CN114195203A - Method for cooperatively recycling and regenerating waste lithium iron phosphate battery and waste nickel-cobalt-manganese-lithium battery - Google Patents
Method for cooperatively recycling and regenerating waste lithium iron phosphate battery and waste nickel-cobalt-manganese-lithium battery Download PDFInfo
- Publication number
- CN114195203A CN114195203A CN202111659959.2A CN202111659959A CN114195203A CN 114195203 A CN114195203 A CN 114195203A CN 202111659959 A CN202111659959 A CN 202111659959A CN 114195203 A CN114195203 A CN 114195203A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- lithium
- waste
- nickel
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for cooperatively recovering and regenerating a waste lithium iron phosphate battery and a waste nickel-cobalt-manganese-lithium battery, which comprises the steps of mixing positive and negative electrode powder of the waste lithium iron phosphate battery, positive and negative electrode powder of the waste nickel-cobalt-manganese-lithium battery and a sulfur source, carrying out vulcanization roasting, and carrying out water leaching on a vulcanization roasting product to obtain a lithium salt solution and enriched slag containing iron oxide and nickel-cobalt-manganese sulfide; leaching the enriched slag containing iron oxide and nickel-cobalt-manganese sulfide by using phosphoric acid to obtain iron phosphate solution and leached slag containing nickel-cobalt-manganese sulfide; and (3) carrying out flotation separation or wet separation on the leached slag containing the nickel-cobalt-manganese sulfide to obtain the nickel-cobalt-manganese sulfide. The method does not need to classify the waste batteries, can uniformly treat various waste batteries, simultaneously realizes the high-efficiency recovery and regeneration of useful resources such as lithium, iron, phosphorus, nickel, cobalt, manganese and the like to obtain LiOH, lithium iron phosphate and nickel cobalt manganese lithium products, has simple process and low cost, is not easy to cause environmental pollution, and is beneficial to large-scale production.
Description
Technical Field
The invention relates to a resource recovery method of waste lithium batteries, in particular to a method for realizing the cooperative recovery and regeneration of waste lithium iron phosphate batteries and waste nickel-cobalt-manganese-lithium batteries based on selective vulcanization and crystalline phase regulation, and belongs to the technical field of resource recovery of waste lithium batteries.
Background
With the mass growth of the world population and the rapid development of economy, the demand of more sustainable and multifunctional energy supply for human beings is urgent. At present, more than 80% of global energy sources come from fossil fuels such as natural gas, coal, petroleum and the like, which undoubtedly aggravates energy crisis and environmental pollution, it is increasingly important to seek more continuous and environmentally-friendly energy supply, and people realize clean production of energy sources by converting wind energy, solar energy, tidal energy, water energy and the like into electric energy. In addition, different types of batteries have been introduced, in particular lithium ion batteries, by means of Li+The storage and output of electric energy are realized by embedding and embedding the positive electrode and the negative electrode, and the electric energy is widely applied in life.
Although the lithium ion battery is called a "green battery", it is not really pollution-free. Compared with lead-acid batteries and nickel-chromium batteries, the lithium batteries do not contain heavy metals such as lead, cadmium and mercury which have high toxicity, but have more complex components, and if the components are discarded at will, the components have great influence on the environment and the human health. Firstly, the lithium battery anode material contains a large amount of heavy metals such as nickel, cobalt and manganese, which can cause serious pollution to soil and underground water on one hand and seriously threaten human life health on the other hand, for example, the metal oxide powder can cause serious damage to human respiratory tract and lung. Electrolyte and organic solvent in the battery are the most toxic parts, side reaction can occur in the battery circulation process to generate highly toxic substances, for example, lithium hexafluorophosphate as the electrolyte has strong corrosivity, hydrolysis of the lithium hexafluorophosphate can generate highly toxic HF gas and other P, F-containing chemicals, and if leakage occurs due to improper operation in the disassembling and processing processes, the electrolyte and the organic solvent can rapidly enter the surrounding environment to generate serious safety problems such as explosion, combustion, water body pollution and the like. Therefore, the standardization and safe recovery of the waste batteries are very necessary.
A commonly used positive electrode material for lithium batteries includes lithium iron phosphate (LiFePO)4) Lithium manganate (LiMn)2O4) Lithium cobaltate (LiCoO)2) Lithium nickel cobalt manganese oxide (LiNi)xCoyMn(1-x-y)O2) Lithium nickel cobalt aluminate (LiNi)xCoyAl(1-x-y)O2) And the types and the proportions of metal elements in the material are different, and the energy density, the stability, the endurance and other performances of the battery are far from each other. Therefore, at present, the waste lithium batteries are classified and then recovered by different methods, and a series of problems of long flow, high construction cost, difficult treatment of emissions and the like exist, so that a method for uniformly treating and recovering the waste batteries is urgently needed.
Disclosure of Invention
Aiming at the defects of long process, high cost and the like caused by the fact that waste lithium iron phosphate batteries and waste nickel cobalt manganese lithium batteries need to be classified, recovered and processed in the prior art, the invention aims to provide the method for realizing the cooperative processing and recovery of two battery systems of the waste lithium iron phosphate batteries and the waste nickel cobalt manganese lithium batteries, the method does not need to classify the waste batteries, can uniformly process the waste batteries, simultaneously realizes the high-efficiency recovery and regeneration of useful resources such as lithium, iron, phosphorus, nickel, cobalt, manganese and the like, obtains LiOH, lithium iron phosphate and nickel cobalt manganese lithium products, and has the advantages of simple process, low cost, difficulty in causing environmental pollution and benefit for large-scale production.
In order to achieve the technical purpose, the invention provides a method for cooperatively recovering and regenerating a waste lithium iron phosphate battery and a waste nickel-cobalt-manganese-lithium battery, which comprises the following steps of:
1) mixing the waste lithium iron phosphate battery positive electrode powder, the waste nickel-cobalt-manganese-lithium battery positive electrode powder and the sulfur source with the waste lithium iron phosphate battery negative electrode powder and/or the waste nickel-cobalt-manganese-lithium battery negative electrode powder, and carrying out vulcanization roasting to obtain a vulcanization roasting product;
2) carrying out water leaching on the vulcanized and roasted product to obtain a lithium salt solution and enriched slag containing iron oxide and nickel cobalt manganese sulfide;
3) leaching the enriched slag containing iron oxide and nickel-cobalt-manganese sulfide by using phosphoric acid to obtain iron phosphate solution and leached slag containing nickel-cobalt-manganese sulfide;
4) and (4) carrying out flotation separation or acid leaching on the leached slag containing the nickel-cobalt-manganese sulfide to obtain the nickel-cobalt-manganese sulfide.
The mixed powder of the waste lithium batteries in the technical scheme of the invention is the anode powder of the lithium iron phosphate batteries, the anode powder of the nickel-cobalt-manganese-lithium batteries and the cathode powder of the lithium iron phosphate batteries and the cathode powder of the nickel-cobalt-manganese-lithium batteries, which comprises the cathode powder mainly made of carbon materials and the anode powder mainly made of active materials of two major types of anode active materials of the lithium iron phosphate, the nickel-cobalt-manganese-lithium batteries in the prior art, the types of the waste lithium batteries are not required to be classified, only a sulfur source is added into the mixed battery anode powder for selective vulcanization roasting, carbon in the cathode powder can create favorable conditions for the vulcanization roasting process of the mixed anode powder, the cathode powder not only can be used as a reducing substance to inhibit sulfur dioxide gas generated in the vulcanization roasting process, but also can be used as an oxidizing sulfur source, the vulcanization reaction temperature can be reduced, the vulcanization reaction is easier to carry out, the selectivity of the vulcanization roasting is improved, transition metals such as nickel, cobalt, manganese and the like are converted into metal sulfides which are insoluble in water and insoluble in phosphoric acid, lithium is mainly converted into lithium sulfate or lithium sulfide which is easily dissolved in water, and iron is converted into oxide and phosphate which are easily leached by phosphoric acid, so that the subsequent separation and recovery process is facilitated. Particularly, the particle size and the crystallinity of the metal sulfide ore can be effectively regulated and controlled in the process of the vulcanizing roasting, which is beneficial to the subsequent flotation separation process, and the mixed powder before the selective vulcanizing roasting is a lithium iron phosphate material and a nickel-cobalt-manganese-lithium material with large particle size, has uniform property, all metal elements are tightly combined, after the selective vulcanizing roasting, as shown in b of fig. 2, it can be seen that the cell material lattice is broken, the metal elements are separated under the action of the sulfur and carbon materials, and selectively sulfurized into metal sulfides and metal oxides with different properties, which lays the foundation for the subsequent separation and recovery of each metal, iron mainly exists in the form of phosphate and iron oxide which are easily leached by phosphoric acid selectively, the nickel, cobalt and manganese mainly exist in a sulfide form, and are easy to be efficiently recovered by flotation through regulation and control of crystallinity and particle size, and lithium is converted into lithium sulfide, lithium sulfate and the like. On the basis, the lithium salt can be efficiently leached by adopting a water leaching method, then the water leaching slag is leached by adopting phosphoric acid, the leachate is purified and purified to generate high-purity ferric phosphate, and the lithium can be supplemented to regenerate the lithium iron phosphate cathode material. The phosphoric acid leaching slag can be purified and decontaminated in a flotation or wet separation (acid leaching) mode to obtain high-purity nickel-cobalt-manganese-sulfide, and the nickel-cobalt-manganese-lithium anode material can be regenerated after lithium supplement, so that the regeneration and utilization of all kinds of waste lithium batteries can be completed in one set of process.
As a preferable scheme, the mass ratio of the waste lithium iron phosphate battery positive electrode powder, the waste nickel cobalt manganese lithium battery positive electrode powder and the waste lithium iron phosphate battery negative electrode powder and/or the waste nickel cobalt manganese lithium battery negative electrode powder is (1-5): 1-8): 1-9; further preferably (1 to 3), (1 to 5), (1 to 6). The proportion of the anode powder of the waste lithium iron phosphate battery and the anode powder of the waste nickel-cobalt-manganese-lithium battery is required to be adjusted and controlled, the carbon content introduced by the cathode powder is controlled to be beneficial to promoting the selective vulcanization reaction of metals such as nickel, cobalt and manganese to be smoothly carried out, the reduction effect of the carbon material in the cathode is utilized to promote the crystal lattice crushing of the anode material, the vulcanization efficiency is improved, meanwhile, the proper reduction environment is controlled to be beneficial to adjusting and controlling the crystallinity and the particle size of the nickel-cobalt-manganese sulfide, and the nickel-cobalt-manganese sulfide is easy to be efficiently recovered by flotation.
As a preferable scheme, the mass ratio of the total mass of the waste lithium iron phosphate battery positive electrode powder, the waste nickel-cobalt-manganese-lithium battery positive electrode powder and the waste lithium iron phosphate battery negative electrode powder and/or the waste nickel-cobalt-manganese-lithium battery negative electrode powder to the sulfur source is 10: 1-1: 3; more preferably 4:1 to 1: 2. The complete sulfuration of metals such as nickel, cobalt, manganese and the like in the anode material can be realized by controlling the proportion of the sulfur source. The waste lithium iron phosphate is beneficial to capturing and converting sulfur into iron sulfide at the initial stage of sulfuration roasting, prevents volatilization of sulfur, and can be used as a sulfur source to provide conditions for sulfuration of nickel, cobalt and manganese at the later stage of roasting, and simultaneously reduces the using amount of sulfur.
As a preferred scheme, the sulfur source is sulfur, sulfide, sulfate, SO2Gas, H2At least one of S gases. Further preferably sulfur or SO2A gas.
As a preferred scheme, the conditions of the sulfurizing roasting are as follows: the temperature is 300-1000 ℃, and the time is 30-150 min. The temperature of the sulfuration roasting is preferably 500-1000 ℃, more preferably 500-800 ℃, and the time is more preferably 90-120 min. The carbon material in the negative electrode powder can promote the vulcanizing roasting to be carried out at a lower temperature, for example, the high-efficiency vulcanization of the positive electrode material can be realized at the temperature of below 1000 ℃, but the lower the temperature is, the weaker the vulcanizing crystallization of the product is, and the relatively poorer the vulcanizing roasting effect is, so the preferable vulcanizing roasting temperature is 500-800 ℃.
As a preferred scheme, the conditions of the water leaching process are as follows: the temperature is 25-95 ℃, the liquid-solid ratio is 5-15 mL:1g, and the leaching time is 1-5 hours. Under the preferable conditions, a higher leaching rate of the lithium salt can be obtained.
As a preferred scheme, the phosphoric acid leaching conditions are as follows: the temperature is 55-95 ℃, the liquid-solid ratio is 8-20 mL:1g, the leaching time is 0.5-5 hours, and the concentration of phosphoric acid is 1-5 mol/L. Under the optimized condition, iron oxide and iron phosphate can be selectively leached out to obtain higher leaching rate of iron, while nickel-cobalt-manganese sulfide is enriched in slag.
As a preferred scheme, the conditions of the flotation separation are as follows: at least one of xanthate, black powder and ethyl thiourethane is used as a collecting agent, terpineol is used as a foaming agent, at least one of water glass, sodium humate, water-soluble starch and sodium hexametaphosphate is used as an inhibitor, and sodium carbonate and/or sodium hydroxide is used as a pH regulator. As a preferable scheme, the using amount of the collecting agent relative to raw ore is 300-600 g/t; the consumption of the foaming agent relative to raw ore is 30-100 g/t; the dosage of the inhibitor relative to the raw ore is 60-120 g/t; the pH value of the system is controlled to be 5-10 by the pH regulator. The flotation efficiency of the metal sulfide can be greatly improved under the optimized flotation conditions.
As a preferable scheme, the leached slag containing the nickel-cobalt-manganese sulfide is subjected to acid leaching to remove other mineral impurities, so that a higher-grade nickel-cobalt-manganese sulfide mineral can be obtained.
As a preferred embodiment, the lithium salt solution is used to prepare LiOH by purification, impurity removal and alkaline precipitation. The purification and impurity removal process comprises the steps of removing metal impurities such as iron, nickel, manganese, cobalt and the like in the water extract by using a sulfuric acid + hydrogen peroxide, a citric acid + hydrogen peroxide, P204 and the like mode, or preferentially precipitating the metal impurities such as iron, nickel, manganese, cobalt and the like directly by using a value-adjusting fractional precipitation mode, wherein the purified lithium solution can pass through Na2CO3Or NaOH is subjected to value adjustment and precipitation to obtain high-purity LiOH, and the method for obtaining high-purity LiOH by lithium salt is easy to realize by referring to the prior art.
As a preferable scheme, the iron phosphate solution is purified to remove impurities and supplement lithium to prepare the lithium iron phosphate. The purification and impurity removal of the ferric phosphate solution can adopt evaporative crystallization to preferentially crystallize the ferric phosphate from the leaching solution by utilizing the difference of solubility and concentration, and other metal impurities are remained in the residual leaching solution, or Na is added2CO3Or precipitating impurity ions of nickel, cobalt and manganese metal by NaOH step by step to obtain a pure ferric phosphate solution, and then evaporating and crystallizing to obtain the high-purity ferric phosphate. The preparation of lithium iron phosphate from a ferric phosphate solution is also a common method in the prior art and can be realized by referring to the prior art. In the lithium supplementing process, the LiOH obtained by recovery can be used as a lithium source, and the lithium supplementing process is realized by roasting iron phosphate, LiOH and the like.
As a preferred embodiment, the nickel-cobalt-manganese sulfide is used for preparing nickel-cobalt-manganese lithium by lithium supplement. In the process of lithium supplement, the recycled LiOH can be used as a lithium source, and the lithium source is realized by oxidizing and roasting nickel cobalt manganese sulfide, LiOH and the like.
The waste lithium battery mainly refers to a common lithium iron phosphate battery and a common nickel-cobalt-manganese-lithium battery in the prior art.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) according to the technical scheme, two lithium battery systems of the waste lithium iron phosphate battery and the waste nickel-cobalt-manganese-lithium battery do not need to be classified, the mixed waste lithium battery can be recycled and regenerated by one set of process flow, and the lithium battery recycling process can be simplified.
2) According to the technical scheme, the selective vulcanization roasting-water leaching-dressing-smelting combined integrated process is used for separating and recovering metals such as lithium, iron, nickel, cobalt, manganese and the like and non-metallic phosphorus and the like in various waste lithium batteries, the separation effect is obvious, the purity of the obtained final product is high, the final product can be directly used as a raw material for preparing a new battery material, and the problems that in the prior art, valuable metals in the waste lithium batteries are high in recovery and utilization cost and difficult to recycle are solved.
3) According to the technical scheme, the waste lithium iron phosphate material and the nickel-cobalt-manganese-lithium material are cooperatively and selectively vulcanized and roasted, the mineral crystalline phase regulation and control in the vulcanization roasting process are promoted by utilizing the difference of the affinity between metals such as iron, nickel, cobalt, manganese and the like and sulfur and the physicochemical property characteristics of intermediate products, iron mainly exists in the form of oxides and phosphates which are easily and selectively leached by phosphoric acid, nickel-cobalt-manganese exists in the form of sulfides which are not easily leached by phosphoric acid, and nickel-cobalt-manganese sulfides are easily and efficiently recovered by flotation through the regulation and control on crystallinity and particle size in the vulcanization roasting process.
4) According to the technical scheme, the water leaching and the dressing and smelting are combined to separate lithium from metals such as iron, nickel, cobalt, manganese and the like, the lithium is preferentially recovered through the water leaching, and the transition metals such as iron, nickel, cobalt, manganese and the like are recovered through the dressing and smelting combined mode, so that the cost can be reduced to a great extent, the influence on the environment is reduced, the recovery rate is effectively improved, and the high-purity raw material for preparing the battery is obtained.
5) The invention utilizes the negative electrode powder, not only promotes the metal vulcanization of the mixed positive electrode powder, but also inhibits the generation of sulfur dioxide gas, reduces the reaction temperature and the reaction difficulty, provides a basis for an environment-friendly, economic and efficient process route, has low impurity content of the negative electrode powder, does not introduce other impurities, is favorable for the regeneration of battery materials, and lays a technical foundation for the mixed recovery of the positive electrode and the negative electrode of various waste batteries in the future.
6) The technical scheme of the invention has the advantages of relatively simple process, conventional equipment and easy realization of industrial production.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a comparison of the mixed powder before sulfiding calcination and the sulfided calcination product.
FIG. 3 is an XRD phase diagram of the leaching residue obtained after phosphoric acid leaching
Detailed Description
The following specific examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
Waste lithium iron phosphate positive powder, waste nickel cobalt manganese lithium positive powder and negative powder (waste nickel cobalt manganese lithium battery negative powder) are mixed according to the proportion of 1:1:1, then the mixed powder and sulfur are mixed according to the mass ratio of 10:7, and then vulcanization roasting is carried out for 120min at 1000 ℃, the obtained roasting product is subjected to SEM detection, the result is shown in figure 2(b), the SEM detection of the mixed powder before roasting is carried out, the result is shown in figure 2(a), the mixed powder before selective vulcanization roasting is large-particle-size lithium iron phosphate and nickel cobalt manganese lithium material, the material is uniform in property, all metal elements are tightly combined, after selective vulcanization roasting, the crystal lattices of the battery material are crushed, the metal elements are separated under the action of sulfur, and are selectively vulcanized into metal sulfides and oxides with different properties, and a foundation is laid for the separation and recovery of subsequent metals. Leaching the obtained vulcanized roasting product for 90min at 85 ℃ according to a liquid-solid ratio of 10:1, wherein the leaching rate of lithium is 94.61%, and adding NaOH into the filtrate after filtration to carry out precipitation and impurity removal to obtain LiOH precipitate; leaching the water leaching slag by phosphoric acid, wherein the concentration of the phosphoric acid is 4mol/L, the liquid-solid ratio is 12:1, the leaching temperature is 60 ℃, the leaching time is 30min, an iron phosphate solution and nickel-cobalt-manganese sulfide leaching slag are obtained, and XRD phase detection is carried out on the leaching slag, so that the result is shown in figure 3, that iron completely enters the solution after the phosphoric acid leaching, and the leaching slag is nickel-cobalt-manganese sulfide. And (3) evaporating and crystallizing the iron phosphate solution to obtain high-purity iron phosphate, wherein the leaching rate of iron is 92.79%.
Grinding the mixed product of the nickel, cobalt and manganese leaching residues until the mixed product is ground to-0.074 mm and accounts for 89.77%, stirring the mixed product for 10min at 1200r/min by a flotation machine and adjusting the concentration of ore pulp to 50%; adding collecting agent black powder (the addition amount of the collecting agent black powder is 500g/t relative to the raw ore) into the ore pulp, stirring for 5min, adding foaming agent terpineol (the addition amount of the foaming agent terpineol is 40g/t relative to the raw ore), stirring for 15min, adding pH regulator sodium hydroxide, and adjusting the pH value of the ore pulp to be 8. And (4) performing rough concentration, wherein the foam scraping time is 2min, and obtaining rough concentrated material and tailing material. The concentrate is purified nickel cobalt manganese sulfide, wherein the recovery rates of nickel, cobalt and manganese are respectively 96.29%, 92.43% and 94.78%. The obtained high-purity iron phosphate and high-purity nickel cobalt manganese sulfide can be regenerated into a battery for utilization through subsequent supplement of a lithium source.
Example 2
Mixing waste lithium iron phosphate positive electrode powder, waste nickel cobalt manganese lithium positive electrode powder and negative electrode powder (the mass of the waste lithium iron phosphate negative electrode powder and the waste nickel cobalt manganese lithium negative electrode powder is 1:1) according to the ratio of 3:2:4, mixing the mixed powder with sulfur according to the mass ratio of 1:2, then carrying out vulcanization roasting at 600 ℃ for 90min, leaching the obtained vulcanization roasting product at room temperature for 120min according to the liquid-solid ratio of 8:1, wherein the leaching rate of lithium is 92.77%, filtering, adding sulfuric acid and hydrogen peroxide into the filtrate for impurity removal, filtering, and adding Na into the filtrate for impurity removal2CO3Adjusting the pH value of the solution to obtain LiOH precipitate; leaching the water leaching residue by using phosphoric acid, wherein the concentration of the phosphoric acid is 2mol/L, the liquid-solid ratio is 10:1, the leaching temperature is 80 ℃, the leaching time is 100min, an iron phosphate solution and nickel-cobalt-manganese sulfide leaching residue are obtained, and the iron phosphate solution is evaporated and crystallized to obtain high-purity iron phosphate, wherein the iron leaching rate is 94.51%.
Grinding the mixed product of the nickel, cobalt and manganese leaching slag until the mixed product is ground to-0.074 mm and accounts for 90.62%, stirring the mixed product for 20min at 800r/min by a flotation machine and adjusting the concentration of ore pulp to 30%; adding collecting agent black powder (the addition amount of the collecting agent black powder is 700g/t relative to the raw ore) into the ore pulp, stirring for 10min, adding foaming agent terpineol (50 g/t relative to the additive of the raw ore), stirring for 10min, adding pH regulator sodium hydroxide, and adjusting the pH value of the ore pulp to 7. And (4) performing rough concentration, wherein the foam scraping time is 10min, and obtaining rough concentrated material and tailing material. The concentrate is a purified nickel-cobalt-manganese sulfide, wherein the recovery rates of nickel, cobalt and manganese are respectively 94.38%, 91.92% and 93.76%. The obtained high-purity iron phosphate and high-purity nickel cobalt manganese sulfide can be regenerated into a battery for utilization through subsequent supplement of a lithium source.
Example 3
Mixing waste lithium iron phosphate positive electrode powder, waste nickel cobalt manganese lithium positive electrode powder and negative electrode powder (the mass of the waste lithium iron phosphate negative electrode powder and the waste nickel cobalt manganese lithium negative electrode powder is 2:1) according to a ratio of 3:5:6, mixing the mixed powder with sulfur according to a mass ratio of 1:2, then carrying out vulcanization roasting at 800 ℃ for 100min, leaching an obtained vulcanization roasting product for 5h at 95 ℃ according to a liquid-solid ratio of 15:1, wherein the leaching rate of lithium is 96.93%, filtering, adding sulfuric acid and hydrogen peroxide into the filtrate for impurity removal, filtering, and adding Na into the filtrate2CO3Adjusting the pH value of the solution to obtain LiOH precipitate; leaching the water leaching residue by using phosphoric acid, wherein the concentration of the phosphoric acid is 5mol/L, the liquid-solid ratio is 20:1, the leaching temperature is 95 ℃, and the leaching time is 5 hours, so as to obtain an iron phosphate solution and nickel-cobalt-manganese sulfide leaching residue, and evaporating and crystallizing the iron phosphate solution to obtain high-purity iron phosphate, wherein the leaching rate of iron is 97.04%.
Grinding the mixed product of the nickel, cobalt and manganese leaching slag until the mixed product is ground to-0.074 mm and accounts for 93.55 percent, stirring the mixed product for 30min at 1000r/min by a flotation machine and adjusting the concentration of ore pulp to 50 percent; adding collecting agent black powder (the addition amount of the collecting agent black powder is 600g/t relative to the raw ore) into the ore pulp, stirring for 30min, adding foaming agent terpineol (the addition amount of the foaming agent terpineol is 70g/t relative to the raw ore), stirring for 30min, adding pH regulator sodium hydroxide, and adjusting the pH value of the ore pulp to 10. And (4) performing rough concentration, wherein the foam scraping time is 15min, and obtaining rough concentrated material and tailing material. The concentrate is purified nickel cobalt manganese sulfide, wherein the recovery rates of nickel, cobalt and manganese are 96.47%, 94.91% and 95.82% respectively. The obtained high-purity iron phosphate and high-purity nickel cobalt manganese sulfide can be regenerated into a battery for utilization through subsequent supplement of a lithium source.
Claims (10)
1. A method for cooperatively recovering and regenerating a waste lithium iron phosphate battery and a waste nickel-cobalt-manganese-lithium battery is characterized by comprising the following steps of: the method comprises the following steps:
1) mixing the waste lithium iron phosphate battery positive electrode powder, the waste nickel-cobalt-manganese-lithium battery positive electrode powder and the sulfur source with the waste lithium iron phosphate battery negative electrode powder and/or the waste nickel-cobalt-manganese-lithium battery negative electrode powder, and carrying out vulcanization roasting to obtain a vulcanization roasting product;
2) carrying out water leaching on the vulcanized and roasted product to obtain a lithium salt solution and enriched slag containing iron oxide and nickel cobalt manganese sulfide;
3) leaching the enriched slag containing iron oxide and nickel-cobalt-manganese sulfide by using phosphoric acid to obtain iron phosphate solution and leached slag containing nickel-cobalt-manganese sulfide;
4) and (4) carrying out flotation separation or acid leaching on the leached slag containing the nickel-cobalt-manganese sulfide to obtain the nickel-cobalt-manganese sulfide.
2. The method for the cooperative recycling and regeneration of the waste lithium iron phosphate battery and the waste nickel cobalt manganese lithium battery according to claim 1, wherein the method comprises the following steps: the mass ratio of the waste lithium iron phosphate battery positive electrode powder, the waste nickel-cobalt-manganese-lithium battery positive electrode powder and the waste lithium iron phosphate battery negative electrode powder and/or the waste nickel-cobalt-manganese-lithium battery negative electrode powder is (1-5): 1-8): 1-9.
3. The method for the cooperative recycling and regeneration of the waste lithium iron phosphate battery and the waste nickel cobalt manganese lithium battery according to claim 1, wherein the method comprises the following steps: the mass ratio of the total mass of the waste lithium iron phosphate battery positive electrode powder, the waste nickel-cobalt-manganese-lithium battery positive electrode powder and the waste lithium iron phosphate battery negative electrode powder and/or the waste nickel-cobalt-manganese-lithium battery negative electrode powder to the sulfur source is 10: 1-1: 3.
4. The method for the cooperative recycling and regeneration of the waste lithium iron phosphate battery and the waste nickel cobalt manganese lithium battery according to claim 1, wherein the method comprises the following steps: the sulfur source is sulfur, sulfide,Sulfate, SO2Gas, H2At least one of S gases.
5. The method for the cooperative recycling and regeneration of the waste lithium iron phosphate battery and the waste nickel cobalt manganese lithium battery according to claim 1, wherein the method comprises the following steps: the conditions of the sulfuration roasting are as follows: the temperature is 300-1000 ℃, and the time is 30-150 min.
6. The method for the cooperative recycling and regeneration of the waste lithium iron phosphate battery and the waste nickel cobalt manganese lithium battery according to claim 1, wherein the method comprises the following steps: the conditions of the water leaching process are as follows: the temperature is 25-95 ℃, the liquid-solid ratio is 5-15 mL:1g, and the leaching time is 1-5 hours.
7. The method for the cooperative recycling and regeneration of the waste lithium iron phosphate battery and the waste nickel cobalt manganese lithium battery according to claim 1, wherein the method comprises the following steps: the conditions of the phosphoric acid leaching are as follows: the temperature is 55-95 ℃, the liquid-solid ratio is 8-20 mL:1g, the leaching time is 0.5-5 hours, and the concentration of phosphoric acid is 1-5 mol/L.
8. The method for the cooperative recycling and regeneration of the waste lithium iron phosphate battery and the waste nickel cobalt manganese lithium battery according to claim 1, wherein the method comprises the following steps: the conditions of the flotation separation are as follows: at least one of xanthate, black powder and ethyl thiourethane is used as a collecting agent, terpineol is used as a foaming agent, at least one of water glass, sodium humate, water-soluble starch and sodium hexametaphosphate is used as an inhibitor, and sodium carbonate and/or sodium hydroxide is used as a pH regulator.
9. The method for the cooperative recycling and regeneration of the waste lithium iron phosphate battery and the waste nickel cobalt manganese lithium battery according to claim 1, wherein the method comprises the following steps:
the using amount of the collecting agent relative to the raw ore is 300-600 g/t;
the dosage of the foaming agent relative to the raw ore is 30-100 g/t;
the dosage of the inhibitor relative to the raw ore is 60-120 g/t;
the pH value of the system is controlled to be 5-10 by the pH regulator.
10. The method for the cooperative recycling and regeneration of the waste lithium iron phosphate battery and the waste nickel cobalt manganese lithium battery according to claim 1, wherein the method comprises the following steps:
preparing LiOH by purifying the lithium salt solution to remove impurities and performing alkaline sedimentation;
preparing lithium iron phosphate by purifying the iron phosphate solution to remove impurities and supplementing lithium;
the nickel-cobalt-manganese sulfide is used for preparing nickel-cobalt-manganese-lithium by supplementing lithium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111659959.2A CN114195203B (en) | 2021-12-30 | 2021-12-30 | Method for cooperatively recycling and regenerating waste lithium iron phosphate battery and waste nickel-cobalt-manganese-lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111659959.2A CN114195203B (en) | 2021-12-30 | 2021-12-30 | Method for cooperatively recycling and regenerating waste lithium iron phosphate battery and waste nickel-cobalt-manganese-lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114195203A true CN114195203A (en) | 2022-03-18 |
| CN114195203B CN114195203B (en) | 2022-10-25 |
Family
ID=80657670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111659959.2A Active CN114195203B (en) | 2021-12-30 | 2021-12-30 | Method for cooperatively recycling and regenerating waste lithium iron phosphate battery and waste nickel-cobalt-manganese-lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114195203B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115367732A (en) * | 2022-09-20 | 2022-11-22 | 中南大学 | Method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium battery in synergic manner |
| CN115747494A (en) * | 2022-09-19 | 2023-03-07 | 中南大学 | Method for extracting metallic lithium from anode material of waste lithium ion battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130312254A1 (en) * | 2011-02-17 | 2013-11-28 | Korea Institute Of Geoscience And Mineral Resources | Method for manufacturing a valuable-metal sulfuric-acid solution from a waste battery, and method for manufacturing a positive electrode active material |
| CN108933308A (en) * | 2018-07-13 | 2018-12-04 | 江西环锂新能源科技有限公司 | A kind of comprehensive reutilization method for scrapping lithium battery positive and negative anodes |
| CN109935922A (en) * | 2019-03-14 | 2019-06-25 | 北京矿冶科技集团有限公司 | A method of recycling valuable metal from waste and old lithium ion battery material |
| CN110835682A (en) * | 2019-09-26 | 2020-02-25 | 北京矿冶科技集团有限公司 | Method for cooperatively treating positive and negative active materials of waste lithium ion battery |
| CN111118294A (en) * | 2020-01-15 | 2020-05-08 | 北京矿冶科技集团有限公司 | Method for recycling valuable metals from waste lithium ion battery materials step by step |
| CN112938921A (en) * | 2021-04-07 | 2021-06-11 | 贵州唯特高新能源科技有限公司 | Method for preparing iron phosphate |
| CN113206227A (en) * | 2021-04-19 | 2021-08-03 | 中南大学 | Method for preparing carbon-based metal sulfide negative electrode material by simultaneously recycling positive and negative electrode materials of waste nickel-cobalt-manganese lithium ion battery |
-
2021
- 2021-12-30 CN CN202111659959.2A patent/CN114195203B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130312254A1 (en) * | 2011-02-17 | 2013-11-28 | Korea Institute Of Geoscience And Mineral Resources | Method for manufacturing a valuable-metal sulfuric-acid solution from a waste battery, and method for manufacturing a positive electrode active material |
| CN108933308A (en) * | 2018-07-13 | 2018-12-04 | 江西环锂新能源科技有限公司 | A kind of comprehensive reutilization method for scrapping lithium battery positive and negative anodes |
| CN109935922A (en) * | 2019-03-14 | 2019-06-25 | 北京矿冶科技集团有限公司 | A method of recycling valuable metal from waste and old lithium ion battery material |
| CN110835682A (en) * | 2019-09-26 | 2020-02-25 | 北京矿冶科技集团有限公司 | Method for cooperatively treating positive and negative active materials of waste lithium ion battery |
| CN111118294A (en) * | 2020-01-15 | 2020-05-08 | 北京矿冶科技集团有限公司 | Method for recycling valuable metals from waste lithium ion battery materials step by step |
| CN112938921A (en) * | 2021-04-07 | 2021-06-11 | 贵州唯特高新能源科技有限公司 | Method for preparing iron phosphate |
| CN113206227A (en) * | 2021-04-19 | 2021-08-03 | 中南大学 | Method for preparing carbon-based metal sulfide negative electrode material by simultaneously recycling positive and negative electrode materials of waste nickel-cobalt-manganese lithium ion battery |
Non-Patent Citations (6)
| Title |
|---|
| JIAO LIN ET AL.: "Conversion Mechanisms of Selective Extraction of Lithium from Spent Lithium-Ion Batteries by Sulfation Roasting", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| JOEY CHUNG-YENJUNG ET AL.: "A review of recycling spent lithium-ion battery cathode materials using hydrometallurgical treatments", 《JOURNAL OF ENERGY STORAGE》 * |
| YUE YANG ET AL.: "Recovering valuable metals from the leaching liquor of blended cathode material of spent lithium-ion battery", 《JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING》 * |
| YUKUN LI: "Recycling of spent lithium-ion batteries in view of green chemistry", 《GREEN CHEMISTRY》 * |
| Z. XIAO ET AL.: "Efficient fabrication of metal sulfides/graphite anode materials derived from spent lithium-ion batteries by gas sulfidation process", 《MATERIALS TODAY ENERGY》 * |
| 郑茹娟: "废旧磷酸盐类及混合锂离子电池回收再利用研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115747494A (en) * | 2022-09-19 | 2023-03-07 | 中南大学 | Method for extracting metallic lithium from anode material of waste lithium ion battery |
| CN115367732A (en) * | 2022-09-20 | 2022-11-22 | 中南大学 | Method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium battery in synergic manner |
| CN115367732B (en) * | 2022-09-20 | 2023-08-22 | 中南大学 | Industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium battery collaborative recycling method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114195203B (en) | 2022-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107267759B (en) | A kind of comprehensive recovering process of anode material for lithium-ion batteries | |
| CN110112481B (en) | Method for preparing lithium iron phosphate positive material by recycling waste lithium iron phosphate batteries | |
| CN106910889B (en) | A method of regenerating positive active material from waste lithium iron phosphate battery | |
| CN108899601B (en) | Method for recovering lithium and iron from lithium iron phosphate | |
| CN114195203B (en) | Method for cooperatively recycling and regenerating waste lithium iron phosphate battery and waste nickel-cobalt-manganese-lithium battery | |
| CN108642304B (en) | Comprehensive recovery method of lithium iron phosphate waste | |
| WO2016026344A1 (en) | Method for recovering lead oxide from waste lead plaster | |
| CN108767353B (en) | Method for producing lithium-rich clean liquid from anode active material of waste lithium ion battery | |
| CN111733326A (en) | Method for efficiently recycling ternary cathode material of waste lithium ion battery | |
| CN112897492B (en) | Method for regenerating and recycling high-impurity lithium iron phosphate waste powder | |
| CN107017444A (en) | A kind of method of metal recovery in waste lithium iron phosphate battery | |
| CN112310500B (en) | Method for separating aluminum element from waste lithium iron phosphate material | |
| CN113912033A (en) | Method for recycling anode and cathode mixed powder of waste lithium iron phosphate battery with pre-positioned lithium extraction | |
| CN112267023B (en) | Two-stage defluorination method for fluorine-containing material | |
| CN112607789A (en) | Process for recovering valuable metals and regenerating anode materials of waste lithium ion batteries | |
| WO2023155543A1 (en) | Method for recycling electrolyte of lithium-ion battery | |
| CN111048862A (en) | Method for efficiently recovering lithium ion battery anode and cathode materials as supercapacitor electrode materials | |
| CN114277251B (en) | Method for separating and recycling metal in waste lithium battery | |
| CN113415793A (en) | Method for preparing high-purity iron phosphate from lithium iron phosphate battery waste | |
| CN112742843A (en) | Method for recycling waste lithium manganate battery through flotation and solid phase sintering | |
| CN115472948A (en) | Method for regenerating sodium-electricity positive electrode material by using waste lithium manganate | |
| CN112725621B (en) | Method for separating nickel, cobalt and manganese from waste lithium battery based on carbonate solid-phase conversion method | |
| CN110233304B (en) | Method for efficiently recycling mixed lithium ion battery anode material | |
| CN111994966A (en) | Method for recycling waste ternary positive electrode under high-temperature condition of hydrogen sulfide atmosphere | |
| CN115321505B (en) | Method for preparing lithium iron phosphate by comprehensively recycling lithium-containing wastewater and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |