CN109207730B - Method and system for recovering lithium from waste lithium iron phosphate batteries - Google Patents
Method and system for recovering lithium from waste lithium iron phosphate batteries Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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- 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 discloses a method and a system for recovering lithium from waste lithium iron phosphate batteries. The method comprises the following steps: disassembling a positive plate from a waste lithium iron phosphate 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 respectively by using a reverse osmosis technology, wherein the other cations comprise iron ions; and precipitating lithium ions in the lithium-containing solution by using a lithium precipitator, and precipitating iron ions in the solution containing other cations by using an alkaline substance, thereby realizing the recovery of lithium. 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 from waste lithium iron phosphate 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. 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. In 2016, the yield of Chinese lithium batteries reaches 78.42 hundred million, and is increased by 40 percent on a year-by-year basis, wherein the yield of power batteries reaches 29.39GWh and exceeds the yield of 3C batteries, so that the lithium batteries become the largest consumer end. With the popularization and promotion of pure electric vehicles, the lithium ion battery market continues to keep high-speed growth, the Chinese lithium battery market scale in 2017 reaches 82GWH, and the composite growth rate in the last three years is 25%. Lithium iron phosphate batteries, batteries and ternary batteries are mainstream in China, and the lithium iron phosphate batteries are more used on large buses due to outstanding safety performance and low cost, and have strong competitive advantages.
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, and has remarkable economic benefit. Therefore, how to scientifically, green and efficiently recover valuable metals such as lithium from waste lithium batteries has become 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 waste lithium iron phosphate is typically recovered, and the lithium is not comprehensively recovered. The existing recovery technology of the waste lithium 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 existing waste battery recovery processes basically precipitate iron and then purify 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 patents CN105375079A and CN102288707A, the lithium iron phosphate battery is disassembled, separated into positive plates, and then added with a lithium source or a carbon source, and after being uniformly mixed, the lithium iron phosphate battery is directly subjected to high-temperature solid phase sintering to obtain a lithium iron phosphate positive electrode material. The process has harsh conditions and complex flow, and the performance stability of the repaired anode material needs to be further verified. And researchers in the industry separate and purify lithium by adopting hydrometallurgical technologies such as alkali-soluble acid leaching and precipitation, for example, a waste lithium iron phosphate power battery in the chinese patent CN102956936A is disassembled to obtain a positive plate, a binder is removed by high-temperature roasting, the roasted slag is subjected to acid leaching to obtain acid leaching slag and acid leaching solution, the acid leaching slag is subjected to alkali leaching to obtain alkali leaching solution, lithium nitrate is added, and a lithium phosphate product is obtained by solid-liquid separation. The lithium yield of the invention reaches 94%, but more alkaline leaching residue and acid leaching solution are generated, which brings environmental risk, and the product is lithium phosphate, so the economic value is relatively low.
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 from waste lithium iron phosphate 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 from waste lithium iron phosphate batteries, which comprises the following steps:
disassembling a positive plate from a waste lithium iron phosphate 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 iron ions;
and precipitating lithium ions in the lithium-containing solution by using a lithium precipitator, and precipitating iron ions in the solution containing other cations by using an alkaline substance, thereby realizing the recovery of lithium.
In some embodiments, the method for recovering lithium from a waste lithium iron phosphate battery specifically includes:
(1) discharging, disassembling and classifying the waste lithium iron phosphate 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 an iron precipitate.
The embodiment of the invention also provides a system for recovering lithium from the waste lithium iron phosphate batteries, which comprises the following steps:
the disassembling mechanism can disassemble and classify the waste lithium iron phosphate 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;
an iron precipitation mechanism for at least precipitating out iron ions in the other cations.
Compared with the prior art, the invention has the beneficial effects that:
1) the method for recovering lithium from the waste lithium iron phosphate batteries has the advantages that the lithium separation technology is advanced, the separation effect is good, lithium ions are preferentially separated from other divalent and trivalent cations by adopting an ultrafiltration-nanofiltration-reverse osmosis combined mode, the process flow is simplified, the process is a physical process, and organic matters or impurity ions cannot be introduced;
2) the method for recovering lithium from waste lithium iron phosphate batteries provided by the invention is novel in separation and purification concept, and preferentially adopts ultrafiltration pretreatment 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 and trivalent metal ions are separated from the acidified leachate, then lithium-containing solution and iron-containing solution are respectively treated, and the products are obtained by impurity removal and concentration, so that the process flow is greatly shortened, the entrainment loss of lithium ions in the 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, has low energy consumption, 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 process of the invention is a closed circulation system, the mother liquor can be recycled, no waste liquor is discharged, and the secondary pollution to the environment is reduced.
Drawings
Fig. 1 is a schematic flow diagram of a method for recovering lithium from spent lithium iron phosphate batteries according to an exemplary embodiment of the present invention.
Detailed Description
In view of the defects of low recovery efficiency, long process and secondary pollution to the environment of the existing waste lithium iron phosphate lithium battery, the inventor of the 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 iron elements. The process greatly reduces the using amount of acid and alkali, avoids the technical processes of organic solvent extraction and the like, 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 solution of the present invention, a method for recovering lithium from a waste lithium iron phosphate battery is provided, which includes:
disassembling a positive plate from a waste lithium iron phosphate 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 iron ions;
and precipitating lithium ions in the lithium-containing solution by using a lithium precipitator, and precipitating iron ions in the solution containing other cations by using an alkaline substance, thereby realizing the recovery of lithium.
In some embodiments, the method for recovering lithium from a waste lithium iron phosphate battery specifically includes:
(1) discharging, disassembling and classifying the waste lithium iron phosphate 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 an iron precipitate.
In some embodiments, the waste lithium iron phosphate batteries mainly use lithium iron phosphate as a positive electrode material or a lithium iron phosphate positive electrode leftover material, such as, but not limited to, waste lithium iron phosphate power batteries, 3C products, waste positive electrode plates produced in a lithium iron phosphate battery production process, and the like.
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, divalent and trivalent ion separation, namely separation of lithium, iron and phosphate radicals, 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 than divalent ions in concentrated water, enabling the interception effect of phosphate radicals and iron ions to be good, and then concentrating a lithium-containing solution again by combining with reverse osmosis to enable the concentration of lithium 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 99.5 wt%, the content of aluminum is less than 0.001 wt%, the content of iron is less than 0.001 wt%, the content of sodium is less than 0.025 wt%, 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 an iron 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 iron precipitate comprises iron phosphate, and the recovered iron phosphate can be used in a downstream battery.
As one of more specific embodiments of the present invention, referring to fig. 1, the method for recovering lithium from a waste lithium iron phosphate battery may specifically include the following steps:
the method comprises the steps of taking waste lithium iron phosphate batteries (including waste lithium iron phosphate power batteries, 3C products and waste positive plates generated in the production process of the lithium iron phosphate batteries) as raw materials, carrying out discharging, breaking, dismantling and screening to obtain the positive plates, carrying out high-temperature treatment to remove binders, leaching valuable metal elements through acid dissolution, and carrying out ultrafiltration membrane-nanofiltration membrane-reverse osmosis treatment on filtrate to respectively obtain lithium-containing solution and iron-containing solution. 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 iron-containing solution obtained by nanofiltration membrane separation, adjusting the pH value to 3-5, precipitating to remove impurities such as aluminum and the like, and then adding alkali to precipitate the iron phosphate, thereby realizing the recovery of lithium. 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.
Another aspect of an embodiment of the present invention also provides a system for recovering lithium from a waste lithium iron phosphate battery, including:
the disassembling mechanism can disassemble and classify the waste lithium iron phosphate 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;
an iron precipitation mechanism for at least precipitating out iron 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 leaching solution 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 bivalent and trivalent cations in the leaching solution, and then uses reverse osmosis to respectively concentrate solutions of univalent ions and bivalent and trivalent ions to realize the separation and concentration of lithium elements and iron elements. The process greatly reduces the using amount of acid and alkali, avoids the technical processes of organic solvent extraction and the like, 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 iron phosphate battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 600g of lithium iron phosphate anode material, treating for 2h in a muffle furnace at 400 ℃, removing the binder, carrying out water quenching, and treating for 60min in ultrasonic oscillation, so that the anode material and the aluminum foil are peeled. 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 2mol/L sulfuric acid, simultaneously adding 30% hydrogen peroxide, controlling the solid-to-liquid ratio at 100g/L, controlling the temperature at 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 | Phosphate radical | Lithium ion source | Iron | SO4 2- |
| Content (wt.) | 1.12 | 62.12 | 4.58 | 36.64 | 155.23 |
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 60g/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 ions such as iron and phosphate radicals by a membrane, enriching the ions on 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. 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
And replacing the iron-containing solution and the phosphate radical solution by iron powder to remove copper, adjusting the pH value to 3 to remove aluminum, and adjusting the pH value again to precipitate the phosphate radical to obtain the iron phosphate. 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 product meets the quality requirement of downstream battery enterprises on raw materials.
Example 2
The method takes a certain type of waste lithium iron phosphate battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 800g of lithium iron phosphate anode material, treating the material in a muffle furnace at 450 ℃ for 2h, removing the binder, carrying out water quenching, and treating the material in ultrasonic oscillation for 60min to peel the anode 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 3mol/L sulfuric acid, simultaneously adding 30% hydrogen peroxide, controlling the solid-to-liquid ratio at 100g/L, controlling the temperature at 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 3 below:
TABLE 3 chemical composition in leachate (unit: g/L)
| Categories | Aluminium | Phosphate radical | Lithium ion source | Iron | SO4 2- |
| Content (wt.) | 1.19 | 67.11 | 4.89 | 37.65 | 169.89 |
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 by using deionized water, controlling the concentration to 50g/L, performing ultrafiltration-nanofiltration-reverse osmosis treatment, 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 ions such as iron and phosphate radicals by a membrane, enriching the ions 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. 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 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 4:
TABLE 4 Battery grade lithium carbonate test results
And replacing the iron-containing solution and the phosphate radical solution by iron powder to remove copper, adjusting the pH value to 3.5 to remove aluminum, and adjusting the pH value again to precipitate the phosphate radical to obtain the iron phosphate. 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 product meets the quality requirement of downstream battery enterprises on raw materials.
Example 3
The method takes a certain type of waste lithium iron phosphate battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 900g of lithium iron phosphate anode material, treating for 2h in a muffle furnace at 500 ℃, removing the binder, quenching in water, and treating for 60min in ultrasonic oscillation to peel the anode 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 8mol/L sulfuric acid, simultaneously adding 30% hydrogen peroxide, controlling the solid-to-liquid ratio at 100g/L, controlling the temperature at 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 the following table 5:
TABLE 5 chemical composition in leachate (unit: g/L)
| Categories | Aluminium | Phosphate radical | Lithium ion source | Iron | SO4 2- |
| Content (wt.) | 1.75 | 71.35 | 4.89 | 38.25 | 161.36 |
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 60g/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 4MPa, the flow rate of concentrated water to be 3.0L/min, intercepting ions such as iron and phosphate radicals by a membrane, enriching the ions on 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. 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
And replacing the iron-containing solution and the phosphate radical solution by iron powder to remove copper, adjusting the pH value to remove aluminum, and adjusting the pH value again to precipitate the phosphate radical to obtain the iron phosphate. 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 product meets the quality requirement of downstream battery enterprises on raw materials.
Example 4
The method takes a certain type of waste lithium iron phosphate battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 1000g of lithium iron phosphate anode material, treating the lithium iron phosphate anode material in a muffle furnace at 600 ℃ for 2h, removing the binder, carrying out water quenching, and treating the lithium iron phosphate anode material in ultrasonic oscillation for 60min to strip the anode 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 2mol/L hydrochloric acid, simultaneously adding 30% hydrogen peroxide, controlling the solid-to-liquid ratio to be 85g/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 measured, and the results are shown in table 7 below:
TABLE 7 chemical composition in leachate (unit: g/L)
| Categories | Aluminium | Phosphate radical | Lithium ion source | Iron | Cl- |
| Content (wt.) | 2.36 | 75.12 | 4.93 | 39.61 | 123.24 |
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 60g/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 3.5MPa, the flow speed of concentrated water to be 4.0L/min, intercepting ions such as iron and phosphate radicals by a membrane, enriching the ions on 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. 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
And replacing the iron-containing solution and the phosphate radical solution by iron powder to remove copper, adjusting the pH value to 3 to remove aluminum, and adjusting the pH value again to precipitate the phosphate radical to obtain the iron phosphate. 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 product meets the quality requirement of downstream battery enterprises on raw materials.
Example 5
The method takes a certain type of waste lithium iron phosphate battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 900g of lithium iron phosphate anode 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 anode 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 perchloric 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 | Phosphate radical | Lithium ion source | Iron | Cl- |
| Content (wt.) | 1.95 | 72.12 | 4.56 | 35.62 | 135.24 |
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 1.5MPa, the pressure of a nanofiltration membrane to be 1.2MPa, the flow rate of concentrated water to be 2.0L/min, intercepting ions such as iron and phosphate radicals by a membrane, enriching the ions on 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. Lithium ions are enriched in fresh water, the enriched lithium-containing solution is further evaporated to enable the concentration of lithium to reach 25g/L, saturated sodium carbonate is added at the temperature of 80 ℃ to precipitate lithium carbonate, and the lithium carbonate is subjected to washing, recrystallization, washing, drying and the like to obtain the battery-grade lithium carbonate. The test results are shown in the following table 10:
TABLE 10 Battery grade lithium carbonate test results
And replacing the iron-containing solution and the phosphate radical solution by iron powder to remove copper, adjusting the pH value to 4.5 to remove aluminum, and adjusting the pH value again to precipitate the phosphate radical to obtain the iron phosphate. 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 product meets the quality requirement of downstream battery enterprises on raw materials.
Example 6
The method takes a certain type of waste lithium iron phosphate battery as a raw material. Firstly, discharging, disassembling and screening the waste battery to obtain the anode material. Weighing 900g of lithium iron phosphate anode material, treating for 6h in a muffle furnace at 300 ℃, removing the binder, carrying out water quenching, and treating for 90min in ultrasonic oscillation, so that the anode material and the aluminum foil are peeled. 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 | Phosphate radical | Lithium ion source | Iron |
| Content (wt.) | 1.95 | 72.12 | 4.56 | 35.62 |
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 ions such as iron and phosphate radicals by a membrane, enriching the ions on 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. 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 for battery grade lithium fluoride
And replacing the iron-containing solution and the phosphate radical solution by iron powder to remove copper, adjusting the pH value to 5 to remove aluminum, and adjusting the pH value again to precipitate the phosphate radical to obtain the iron phosphate. 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 product meets the quality requirement 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, lithium is recovered from the waste lithium iron phosphate battery, and high-quality battery-grade lithium carbonate is 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 (17)
1. A method for recovering lithium from waste lithium iron phosphate batteries is characterized by comprising the following steps:
(1) discharging, disassembling and classifying the waste lithium iron phosphate battery to obtain a positive plate;
(2) calcining the positive plate, and performing high-temperature treatment at least for removing the binder in the positive plate, wherein the calcining time is 0.5-6 h, and the calcining 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) 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 leaching solution by using a nanofiltration membrane to obtain a lithium-containing solution and a solution containing other cationsConcentrating and enriching a lithium-containing solution and a solution containing other cations by adopting a reverse osmosis membrane respectively to obtain a concentrated lithium-containing solution and a solution containing other cations, wherein the other cations comprise iron ions; wherein the pore diameter of the ultrafiltration membrane is
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,
(5) adding a lithium precipitator into 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 99.5 wt%, the content of aluminum is less than 0.001 wt%, the content of iron is less than 0.001 wt%, the content of sodium is less than 0.025 wt%, and the content of magnesium is less than 0.008 wt%;
(6) and (3) removing impurities from the solution containing other cations, adding an alkaline substance, reacting to obtain an iron precipitate, and recovering lithium.
2. The method for recovering lithium from waste lithium iron phosphate batteries according to claim 1, characterized in that: the waste lithium iron phosphate battery takes lithium iron phosphate as a positive electrode material or a lithium iron phosphate positive electrode leftover material.
3. The method for recovering lithium from waste lithium iron phosphate batteries according to claim 2, characterized in that: the waste lithium iron phosphate batteries comprise waste lithium iron phosphate power batteries or 3C products.
4. The method for recovering lithium from waste lithium iron phosphate batteries according to claim 1, wherein the acidic substance in the step (3) is selected from any one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid and hydrofluoric acid.
5. The method for recovering lithium from waste lithium iron phosphate batteries according to claim 1, wherein in the step (4), the pore diameter of the ultrafiltration membrane is set to be equal to
6. The method for recovering lithium from waste lithium iron phosphate batteries according to claim 1, wherein the concentration of the lithium-containing solution concentrated in the step (4) is more than 15 g/L.
7. The method for recovering lithium from waste lithium iron phosphate batteries according to claim 1, wherein the nanofiltration membrane in the step (4) is made of a combination of any two or more of polyamide, polysulfone, polyvinyl alcohol, sulfonated polysulfone, sulfonated polyethersulfone and cellulose acetate.
8. The method for recovering lithium from waste lithium iron phosphate batteries according to claim 7, wherein the nanofiltration membrane in the step (4) is made of a polyamide and polysulfone composite membrane, and has a membrane cut-off molecular weight of 50-1000 daltons.
9. The method for recovering lithium from waste lithium iron phosphate batteries according to claim 7, wherein the nanofiltration membrane in the step (4) comprises a plate-type nanofiltration membrane or a roll-type nanofiltration membrane.
10. The method for recovering lithium from waste lithium iron phosphate batteries according to claim 1, wherein the 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 an iron precipitate.
11. The method for recovering lithium from spent lithium iron phosphate batteries according to claim 10, wherein the method comprises the following steps: the copper removing agent is selected from any one or combination of more than two of sodium sulfide, nickel sulfide and iron.
12. The method for recovering lithium from spent lithium iron phosphate batteries according to claim 10, 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.
13. The method for recovering lithium from spent lithium iron phosphate batteries according to claim 10, wherein the method comprises the following steps: the concentration of the alkaline substance is 0.5-8 mol/L.
14. The method for recovering lithium from spent lithium iron phosphate batteries according to claim 10, wherein the method comprises the following steps: the iron precipitate comprises iron phosphate.
15. A system for recovering lithium from spent lithium iron phosphate batteries, used in the method according to any one of claims 1 to 14, characterized in that it comprises:
the disassembling mechanism can disassemble and classify the waste lithium iron phosphate 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;
an iron precipitation mechanism for at least precipitating out iron ions in the other cations.
16. The system for recovering lithium from spent lithium iron phosphate batteries according to claim 15, 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.
17. The system for recovering lithium from spent lithium iron phosphate batteries according to claim 15, further comprising: and the impurity removal mechanism is at least used for removing impurities of the solution containing other cations.
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| CN110165324B (en) * | 2019-06-24 | 2021-07-16 | 中国科学院青海盐湖研究所 | Method and system for recovering positive electrode from waste lithium battery and regenerating and repairing positive electrode |
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| CN115784266A (en) * | 2022-11-04 | 2023-03-14 | 西北矿冶研究院 | Process for recycling lithium element in waste lithium iron phosphate |
| CN115893457A (en) * | 2022-11-25 | 2023-04-04 | 河南佰利新能源材料有限公司 | Method for recovering lithium carbonate and iron phosphate from waste lithium iron phosphate and application thereof |
| CN116692952B (en) * | 2023-06-30 | 2024-04-05 | 江西三吨锂业有限公司 | Method for treating waste lithium iron phosphate anode material and co-producing FeOOH and lithium phosphate |
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| CN102956936B (en) * | 2011-08-25 | 2015-04-15 | 深圳市格林美高新技术股份有限公司 | Method for treating lithium iron phosphate cathode material of waste and old power lithium battery of automobile |
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