable metals. The acid leaching residue is mainly carbon powder and other acid insoluble substances. The chemical components in the leachate were detected, and the results are shown in table 3 below:
TABLE 3 chemical composition in leachate (unit: g/L)
| Categories | Aluminium | Cobalt | Lithium ion source | Iron | SO4 2- |
| Content (wt.) | 1.55 | 60.57 | 7.48 | 0.028 | 156.25 |
Adjusting the pH value of acid leaching solution to about 3.5 by using alkali, diluting and adjusting the concentration of total anions and cations by using deionized water to be controlled to 60g/L, entering an ultrafiltration-nanofiltration-reverse osmosis treatment process, controlling the pressure of an ultrafiltration membrane to be 1.2MPa, the pressure of a nanofiltration membrane to be 6MPa, the flow rate of concentrated water to be 5.0L/min, intercepting cobalt plasma by a membrane, enriching the cobalt plasma on the side of the concentrated water, and entering lithium ions into fresh water, and respectively detecting to obtain a lithium-containing solution and other ion mixed solutions, wherein the single-stage interception rate of the cobalt ions reaches 95.1%. Lithium ions are enriched in fresh water, the enriched lithium-containing solution is further evaporated to enable the lithium concentration to reach 30g/L, saturated sodium carbonate is added at the temperature of 85 ℃ to precipitate lithium carbonate, and battery-grade lithium carbonate is obtained through processing such as washing, recrystallization, washing, drying and the like, and the detection results are shown in the following table 4:
TABLE 4 Battery grade lithium carbonate test results
Replacing cobalt-containing solution with iron powder, controlling pH to 4 with sodium hydroxide to remove impurities such as copper, iron, aluminum, etc., filtering, precipitating cobalt with 6.0mol/L sodium hydroxide to obtain Co (OH)2And (5) producing the product. The process flow is short, the environment is protected, lithium is preferentially separated, the operation is simple and convenient, the large-scale production is easy, and the lithium carbonate and cobalt hydroxide products meet the quality requirements of downstream battery enterprises on raw materials.
Example 3
The method takes a certain type of waste lithium cobalt oxide battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 1000g of lithium cobaltate positive electrode material, treating the lithium cobaltate positive electrode material in a muffle furnace at 500 ℃ for 1h, removing the binder, carrying out water quenching, and treating the lithium cobaltate positive electrode material in ultrasonic oscillation for 60min to strip the positive electrode material from the aluminum foil. The large-mesh sieve pores are adopted to remove and separate the aluminum foil, and the aluminum foil can be directly used for aluminum smelting after being washed. Treating the obtained black fine slag with 4mol/L sulfuric acid, simultaneously adding 30% hydrogen peroxide, controlling the solid-to-liquid ratio to be 75g/L, controlling the temperature to be 85 ℃, continuously stirring for 4h, and then filtering to obtain a leaching solution of valuable metals. The acid leaching residue is mainly carbon powder and other acid insoluble substances. The chemical components in the leachate were measured, and the results are shown in the following table 5:
TABLE 5 chemical composition in leachate (unit: g/L)
| Categories | Aluminium | Cobalt | Lithium ion source | Iron | SO4 2- |
| Content (wt.) | 2.34 | 57.53 | 6.41 | 0.029 | 168.37 |
Adjusting the pH value of the acid leaching solution to about 2 by using alkali, diluting and adjusting the concentration of total anions and cations to 50g/L, performing ultrafiltration-nanofiltration-reverse osmosis treatment, controlling the pressure of an ultrafiltration membrane to be 0.8MPa, the pressure of a nanofiltration membrane to be 3.5MPa, the flow rate of concentrated water to be 3.0L/min, intercepting cobalt plasma by a membrane, enriching the cobalt plasma on the side of the concentrated water, and allowing lithium ions to enter fresh water, and respectively detecting to obtain a lithium-containing solution and other ion mixed solutions, wherein the cobalt ion single-stage interception rate reaches 95.0%. Lithium ions are enriched in fresh water, the enriched lithium-containing solution is further evaporated to enable the lithium concentration to reach 30g/L, saturated sodium carbonate is added at the temperature of 85 ℃ to precipitate lithium carbonate, and battery-grade lithium carbonate is obtained through processing such as washing, recrystallization, washing, drying and the like, and the detection results are shown in the following table 6:
TABLE 6 detection results of battery grade lithium carbonate
Removing impurities such as copper, iron and aluminum from the cobalt-containing solution by iron powder replacement and controlling the pH value to 5.0 with sodium hydroxide, filtering, and precipitating cobalt from the filtrate with 8.0mol/L sodium hydroxide to obtain Co (OH)2And (5) producing the product. The process flow is short, the environment is protected, lithium is preferentially separated, the operation is simple and convenient, the large-scale production is easy, and the lithium carbonate and cobalt hydroxide products meet the quality requirements of downstream battery enterprises on raw materials.
Example 4
The method takes a certain type of waste lithium cobalt oxide battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 1200g of lithium cobaltate positive electrode material, treating the lithium cobaltate positive electrode material in a muffle furnace at 550 ℃ for 2h, removing the binder, carrying out water quenching, and treating the lithium cobaltate positive electrode material in ultrasonic oscillation for 75min to strip the positive electrode material from the aluminum foil. The large-mesh sieve pores are adopted to remove and separate the aluminum foil, and the aluminum foil can be directly used for aluminum smelting after being washed. Treating the obtained black fine slag with 4mol/L hydrochloric acid, simultaneously adding 30% hydrogen peroxide, controlling the solid-to-liquid ratio to be 80g/L, controlling the temperature to be 80 ℃, continuously stirring for 4h, and then filtering to obtain a leaching solution of valuable metals. The acid leaching residue is mainly carbon powder and other acid insoluble substances. The chemical components in the leachate were measured, and the results are shown in table 7 below:
TABLE 7 chemical composition in leachate (unit: g/L)
| Categories | Aluminium | Cobalt | Lithium ion source | Iron | Cl- |
| Content (wt.) | 1.12 | 58.30 | 7.11 | 0.027 | 97.69 |
Adjusting the pH value of the acid leaching solution to about 3.5 by using alkali, diluting and adjusting the concentration of total anions and cations to 55g/L, performing ultrafiltration-nanofiltration-reverse osmosis treatment, controlling the pressure of an ultrafiltration membrane to be 0.5MPa, the pressure of a nanofiltration membrane to be 4MPa, the flow rate of concentrated water to be 3.0L/min, intercepting cobalt plasma by a membrane, enriching the cobalt plasma on the side of the concentrated water, and allowing lithium ions to enter fresh water, and respectively detecting to obtain a lithium-containing solution and other ion mixed solutions, wherein the single-stage interception rate of the cobalt ions reaches 95.5%. Lithium ions are enriched in fresh water, the enriched lithium-containing solution is further evaporated to enable the lithium concentration to reach 30g/L, saturated sodium carbonate is added at the temperature of 85 ℃ to precipitate lithium carbonate, and battery-grade lithium carbonate is obtained through processing such as washing, recrystallization, washing, drying and the like, wherein the detection results are shown in the following table 8:
TABLE 8 detection results of battery grade lithium carbonate
Removing impurities such as copper, iron and aluminum from the cobalt-containing solution by iron powder replacement and controlling the pH value to 4.5 with sodium hydroxide, filtering, and precipitating cobalt from the filtrate with 1.0mol/L sodium hydroxide to obtain Co (OH)2And (5) producing the product. The process flow is short, the environment is protected, lithium is preferentially separated, the operation is simple and convenient, the large-scale production is easy, and the lithium carbonate and cobalt hydroxide products meet the quality requirements of downstream battery enterprises on raw materials.
Example 5
The method takes a certain type of waste lithium cobalt oxide battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 900g of lithium cobaltate positive electrode material, treating for 0.5h in a muffle furnace at 800 ℃, removing the binder, quenching with water, and treating for 90min in ultrasonic oscillation to peel the positive electrode material from the aluminum foil. The large-mesh sieve pores are adopted to remove and separate the aluminum foil, and the aluminum foil can be directly used for aluminum smelting after being washed. Treating the obtained black fine slag with 10mol/L hydrochloric acid, simultaneously adding 30% hydrogen peroxide, controlling the solid-to-liquid ratio to be 120g/L, controlling the temperature to be 80 ℃, continuously stirring for 2h, and then filtering to obtain a leaching solution of valuable metals. The acid leaching residue is mainly carbon powder and other acid insoluble substances. The chemical components in the leachate were measured, and the results are shown in the following table 9:
TABLE 9 chemical composition in leachate (unit: g/L)
| Categories | Aluminium | Cobalt | Lithium ion source | Iron | Cl- |
| Content (wt.) | 0.96 | 65.30 | 7.82 | 0.057 | 129.35 |
Adjusting the pH value of the acid leaching solution to about 3.5 by using alkali, diluting and adjusting the concentration of total anions and cations to 40g/L, performing ultrafiltration-nanofiltration-reverse osmosis treatment, controlling the pressure of an ultrafiltration membrane to be 0.5MPa, the pressure of a nanofiltration membrane to be 1.2MPa, the flow rate of concentrated water to be 2.0L/min, intercepting cobalt plasma by a membrane, enriching the cobalt plasma on the side of the concentrated water, and allowing lithium ions to enter fresh water, and respectively detecting to obtain a lithium-containing solution and other ion mixed solutions, wherein the single-stage interception rate of the cobalt ions reaches 95.2%. Lithium ions are enriched in fresh water, the enriched lithium-containing solution is further evaporated to enable the lithium concentration to reach 25g/L, saturated sodium carbonate is added at the temperature of 80 ℃ to precipitate lithium carbonate, and battery-grade lithium carbonate is obtained through processing such as washing, recrystallization, washing, drying and the like, and the detection results are shown in the following table 10:
TABLE 10 Battery grade lithium carbonate test results
Removing impurities such as copper, iron and aluminum from the cobalt-containing solution by iron powder replacement and controlling the pH value to 4.5 with sodium hydroxide, filtering, and precipitating cobalt from the filtrate with 8.0mol/L sodium hydroxide to obtain Co (OH)2And (5) producing the product. The process flow is short, the environment is protected, lithium is preferentially separated, the operation is simple and convenient, the large-scale production is easy, and the lithium carbonate and cobalt hydroxide products meet the quality requirements of downstream battery enterprises on raw materials.
Example 6
The method takes a certain type of waste lithium cobalt oxide battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 900g of lithium cobaltate positive electrode material, treating the lithium cobaltate positive electrode material in a muffle furnace at 300 ℃ for 6h, removing the binder, carrying out water quenching, and treating the lithium cobaltate positive electrode material in ultrasonic oscillation for 90min to strip the positive electrode material from the aluminum foil. The large-mesh sieve pores are adopted to remove and separate the aluminum foil, and the aluminum foil can be directly used for aluminum smelting after being washed. Treating the obtained black fine slag with 1mol/L nitric acid, simultaneously adding 30% hydrogen peroxide, controlling the solid-to-liquid ratio to be 40g/L, controlling the temperature to be 90 ℃, continuously stirring for 2h, and then filtering to obtain a leaching solution of valuable metals. The acid leaching residue is mainly carbon powder and other acid insoluble substances. The chemical components in the leachate were measured, and the results are shown in the following table 11:
TABLE 11 chemical composition in leachate (unit: g/L)
| Categories | Aluminium | Cobalt | Lithium ion source | Iron |
| Content (wt.) | 0.56 | 62.25 | 7.16 | 0.059 |
Adjusting the pH value of the acid leaching solution to about 10 by using alkali, diluting and adjusting the concentration of total anions and cations to 40g/L, performing ultrafiltration-nanofiltration-reverse osmosis treatment, controlling the pressure of an ultrafiltration membrane to be 0.1MPa, the pressure of a nanofiltration membrane to be 0.1MPa and the flow speed of concentrated water to be 0.1L/min, intercepting cobalt plasma by a membrane, enriching the cobalt plasma at the concentrated water side, and allowing lithium ions to enter fresh water, and respectively detecting to obtain a lithium-containing solution and other ion mixed solutions, wherein the single-stage interception rate of the cobalt ions reaches 96%. Lithium ions are enriched in fresh water, the enriched lithium-containing solution is further evaporated to enable the concentration of lithium to reach 35g/L, sodium fluoride is added at the temperature of 80 ℃ to precipitate lithium fluoride, and the battery-grade lithium fluoride is obtained through the treatment of washing, recrystallization, washing, drying and the like. The test results are shown in the following table 12:
TABLE 12 detection results of battery grade lithium fluoride
Removing impurities such as copper, iron and aluminum from the cobalt-containing solution by replacing with iron powder and controlling the pH to 3 with potassium hydroxide, filtering, precipitating cobalt from the filtrate with 0.5mol/L potassium hydroxide to obtain Co (OH)2And (5) producing the product. The process flow is short, the environment is protected, lithium is preferentially separated, the operation is simple and convenient, the large-scale production is easy, and the lithium fluoride and the cobalt hydroxide products meet the quality requirements of downstream battery enterprises on raw materials.
In conclusion, according to the technical scheme, lithium is preferentially separated by adopting a physical nanofiltration membrane method, and lithium carbonate recovered by adopting an ultrafiltration-nanofiltration-reverse osmosis combined technology has high purity, and the lithium carbonate separation method has the characteristics of simple process, environmental friendliness, low acid and alkali consumption, good and stable membrane separation effect, easiness in operation and suitability for industrial continuous production.
In addition, the inventor also refers to the mode of examples 1-6, tests are carried out by other raw materials, conditions and the like listed in the specification, and lithium and cobalt are recovered from waste lithium cobaltate batteries, so that high-quality battery-grade lithium carbonate and cobalt hydroxide products are obtained.
It should be noted that, in the present context, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in steps, processes, methods or experimental facilities including the element.
It should be understood that the above preferred embodiments are only for illustrating the present invention, and other embodiments of the present invention are also possible, but those skilled in the art will be able to adopt the technical teaching of the present invention and equivalent alternatives or modifications thereof without departing from the scope of the present invention.
Claims (16)
1. A method for recovering lithium and cobalt from waste lithium cobalt oxide batteries is characterized by comprising the following steps:
(1) discharging, disassembling and classifying the waste lithium cobalt oxide battery to obtain a positive plate;
(2) performing high-temperature calcination treatment on the positive plate, wherein the high-temperature calcination treatment is at least used for removing the binder in the positive plate, the calcination time is 0.5-6 h, and the calcination temperature is 300-800 ℃;
(3) soaking the high-temperature treated positive plate in an acidic substance, adding hydrogen peroxide, controlling the solid-to-liquid ratio to be 40-120 g/L, and stirring at 30-90 ℃ to leach valuable metal elements in the positive plate to obtain an acidified leachate, wherein the concentration of the acidic substance is 1-10 mol/L;
(4) respectively inputting the acidified leachate obtained in the step (3) into an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane, wherein the pore diameter of the ultrafiltration membrane is 10-1200A, the working pressure is 0.1-1.5 MPa, the working pressure of the nanofiltration membrane is 0.1-6 MPa, the flow rate of a single membrane is 0.1-5L/min, the working pH value is 2-10, and finally, a concentrated lithium-containing solution and a solution containing other cations are obtained, wherein the solution containing other cations is cobalt ions;
(5) adding a lithium precipitator into the lithium-containing solution to precipitate and separate out lithium ions in the lithium-containing solution, and reacting to obtain a lithium precipitate, wherein the lithium precipitator is selected from sodium carbonate, sodium bicarbonate or sodium fluoride, the lithium precipitate is selected from lithium carbonate or lithium fluoride, the content of lithium carbonate or lithium fluoride in the lithium precipitate is more than 99.5wt%, the content of aluminum is less than 0.001wt%, the content of iron is less than 0.001wt%, the content of sodium is less than 0.025wt%, and the content of magnesium is less than 0.008 wt%;
(6) and removing impurities from the solution containing other cations, adding an alkaline substance to precipitate cobalt ions in the solution containing other cations, reacting to obtain a cobalt precipitate, and recovering lithium and cobalt.
2. The method for recovering lithium and cobalt from waste lithium cobaltate batteries as claimed in claim 1, wherein the method comprises the following steps: the waste lithium cobalt oxide battery is selected from a mobile phone battery, a notebook computer battery, a digital camera battery or a high-voltage lithium cobalt oxide power battery.
3. The method for recovering lithium and cobalt from waste lithium cobaltate batteries as claimed in claim 1, wherein the method comprises the following steps: the acidic substance is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid and hydrofluoric acid.
4. The method for recovering lithium and cobalt from waste lithium cobaltate batteries as claimed in claim 1, wherein the method comprises the following steps: the pore diameter of the ultrafiltration membrane is 20-1000A.
5. The method for recovering lithium and cobalt from waste lithium cobaltate batteries as claimed in claim 1, wherein the method comprises the following steps: the concentration of the lithium-containing solution after concentration is more than 15 g/L.
6. The method for recovering lithium and cobalt from waste lithium cobaltate batteries as claimed in claim 1, wherein the method comprises the following steps: the nanofiltration membrane is made of a combination of any two or more of polyamide, polysulfone, polyvinyl alcohol, sulfonated polysulfone, sulfonated polyether sulfone and cellulose acetate.
7. The method for recovering lithium and cobalt from waste lithium cobaltate batteries as claimed in claim 6, wherein the method comprises the following steps: the nanofiltration membrane is made of a polyamide and polysulfone composite membrane, and the molecular weight cut-off of the membrane is 50-1000 daltons.
8. The method for recovering lithium and cobalt from waste lithium cobaltate batteries as claimed in claim 1, wherein the method comprises the following steps: the nanofiltration membrane is selected from a plate type nanofiltration membrane or a roll type nanofiltration membrane.
9. The method for recovering lithium and cobalt from waste lithium cobaltate batteries as claimed in claim 1, wherein the step (6) comprises the following steps: and (4) adding a copper removing agent into the solution containing other cations obtained in the step (4), adjusting the pH value to 3-5, adding an alkaline substance, and reacting to obtain a cobalt precipitate.
10. The method for recovering lithium and cobalt from spent lithium cobaltate batteries according to claim 9, wherein the method comprises the following steps: the copper removing agent is selected from any one or the combination of more than two of sodium sulfide, nickel sulfide and iron.
11. The method for recovering lithium and cobalt from spent lithium cobaltate batteries according to claim 9, wherein the method comprises the following steps: the alkaline substance is selected from one or the combination of more than two of sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide and calcium hydroxide.
12. The method for recovering lithium and cobalt from spent lithium cobaltate batteries according to claim 9, wherein the method comprises the following steps: the concentration of the alkaline substance is 0.5-8 mol/L.
13. The method for recovering lithium and cobalt from spent lithium cobaltate batteries according to claim 9, wherein the method comprises the following steps: the cobalt precipitate is selected from cobalt hydroxide, cobalt carbonate, cobalt oxide or cobaltosic oxide.
14. A system for recovering lithium and cobalt from spent lithium cobalt oxide batteries, for use in the method according to any one of claims 1 to 13, characterized in that it comprises:
the disassembling mechanism can disassemble and classify the waste lithium cobalt oxide batteries to obtain positive plates;
the acidification leaching mechanism can leach valuable metal elements in the positive plate to obtain an acidification leaching solution;
the combined system of ultrafiltration-nanofiltration-reverse osmosis comprises an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane, and is at least used for separating and concentrating lithium ions in acidified leachate from other cations;
a lithium precipitation mechanism for precipitating lithium ions at least;
a cobalt precipitation mechanism for at least precipitating out cobalt ions in the other cations.
15. The system for recovering lithium and cobalt from spent lithium cobaltate batteries according to claim 14, further comprising: and the high-temperature treatment mechanism is at least used for carrying out high-temperature treatment on the positive plate so as to remove the binder in the positive plate.
16. The system for recovering lithium and cobalt from spent lithium cobaltate batteries according to claim 14, further comprising: and the impurity removal mechanism is at least used for removing impurities of the solution containing other cations.
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| CN110311187A (en) * | 2019-07-16 | 2019-10-08 | 四川思达能环保科技有限公司 | The method of lithium battery recovery processing |
| CN110756191B (en) * | 2019-10-16 | 2022-06-28 | 许昌学院 | Method for preparing CoPi catalyst by green recovery of waste lithium cobaltate batteries |
| CN110951968A (en) * | 2019-10-31 | 2020-04-03 | 华北科技学院 | Method for recycling cobalt ions from waste lithium batteries |
| US11905180B2 (en) * | 2020-04-21 | 2024-02-20 | Toray Industries, Inc. | Method for recovering rare metal salt |
| CN112251617B (en) * | 2020-09-30 | 2022-11-04 | 湖南金凯循环科技有限公司 | Method for recovering lithium from waste metal lithium battery |
| CN112410565B (en) * | 2020-11-18 | 2022-10-04 | 上海第二工业大学 | Method for recycling valuable metal elements from waste ternary lithium ion battery positive electrode material |
| CN114570205A (en) * | 2020-11-30 | 2022-06-03 | 周思齐 | Method for separating alkali metal elements from alkali metal-containing solution |
| CN112707447A (en) * | 2020-12-25 | 2021-04-27 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Method for recycling and regenerating anode material from waste lithium cobalt oxide battery |
| CN113611876A (en) * | 2021-08-05 | 2021-11-05 | 哈尔滨工业大学 | Method for recycling anode material of waste lithium ion battery as electrocatalyst |
| CN113981226B (en) * | 2021-09-29 | 2023-09-05 | 贵州中伟资源循环产业发展有限公司 | Method for preprocessing ternary positive plate to be recycled |
| CN114134329B (en) * | 2021-11-30 | 2023-12-22 | 中国科学院宁波材料技术与工程研究所 | Method for recycling valuable metals in positive electrode material by utilizing aluminum foil of current collector of waste lithium ion battery |
| CN114665182B (en) * | 2022-04-25 | 2024-04-30 | 中国科学院青海盐湖研究所 | Method for separating and recycling current collector and negative electrode material in negative electrode of waste lithium ion battery |
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Effective date of registration: 20221226 Address after: Room 506, Office Building, No. 128 Chuangye Road, Chengzhong District, Xining City, Qinghai Province, 810,000 Patentee after: Qinghai Zhongkedefang Energy Technology Research Co.,Ltd. Address before: 810008, Xinning Road, Xining, Qinghai, 18 Patentee before: QINGHAI INSTITUTE OF SALT LAKES, CHINESE ACADEMY OF SCIENCES |
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