CN115196609A - Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof - Google Patents
Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof Download PDFInfo
- Publication number
- CN115196609A CN115196609A CN202211118349.6A CN202211118349A CN115196609A CN 115196609 A CN115196609 A CN 115196609A CN 202211118349 A CN202211118349 A CN 202211118349A CN 115196609 A CN115196609 A CN 115196609A
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- leaching
- iron
- lithium
- precipitation reaction
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The application discloses a method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof, relating to the technical field of lithium batteries and comprising the following steps: (1) Adding a reducing agent into the mixed slurry of the lithium iron phosphate lithium extraction slag and water to carry out reduction leaching reaction to obtain leaching slag b and leaching solution a containing phosphorus and iron; (2) Adding an oxidant into the leaching solution a for precipitation reaction to obtain iron phosphate slurry; (3) And obtaining a solid-phase material of the iron phosphate slurry, and washing and calcining the solid-phase material to obtain the iron phosphate. The method realizes the comprehensive utilization of the lithium iron phosphate lithium extraction slag to prepare the iron phosphate for the battery, and has the advantages of mild leaching conditions, high leaching rate and precipitation rate of phosphorus and iron and high product purity.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to a method for recovering iron phosphate from lithium iron phosphate extraction slag and application thereof.
Background
Because of low price and good safety, the lithium iron phosphate is widely applied to the field of electric automobiles. With the rapid development of new energy industry in China, the number of scrapped lithium iron phosphate batteries increases year by year. The waste lithium iron phosphate powder contains about 4% of lithium, 31% of iron and 17% of phosphorus, which are important secondary resources, and the resource utilization is needed urgently. The conventional lithium iron phosphate recovery method comprises the steps of firstly carrying out selective lithium extraction through oxidation acid leaching to obtain a lithium-rich leaching solution and a lithium extraction slag, wherein the lithium extraction slag contains about 90% of iron element and phosphorus element, and part of residual carbon and impurity metals, wherein the impurity metals mainly comprise copper, nickel and cobalt.
The existing lithium iron phosphate lithium extraction slag recovery mode mainly dissolves iron phosphate with inorganic acids such as high-concentration sulfuric acid and phosphoric acid, and alkali is added into leachate to adjust pH value so as to precipitate the iron phosphate, but a large amount of acid and alkali can be used for leaching and precipitation, so that the reagent cost is high, the economic benefit is low, the waste salt production amount is large, and strong acid has strong corrosivity on equipment. Meanwhile, the leaching rate of iron and phosphorus elements in the strong acid leaching process is low, so that iron and phosphorus resource waste is large.
In the prior art, phosphorus element and iron element in the lithium extraction slag are leached by high-concentration phosphoric acid, then the ferric phosphate dihydrate is prepared by adding water to dilute and regulate pH, and phosphoric acid is evaporated and recycled, but the evaporation amount is too much due to adding a large amount of water in the precipitation process. In the prior art, iron powder is used and phosphoric acid is supplemented to adjust the iron-phosphorus ratio, so that the leaching of iron phosphate in the lithium extraction slag is realized, but the process can lead the precipitated product to be only about 60 percent from the lithium extraction slag and 40 percent from the added Fe and P.
Iron phosphate is currently mainly prepared by supplementing phosphate and an oxidizing agent to a ferrous sulfate solution, and commonly used phosphate comprises diammonium hydrogen phosphate, phosphoric acid and the like. This method is costly because phosphates are expensive. Therefore, a method for recovering iron phosphate from lithium iron phosphate lithium extraction slag with mild conditions, low reagent cost, high leaching rate and high precipitation rate is urgently needed, iron phosphate prepared from the lithium iron phosphate lithium extraction slag can not only eliminate solid waste, but also create higher economic value, and the obtained iron phosphate can be reused for preparing lithium iron phosphate batteries, so that green recovery and recycling of the waste lithium iron phosphate batteries are realized.
Disclosure of Invention
The application provides a method for recovering iron phosphate from lithium iron phosphate lithium extraction residues and application thereof, which can solve the problems of high reagent cost, large waste salt production amount and strong corrosion of strong acid to equipment caused by using a large amount of acid and alkali in leaching and precipitation reactions in the prior art, and simultaneously, the leaching rate of iron and phosphorus in the strong acid leaching process in the prior art is low, so that the waste of iron and phosphorus resources is large; by introducing a proper reducing agent, on one hand, the strong acid condition of the leaching reaction can be optimized, on the other hand, the leaching of other metal ions can be prevented, the leaching rate of iron and phosphorus elements is improved, and further, the purity of the product iron phosphate is improved; moreover, the method improves the precipitation rate of the hydrated iron phosphate by selecting a proper oxidant and controlling the technological conditions of the precipitation reaction.
In a first aspect, the application provides a method for recovering iron phosphate from lithium iron phosphate extraction slag, which comprises the following steps:
(1) Adding a reducing agent into the mixed slurry of the lithium iron phosphate lithium extraction slag and water to carry out reduction leaching reaction to obtain leaching slag b and leaching solution a containing phosphorus and iron;
(2) Adding an oxidant into the leaching solution a for precipitation reaction to obtain iron phosphate slurry;
(3) And (3) obtaining a solid-phase material (ferric phosphate dihydrate) of the ferric phosphate slurry, and washing and calcining the solid-phase material to obtain the ferric phosphate (anhydrous ferric phosphate).
According to the method, the residual lithium extraction slag obtained after selective lithium extraction from waste lithium iron phosphate through oxidation acid leaching is used as an initial raw material, wherein the lithium extraction slag mainly comprises iron phosphate, a small amount of carbon black and other metal impurities; at the moment, on one hand, the solid wastes can be consumed, and on the other hand, high economic value can be created; adding a reducing agent such as sulfur or sulfide in a proper proportion into the mixed slurry of the lithium extraction slag and water, wherein the sulfide can reduce ferric ions in the lithium extraction slag into ferrous ions under the mild acid leaching condition, and the leaching rate of iron elements and phosphorus elements is higher than that of the strong acid leaching process in the prior art; the sulfide can also inhibit the leaching of other metal ions, such as copper ions, nickel ions and cobalt ions, so that the purity of the calcined anhydrous iron phosphate is higher;
in addition, the leachate a is a ferrous iron solution, the conversion from a ferrous iron ion solution to a ferric iron ion solution can be realized by selecting an appropriate oxidant and an appropriate proportion, and meanwhile, the conditions of the precipitation reaction are controlled to obtain a product iron phosphate with high precipitation rate and appropriate morphology, and the process flow is shown in fig. 1.
In some of these embodiments, the sulfide is selected from at least one of sodium sulfide, potassium sulfide, hydrogen sulfide, or ammonium sulfide. Preferably, the sulfide is selected from at least one of sodium sulfide or ammonium sulfide.
Specifically, in one example, the sulfide is sodium sulfide; in another example, the sulfide is ammonium sulfide; or in other examples, the sulfide includes sodium sulfide and also includes ammonium sulfide.
Sodium sulfide, potassium sulfide, hydrogen sulfide or ammonium sulfide can generate new sulfide with other impurity metal ions (such as copper ions, nickel ions and cobalt ions) in the mixed slurry, so that leaching of other impurity metal ions is inhibited, and the purity of the product ferric sulfate is improved.
In some embodiments, in the step (1), the usage amount of the reducing agent is 1 to 1.5 times of the molar amount of iron in the lithium iron phosphate lithium extraction slag.
Illustratively, the dosage of the reducing agent is 1 time, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times or a range formed by any two of the above values of the molar weight of iron in the lithium iron phosphate lithium extraction slag. At this moment, leach effectually, and can also realize low-cost when guaranteeing to leach the effect, if the quantity of reductant is too little, then can lead to the leaching effect of iron element and phosphorus element not good, if the quantity of reductant is too much, on the one hand, the effect is not obvious on promoting the leaching rate, and on the other hand can the increase cost.
In some of these embodiments, in step (1), the conditions of the reductive leaching reaction are: under the acidic condition that the pH value is 1-1.4, the leaching temperature is controlled to be 40-60 ℃, the leaching time is 1-2h, and the solid-to-liquid ratio is 5-10mL/g. The acidic conditions may be adjusted using acidic reagents conventional in the art, such as sulfuric acid, nitric acid, hydrochloric acid, and the like.
Illustratively, the acidic conditions have a pH of 1, 1.1, 1.2, 1.3, 1.4, or a range consisting of any two of the foregoing values.
Illustratively, the leaching temperature during the reduction leaching reaction is 40 ℃, 43 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 55 ℃, 58 ℃, 60 ℃ or a range consisting of any two of the above values.
Illustratively, the leaching time during the reduction leaching reaction is 1h, 1.1h, 1.2h, 1.4h, 1.5h, 1.6h, 1.8h, 2h, or a range consisting of any two of the above values.
Illustratively, the solid-to-liquid ratio during the reduction leaching reaction is 5mL/g, 6mL/g, 7mL/g, 8mL/g, 9mL/g, 10mL/g, or a range consisting of any two of the foregoing values.
In some of these embodiments, in step (2), the oxidizing agent is selected from at least one of manganese dioxide or sodium chlorate; the dosage of the oxidant is 1 to 2 times of the molar weight of the iron in the leaching solution a.
Specifically, in one example, the oxidizing agent is manganese dioxide; in another example, the oxidizing agent is sodium chlorate; or in other examples, the oxidizing agent comprises manganese dioxide and also comprises sodium chlorate;
illustratively, the dosage of the oxidant is 1 time, 1.1 times, 1.3 times, 1.5 times, 1.6 times, 1.8 times, 2 times or a range composed of any two of the foregoing values of the molar weight of iron in the lithium iron phosphate lithium extraction slag.
Preferably, the oxidant is manganese dioxide, and the dosage of the oxidant is 1 to 2 times of the molar weight of iron in the lithium iron phosphate lithium extraction slag.
In some embodiments, in step (2), the precipitation reaction comprises a first-stage precipitation reaction and a second-stage precipitation reaction;
the conditions of the first stage precipitation reaction are as follows: preserving the heat for 50 to 70min at the temperature of 50 to 70 ℃;
the conditions for the second stage precipitation reaction are therefore: keeping the temperature for 130 to 150min under the condition of 90 to 105 ℃;
the heating rate of the first-stage precipitation reaction and/or the second-stage precipitation reaction is 6 to 8 ℃/min. The low-temperature environment of the first-stage precipitation reaction is used for obtaining a proper iron phosphate seed crystal, and the iron phosphate seed crystal generated at a low temperature can generate a large amount of ferric phosphate dihydrate in the high-temperature environment (90-105 ℃) of the second-stage precipitation reaction; moreover, by adding a proper oxidizing agent and the synergistic cooperation of the first-stage precipitation reaction and the second-stage precipitation reaction, the method is favorable for the generation of a large amount of compact ferric phosphate dihydrate with uniform appearance.
The first-stage precipitation reaction is a formation stage of iron phosphate crystal seeds, namely adding an oxidant into leachate a containing phosphorus elements and iron elements, fully stirring, slowly heating the solution to a proper temperature (50 to 70 ℃), and keeping the temperature for a certain time (50 to 70min) after precipitation is formed so as to generate proper iron phosphate crystal seeds, and then carrying out second-stage precipitation reaction, namely continuously heating to a preset temperature (90 to 105 ℃) and keeping the temperature for a certain time (130 to 150min) so as to obtain iron phosphate slurry, wherein the iron phosphate in the iron phosphate slurry is ferric phosphate dihydrate; and regulating and controlling the heat preservation temperature and the heat preservation time of the second-stage precipitation reaction, and being beneficial to improving the precipitation rate of the ferric phosphate dihydrate.
When the oxidizing agent is manganese dioxide, the first-stage precipitation reaction is completed, and then the first-stage precipitation reaction is filtered to remove the manganese dioxide remaining in the reaction, and then the second-stage precipitation reaction is carried out, wherein the temperature is raised and maintained. The remaining manganese dioxide cannot be dissolved continuously, and the manganese dioxide which cannot be dissolved can be mixed into the iron phosphate slurry, so that the solid-phase material of the obtained iron phosphate slurry is impure.
In a second aspect, the present application provides iron phosphate prepared by any one of the methods described above.
In a third aspect, the present application provides the iron phosphate prepared by any one of the methods described above and/or an application of the iron phosphate described above in the field of lithium iron phosphate batteries.
The beneficial effects brought by the technical scheme provided by some embodiments of the application at least comprise:
the method realizes the comprehensive utilization of the lithium iron phosphate lithium extraction slag to prepare the iron phosphate for the battery, and has the advantages of mild leaching conditions, high leaching rate and precipitation rate of phosphorus and iron elements, and high product purity; in addition, a proper reducing agent is introduced in the leaching process, so that the leaching rate of the phosphorus element and the iron element is improved, the leaching of other impurity metals in the lithium iron phosphate lithium extraction slag is inhibited, the purity of the precipitated ferric phosphate dihydrate is high, and the purity of the product ferric phosphate is high; in addition, a large amount of alkali is not needed for neutralization in the precipitation process, a proper oxidant is selected, and the technological conditions of the precipitation reaction are controlled, so that the precipitation rate of the ferric phosphate dihydrate is improved, and the method has the advantages of low cost and good economy.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic diagram of a principle process flow of preparing iron phosphate from lithium iron phosphate lithium extraction slag according to the present application;
fig. 2 is an XRD pattern of the iron phosphate prepared in example 1 of the present application;
FIG. 3 is a scanning electron micrograph of iron phosphate prepared according to example 1 of the present application;
FIG. 4 is a scanning electron micrograph of iron phosphate obtained in comparative example 6 of the present application without performing a low temperature incubation period.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
The present application is further illustrated by the following examples.
Example 1
Step 1: adding 1kg of blocky lithium iron phosphate lithium extraction slag into water, wherein the liquid-solid ratio is 8mL/g, fully stirring to disperse the blocky lithium iron phosphate lithium extraction slag, and then adding sulfuric acid and sodium sulfide, wherein the using amount of the sodium sulfide is 1.2 times of the molar amount of iron in the lithium iron phosphate lithium extraction slag; reacting for 1h at 50 ℃, and supplementing sulfuric acid to adjust the pH value to 1.1; then filtering the slurry for solid-liquid separation to obtain leaching residues and leaching solution containing phosphorus and iron; leaching rate of reduction leaching reaction: 98.7 percent of Fe element and 98.5 percent of P element.
Step 2: heating the leachate obtained in the step 1 to 60 ℃ at a heating rate of 7 ℃/min, adding manganese dioxide, fully stirring, preserving heat for 60min, and filtering to obtain a ferric phosphate-containing solution, wherein the use amount of manganese dioxide is 1.5 times of the molar weight of iron in the leachate; heating the ferric phosphate-containing solution to 100 ℃ at a heating rate of 7 ℃/min, and then preserving heat for 140min to obtain ferric phosphate slurry; precipitation rate of the precipitation reaction: 95.7 percent of Fe element and 94.8 percent of P element.
And step 3: filtering the iron phosphate slurry obtained in the step (2) to obtain a ferric phosphate dihydrate solid product; washing the obtained ferric phosphate dihydrate solid with deionized water, and calcining for 1h at 500 ℃ to obtain an anhydrous ferric phosphate product.
The anhydrous ferric phosphate product contains 0.003 percent of Cu, 0.004 percent of Ni, 0.005 percent of Co and 0.0002 percent of Zn. Fig. 2 is an XRD characterization diagram of the anhydrous iron phosphate product, and fig. 3 is an SEM scanning electron microscope diagram of the anhydrous iron phosphate product, which shows that the anhydrous iron phosphate prepared in this example is a smooth and compact spheroidal structure with uniform particle size.
Example 2
Step 1: adding 1kg of blocky lithium iron phosphate lithium extraction residues into water, wherein the liquid-solid ratio is 8mL/g, fully stirring to disperse the blocky lithium iron phosphate lithium extraction residues, and then adding sulfuric acid and ammonium sulfide, wherein the using amount of the ammonium sulfide is 1.1 times of the molar amount of iron in the lithium iron phosphate lithium extraction residues; reacting for 1h at 50 ℃, and supplementing sulfuric acid to adjust the pH value to 1.2; then filtering the slurry for solid-liquid separation to obtain leaching residues and leaching solution containing phosphorus and iron elements; leaching rate of reduction leaching reaction: 99.5 percent of Fe element and 98.7 percent of P element.
And 2, step: heating the leachate obtained in the step 1 to 60 ℃ at a heating rate of 7 ℃/min, adding manganese dioxide, fully stirring, preserving heat for 60min, and filtering to obtain a ferric phosphate-containing solution, wherein the use amount of manganese dioxide is 1.6 times of the molar weight of iron in the leachate; heating the ferric phosphate-containing solution to 95 ℃ at a heating rate of 7 ℃/min, and then preserving heat for 140min to obtain ferric phosphate slurry; precipitation rate of precipitation reaction: 96.8 percent of Fe element and 95.6 percent of P element.
And step 3: filtering the iron phosphate slurry obtained in the step (2) to obtain a ferric phosphate dihydrate solid product; washing the obtained ferric phosphate dihydrate solid with deionized water, and calcining for 1h at 500 ℃ to obtain an anhydrous ferric phosphate product.
The anhydrous ferric phosphate product contains 0.004 percent of Cu, 0.002 percent of Ni, 0.003 percent of Co and 0.0003 percent of Zn.
Example 3
Step 1: adding 1kg of blocky lithium iron phosphate lithium extraction residues into water, wherein the liquid-solid ratio is 8mL/g, fully stirring to disperse the blocky lithium iron phosphate lithium extraction residues, and then adding sulfuric acid and potassium sulfide, wherein the dosage of the potassium sulfide is 1.2 times of the molar weight of iron in the lithium iron phosphate lithium extraction residues; reacting for 1h at 60 ℃, and supplementing sulfuric acid to adjust the pH value to 1.3; then filtering the slurry for solid-liquid separation to obtain leaching residues and leaching solution containing phosphorus and iron elements; leaching rate of reduction leaching reaction: 97.5 percent of Fe element and 97.7 percent of P element.
And 2, step: heating the leachate obtained in the step 1 to 60 ℃ at a heating rate of 7 ℃/min, adding sodium chlorate, fully stirring, and keeping the temperature for 60min, wherein the using amount of the sodium chlorate is 1 time of the molar amount of iron in the leachate; heating the ferric phosphate-containing solution to 95 ℃ at a heating rate of 7 ℃/min, and then preserving heat for 140min to obtain ferric phosphate slurry; precipitation rate of precipitation reaction: 96.8 percent of Fe element and 95.6 percent of P element.
And 3, step 3: filtering the iron phosphate slurry obtained in the step (2) to obtain a ferric phosphate dihydrate solid product; washing the obtained ferric phosphate dihydrate solid with deionized water, and calcining for 1h at 500 ℃ to obtain an anhydrous ferric phosphate product.
The anhydrous ferric phosphate product contains 0.002% of Cu, 0.005% of Ni, 0.002% of Co and 0.0001% of Zn.
Example 4
Step 1: adding 1kg of blocky lithium iron phosphate lithium extraction slag into water, wherein the liquid-solid ratio is 8mL/g, fully stirring to disperse the blocky lithium iron phosphate lithium extraction slag, and then adding sulfuric acid and sulfur, wherein the dosage of the sulfur is 1 time of the molar weight of iron in the lithium iron phosphate lithium extraction slag; reacting for 1h at 60 ℃, and supplementing sulfuric acid to adjust the pH value to 1.1; then filtering the slurry for solid-liquid separation to obtain leaching residues and leaching solution containing phosphorus and iron elements; leaching rate of reduction leaching reaction: 98.3 percent of Fe element and 98.1 percent of P element.
Step 2: heating the leachate obtained in the step 1 to 60 ℃ at a heating rate of 7 ℃/min, adding manganese dioxide, fully stirring, preserving heat for 60min, and filtering to obtain a ferric phosphate-containing solution, wherein the use amount of manganese dioxide is 1 time of the molar weight of iron in the leachate; heating the ferric phosphate-containing solution to 95 ℃ at a heating rate of 7 ℃/min, and then preserving heat for 140min to obtain ferric phosphate slurry; precipitation rate of precipitation reaction: 96.8 percent of Fe element and 95.6 percent of P element.
And 3, step 3: filtering the iron phosphate slurry obtained in the step (2) to obtain a dihydrate ferric phosphate solid product; washing the obtained ferric phosphate dihydrate solid with deionized water, and calcining at 500 ℃ for 1h to obtain an anhydrous ferric phosphate product.
The content of Cu in the anhydrous ferric phosphate product is 0.003 percent, the content of Ni is 0.007 percent, the content of Co is 0.005 percent, and the content of Zn is 0.002 percent.
Comparative example 1
Step 1: adding 1kg of blocky lithium iron phosphate lithium extraction slag into water, fully stirring the blocky lithium iron phosphate lithium extraction slag to disperse the blocky lithium iron phosphate lithium extraction slag at a liquid-solid ratio of 8mL/g, reacting the mixture for 1 hour at 60 ℃, and supplementing sulfuric acid to adjust the pH value to 1.1; then filtering the slurry for solid-liquid separation to obtain leaching residues and leaching solution containing phosphorus and iron; leaching rate of reduction leaching reaction: 46.5 percent of Fe element and 45.9 percent of P element. In this case, the leaching rates of iron and phosphorus are greatly reduced because the reducing agent is not added.
Step 2: heating the leachate obtained in the step 1 to 60 ℃ at a heating rate of 7 ℃/min, adding sodium chlorate, fully stirring, and keeping the temperature for 60min, wherein the use amount of the sodium chlorate is 1 time of the molar amount of iron in the leachate; heating the ferric phosphate-containing solution to 95 ℃ at a heating rate of 7 ℃/min, and then preserving heat for 140min to obtain ferric phosphate slurry; precipitation rate of the precipitation reaction: 95.7 percent of Fe element and 94.8 percent of P element.
And step 3: filtering the iron phosphate slurry obtained in the step (2) to obtain a ferric phosphate dihydrate solid product; washing the obtained ferric phosphate dihydrate solid with deionized water, and calcining for 1h at 500 ℃ to obtain an anhydrous ferric phosphate product.
The anhydrous iron phosphate product contains 0.01% of Cu, 0.015% of Ni, 0.012% of Co and 0.01% of Zn.
Compared with the embodiment 1, the comparative example 1 has no reducing agent, and the reducing leaching reaction is only carried out under the acidic condition of pH 1.1, on one hand, the sulfide reducing agent can promote the conversion of ferric ions to ferrous ions, so that the reducing leaching reaction is facilitated, and on the other hand, the sulfide reducing agent can also inhibit the leaching of other impurity metal ions; in comparative example 1, since the sulfide reducing agent was not added in an acidic environment, the leaching rate was low, and was only 46.5% of Fe element and 45.9% of P element, which were lower than 98.7% of Fe element and 98.5% of P element in example 1, and was about 50% lower. Moreover, the anhydrous iron phosphate product of comparative example 1 had significantly higher levels of impurities than example 1.
Comparative example 2
Step 1: adding 1kg of blocky lithium iron phosphate lithium extraction residues into water, wherein the liquid-solid ratio is 8mL/g, fully stirring to disperse the blocky lithium iron phosphate lithium extraction residues, and then adding sulfuric acid and sodium sulfide, wherein the using amount of the sodium sulfide is 1.2 times of the molar amount of iron in the lithium iron phosphate lithium extraction residues; reacting for 1h at 50 ℃, and supplementing sulfuric acid to adjust the pH value to 1.1; then filtering the slurry for solid-liquid separation to obtain leaching residues and leaching solution containing phosphorus and iron; leaching rate of reduction leaching reaction: 98.7 percent of Fe element and 97.9 percent of P element.
Step 2: heating the leachate obtained in the step 1 to 60 ℃ at a heating rate of 7 ℃/min, and keeping the temperature for 60min to obtain a ferric phosphate-containing solution; heating the ferric phosphate-containing solution to 95 ℃ at a heating rate of 7 ℃/min, and then preserving heat for 140min to obtain ferric phosphate slurry; precipitation rate of the precipitation reaction: 43.8 percent of Fe element and 41.5 percent of P element. Because manganese dioxide and/or sodium chlorate are not added as oxidants in the precipitation process, the precipitation rate of iron elements and phosphorus elements is greatly reduced.
And 3, step 3: filtering the iron phosphate slurry obtained in the step (2) to obtain a ferric phosphate dihydrate solid product; washing the obtained ferric phosphate dihydrate solid with deionized water, and calcining at 500 ℃ for 1h to obtain an anhydrous ferric phosphate product.
The content of Cu in the anhydrous ferric phosphate product is 0.002%, the content of Ni is 0.005%, the content of Co is 0.004%, and the content of Zn is 0.003%.
Comparative example 3
Step 1: adding 1kg of blocky lithium iron phosphate lithium extraction slag into water, wherein the liquid-solid ratio is 8mL/g, fully stirring to disperse the blocky lithium iron phosphate lithium extraction slag, and then adding sulfuric acid and sodium sulfide, wherein the using amount of the sodium sulfide is 0.5 times of the molar amount of iron in the lithium iron phosphate lithium extraction slag; reacting for 1h at 50 ℃, and supplementing sulfuric acid to adjust the pH value to 1.1; and then filtering the slurry for solid-liquid separation to obtain leaching residues and leaching solution containing phosphorus and iron. Leaching rate of reduction leaching reaction: 78.3 percent of Fe element and 79.1 percent of P element; the dosage of the reducing agent sodium sulfide is only 0.5 times of the molar weight of the iron, so that the leaching rate of the iron element and the phosphorus element is obviously reduced, and the dosage of the reducing agent is in a proper range, thereby being beneficial to leaching of the iron element and the phosphorus element.
Step 2: heating the leachate obtained in the step 1 to 60 ℃ at a heating rate of 7 ℃/min, adding manganese dioxide, fully stirring, preserving heat for 60min, and filtering to obtain a ferric phosphate solution, wherein the use amount of manganese dioxide is 1.5 times of the molar weight of iron in the solution; heating the ferric phosphate-containing solution to 95 ℃ at a heating rate of 7 ℃/min, and then preserving heat for 140min to obtain ferric phosphate slurry; precipitation rate of precipitation reaction: 95.3 percent of Fe element and 95.8 percent of P element.
And 3, step 3: filtering the iron phosphate slurry obtained in the step (2) to obtain a dihydrate ferric phosphate solid product; washing the obtained ferric phosphate dihydrate solid with deionized water, and calcining at 500 ℃ for 1h to obtain an anhydrous ferric phosphate product.
The content of Cu in the anhydrous iron phosphate product is 0.006%, the content of Ni is 0.007%, the content of Co is 0.006%, and the content of Zn is 0.004%. Since the addition amount of sodium sulfide is too small, it cannot completely inhibit leaching of other metal ions, resulting in an increase in the content of impurities in the product.
Comparative example 4
Step 1: adding 1kg of blocky lithium iron phosphate lithium extraction slag into water, wherein the liquid-solid ratio is 8mL/g, fully stirring to disperse the blocky lithium iron phosphate lithium extraction slag, and then adding sulfuric acid and sodium sulfide, wherein the dosage of the sodium sulfide is 1.2 times of the molar weight of iron in the lithium iron phosphate lithium extraction slag. Reacting for 1h at 50 ℃, and supplementing sulfuric acid to adjust the pH value to 1.1; then filtering the slurry for solid-liquid separation to obtain leaching residues and leaching solution containing phosphorus and iron; leaching rate of reduction leaching reaction: 98.5 percent of Fe element and 98.3 percent of P element.
Step 2: heating the leachate obtained in the step 1 to 60 ℃ at a heating rate of 7 ℃/min, adding manganese dioxide, fully stirring, keeping the temperature for 60min, and filtering to obtain a ferric phosphate-containing solution, wherein the dosage of manganese dioxide is 0.5 time of the molar weight of iron in the solution; heating the ferric phosphate-containing solution to 95 ℃ at a heating rate of 7 ℃/min, and then preserving heat for 140min to obtain ferric phosphate slurry; precipitation rate of the precipitation reaction: 79.3 percent of Fe element and 80.2 percent of P element. Because the dosage of the manganese dioxide used as the oxidant is only 0.5 times of the molar quantity of the iron, the precipitation rate of the iron element and the phosphorus element in the precipitation process is obviously reduced.
And step 3: filtering the iron phosphate slurry obtained in the step (2) to obtain a ferric phosphate dihydrate solid product; washing the obtained ferric phosphate dihydrate solid with deionized water, and calcining at 500 ℃ for 1h to obtain an anhydrous ferric phosphate product.
The content of Cu in the anhydrous ferric phosphate product is 0.003 percent, the content of Ni is 0.002 percent, the content of Co is 0.002 percent, and the content of Zn is 0.003 percent.
Comparative example 5
Step 1: adding 1kg of blocky lithium iron phosphate lithium extraction slag into water, wherein the liquid-solid ratio is 8mL/g, fully stirring to disperse the blocky lithium iron phosphate lithium extraction slag, and then adding sulfuric acid and sodium sulfide, wherein the using amount of the sodium sulfide is 1.2 times of the molar amount of iron in the lithium iron phosphate lithium extraction slag; reacting for 1h at 50 ℃, and supplementing sulfuric acid to adjust the pH value to 1.1; then filtering the slurry for solid-liquid separation to obtain leaching residues and leaching solution containing phosphorus and iron; leaching rate of reduction leaching reaction: 98.6 percent of Fe element and 98.2 percent of P element.
Step 2: heating the leachate obtained in the step 1 to 60 ℃ at a heating rate of 7 ℃/min, adding sodium chlorate, fully stirring, keeping the temperature for 140min, and filtering, wherein the using amount of the sodium chlorate is 1 time of the molar amount of iron in the leachate, so as to obtain iron phosphate slurry; precipitation rate of precipitation reaction: 68.4 percent of Fe element and 67.5 percent of P element. Because the temperature is not continuously raised after the heat preservation, the precipitation rate of the iron element and the phosphorus element is greatly reduced.
And step 3: filtering the iron phosphate slurry obtained in the step (2) to obtain a dihydrate ferric phosphate solid product; washing the obtained ferric phosphate dihydrate solid with deionized water, and calcining at 500 ℃ for 1h to obtain an anhydrous ferric phosphate product.
The content of Cu in the anhydrous iron phosphate product is 0.003 percent, the content of Ni is 0.005 percent, the content of Co is 0.004 percent, and the content of Zn is 0.003 percent.
Comparative example 6
Step 1: adding 1kg of blocky lithium iron phosphate lithium extraction slag into water, wherein the liquid-solid ratio is 8mL/g, fully stirring to disperse the blocky lithium iron phosphate lithium extraction slag, and then adding sulfuric acid and sodium sulfide, wherein the using amount of the sodium sulfide is 1.2 times of the molar amount of iron in the lithium iron phosphate lithium extraction slag; reacting for 1h at 50 ℃, and supplementing sulfuric acid to adjust the pH value to 1.1; then filtering the slurry for solid-liquid separation to obtain leaching residues and leaching solution containing phosphorus and iron elements; leaching rate of reduction leaching reaction: 98.3 percent of Fe element and 97.9 percent of P element.
Step 2: heating the leachate obtained in the step 1 to 95 ℃ at a heating rate of 7 ℃/min, adding sodium chlorate, fully stirring, preserving heat for 140min, and filtering, wherein the use amount of the sodium chlorate is 1 time of the molar amount of iron in the leachate, so as to obtain iron phosphate slurry; precipitation rate of precipitation reaction: 94.6 percent of Fe element and 94.7 percent of P element. However, the shape of the product is changed due to the fact that a heat preservation (iron phosphate crystal seed formation) stage at a low temperature is not performed, and the product is of an irregular porous structure (as shown in fig. 4), and the electrochemical performance of a lithium iron phosphate battery prepared subsequently is greatly reduced due to the iron phosphate product.
And 3, step 3: filtering the iron phosphate slurry obtained in the step (2) to obtain a ferric phosphate dihydrate solid product; washing the obtained ferric phosphate dihydrate solid with deionized water, and calcining for 1h at 500 ℃ to obtain an anhydrous ferric phosphate product.
The content of Cu in the anhydrous iron phosphate product is 0.003 percent, the content of Ni is 0.004 percent, the content of Co is 0.003 percent, and the content of Zn is 0.003 percent.
The test method comprises the following steps:
1) Molar iron test
And testing the mass of iron in the lithium extraction slag or the leaching solution by using an inductively coupled plasma emission spectrometer, wherein the molar weight of the iron is the mass obtained by the test divided by the relative atomic mass of the iron.
2) Leaching Rate test
The leaching rate of the iron element and the phosphorus element in the lithium iron phosphate lithium extraction slag leaching process refers to the ratio percentage of the difference value of the content of the iron element and the phosphorus element in the lithium extraction slag and the content of the iron element and the phosphorus element in the leaching slag to the content of the iron element and the phosphorus element in the lithium extraction slag.
3) Precipitation rate test
The precipitation rate of the iron element and the phosphorus element in the iron phosphate precipitation process refers to the ratio percentage of the difference between the content of the iron element and the phosphorus element in the liquid before precipitation and the content of the iron element and the phosphorus element in the liquid after precipitation to the content of the iron element and the phosphorus element in the liquid before precipitation.
4) Measurement of impurity content
And testing the quality of impurities in the anhydrous iron phosphate product by using an inductively coupled plasma emission spectrometer, wherein the content of the impurities is the quality of the impurities obtained by testing divided by the total quality of the anhydrous iron phosphate product.
The above description is only a preferred embodiment of the present application and should not be taken as limiting the present application, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (9)
1. A method for recovering iron phosphate from lithium iron phosphate lithium extraction slag is characterized by comprising the following steps:
(1) Adding a reducing agent into the mixed slurry of the lithium iron phosphate lithium extraction slag and water to carry out reduction leaching reaction to obtain leaching slag b and leaching solution a containing phosphorus and iron; the reducing agent comprises sulfide or sulfur;
(2) Adding an oxidant into the leaching solution a for precipitation reaction to obtain iron phosphate slurry;
(3) And obtaining a solid-phase material of the iron phosphate slurry, and washing and calcining the solid-phase material to obtain the iron phosphate.
2. The method according to claim 1, wherein in step (1), the sulfide is selected from at least one of sodium sulfide, potassium sulfide, hydrogen sulfide, or ammonium sulfide.
3. The method according to claim 1, wherein in the step (1), the dosage of the reducing agent is 1 to 1.5 times of the molar quantity of iron in the lithium iron phosphate lithium extraction slag.
4. The method according to claim 1, wherein in step (1), the conditions of the reductive leaching reaction are as follows: under the acidic condition that the pH value is 1-1.4, the leaching temperature is controlled to be 40-60 ℃, the leaching time is 1-2h, and the solid-to-liquid ratio is 5-10mL/g.
5. The method according to claim 1, wherein in step (2), the oxidizing agent is selected from at least one of manganese dioxide or sodium chlorate;
the dosage of the oxidant is 1 to 2 times of the molar weight of the iron in the leaching solution a.
6. The method according to claim 5, wherein in the step (2), the precipitation reaction comprises a first-stage precipitation reaction and a second-stage precipitation reaction;
the conditions of the first stage precipitation reaction are as follows: preserving the heat for 50 to 70min at the temperature of 50 to 70 ℃;
the conditions for the second stage precipitation reaction are therefore: keeping the temperature for 130 to 150min under the condition of 90 to 105 ℃;
the temperature rise rate of the first-stage precipitation reaction and/or the second-stage precipitation reaction is 6 to 8 ℃/min.
7. The method of claim 6, wherein when the oxidizing agent comprises manganese dioxide, a filtration process is further included between the first stage precipitation reaction and the second stage precipitation reaction.
8. Iron phosphate produced by the method according to any one of claims 1 to 7.
9. The iron phosphate prepared by the method according to any one of claims 1 to 7 and/or the iron phosphate according to claim 8, for use in the field of lithium iron phosphate batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211118349.6A CN115196609B (en) | 2022-09-15 | 2022-09-15 | Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211118349.6A CN115196609B (en) | 2022-09-15 | 2022-09-15 | Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115196609A true CN115196609A (en) | 2022-10-18 |
| CN115196609B CN115196609B (en) | 2023-01-13 |
Family
ID=83572813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211118349.6A Active CN115196609B (en) | 2022-09-15 | 2022-09-15 | Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115196609B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115626624A (en) * | 2022-10-26 | 2023-01-20 | 衢州华友钴新材料有限公司 | Method for preparing battery-grade lithium iron phosphate from waste lithium iron phosphate powder |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015183292A (en) * | 2014-03-26 | 2015-10-22 | 三菱マテリアル株式会社 | Recovery method of cobalt and nickel |
| CN106910889A (en) * | 2017-02-27 | 2017-06-30 | 中南大学 | A kind of method that positive active material is regenerated from waste lithium iron phosphate battery |
| CN109231181A (en) * | 2018-11-26 | 2019-01-18 | 广东佳纳能源科技有限公司 | Processing method, ternary precursor, battery-grade iron phosphate and the lithium ion battery of iron vitriol dreg of yellow sodium |
| CN111009660A (en) * | 2019-11-26 | 2020-04-14 | 宁夏百川新材料有限公司 | Method for preparing lithium iron phosphate positive electrode material from waste lithium iron phosphate battery |
| CN111924817A (en) * | 2020-07-24 | 2020-11-13 | 中南大学 | Method for comprehensively utilizing waste lithium iron phosphate anode material |
| CN111977627A (en) * | 2020-09-04 | 2020-11-24 | 中南大学 | Method for recycling lithium iron phosphate anode material of lithium ion battery |
| CN113023701A (en) * | 2021-02-26 | 2021-06-25 | 广东邦普循环科技有限公司 | Method for separating ferronickel from laterite-nickel ore leaching solution and preparing ferric phosphate and application |
| CN113285135A (en) * | 2021-05-07 | 2021-08-20 | 宁夏百川新材料有限公司 | Method for recycling multiple components of waste lithium iron phosphate battery |
| CN113772649A (en) * | 2021-10-26 | 2021-12-10 | 中南大学 | Method for preparing battery-grade iron phosphate by recycling waste lithium iron phosphate positive electrode powder |
| CN113845100A (en) * | 2021-11-16 | 2021-12-28 | 湖北融通高科先进材料有限公司 | Iron phosphate and preparation method and application thereof |
| WO2022050248A1 (en) * | 2020-09-03 | 2022-03-10 | 三菱マテリアル株式会社 | Method for separating cobalt and nickel |
| CN114655969A (en) * | 2022-03-28 | 2022-06-24 | 北京科技大学 | Method for preparing lithium carbonate and iron phosphate by recycling high-impurity lithium iron phosphate positive electrode waste |
| CN115043383A (en) * | 2022-08-16 | 2022-09-13 | 矿冶科技集团有限公司 | High-tap-density battery-grade iron phosphate and preparation method thereof |
-
2022
- 2022-09-15 CN CN202211118349.6A patent/CN115196609B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015183292A (en) * | 2014-03-26 | 2015-10-22 | 三菱マテリアル株式会社 | Recovery method of cobalt and nickel |
| CN106910889A (en) * | 2017-02-27 | 2017-06-30 | 中南大学 | A kind of method that positive active material is regenerated from waste lithium iron phosphate battery |
| CN109231181A (en) * | 2018-11-26 | 2019-01-18 | 广东佳纳能源科技有限公司 | Processing method, ternary precursor, battery-grade iron phosphate and the lithium ion battery of iron vitriol dreg of yellow sodium |
| CN111009660A (en) * | 2019-11-26 | 2020-04-14 | 宁夏百川新材料有限公司 | Method for preparing lithium iron phosphate positive electrode material from waste lithium iron phosphate battery |
| CN111924817A (en) * | 2020-07-24 | 2020-11-13 | 中南大学 | Method for comprehensively utilizing waste lithium iron phosphate anode material |
| WO2022050248A1 (en) * | 2020-09-03 | 2022-03-10 | 三菱マテリアル株式会社 | Method for separating cobalt and nickel |
| CN111977627A (en) * | 2020-09-04 | 2020-11-24 | 中南大学 | Method for recycling lithium iron phosphate anode material of lithium ion battery |
| CN113023701A (en) * | 2021-02-26 | 2021-06-25 | 广东邦普循环科技有限公司 | Method for separating ferronickel from laterite-nickel ore leaching solution and preparing ferric phosphate and application |
| CN113285135A (en) * | 2021-05-07 | 2021-08-20 | 宁夏百川新材料有限公司 | Method for recycling multiple components of waste lithium iron phosphate battery |
| CN113772649A (en) * | 2021-10-26 | 2021-12-10 | 中南大学 | Method for preparing battery-grade iron phosphate by recycling waste lithium iron phosphate positive electrode powder |
| CN113845100A (en) * | 2021-11-16 | 2021-12-28 | 湖北融通高科先进材料有限公司 | Iron phosphate and preparation method and application thereof |
| CN114655969A (en) * | 2022-03-28 | 2022-06-24 | 北京科技大学 | Method for preparing lithium carbonate and iron phosphate by recycling high-impurity lithium iron phosphate positive electrode waste |
| CN115043383A (en) * | 2022-08-16 | 2022-09-13 | 矿冶科技集团有限公司 | High-tap-density battery-grade iron phosphate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 唐小林等: "废旧磷酸亚铁锂正极材料湿法回收研究进展", 《有色金属(冶炼部分)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115626624A (en) * | 2022-10-26 | 2023-01-20 | 衢州华友钴新材料有限公司 | Method for preparing battery-grade lithium iron phosphate from waste lithium iron phosphate powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115196609B (en) | 2023-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113044821B (en) | Method for recycling nickel-iron alloy and application | |
| CN111675203B (en) | Method for recovering lithium from waste lithium iron phosphate batteries and method for recovering lithium and iron phosphate | |
| CN108550939B (en) | A method of selective recovery lithium and lithium carbonate is prepared from waste lithium cell | |
| CN113443640B (en) | Method for preparing battery-grade lithium carbonate and battery-grade iron phosphate by using waste positive and negative electrode powder of lithium iron phosphate battery | |
| CA3184994A1 (en) | Process for recycling cobalt & nickel from lithium-ion batteries | |
| CN111254294B (en) | Method for selectively extracting lithium from waste lithium ion battery powder and recovering manganese dioxide through electrolytic separation | |
| CN113277489A (en) | Method for preparing high-purity iron phosphate by using ferrophosphorus waste | |
| CN109179359A (en) | A method of extracting lithium and ferric phosphate from LiFePO4 waste material | |
| CN113896211A (en) | Resource treatment method for waste lithium iron phosphate batteries | |
| CN112159897B (en) | Method for purifying nickel-cobalt-manganese leaching solution | |
| CN115109936B (en) | Method for recovering valuable metals from waste batteries | |
| CN115196609B (en) | Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof | |
| CN113430370B (en) | Method for selectively extracting cobalt and nickel from nickel sulfide concentrate | |
| CN112342383B (en) | Method for separating and recovering nickel, cobalt, manganese and lithium in ternary waste | |
| CN115709979B (en) | Method for preparing battery-grade manganese iron phosphate by taking high-iron manganese ore as raw material | |
| CN114560767B (en) | Method for preparing ferrous oxalate by siderite | |
| CN115784188A (en) | Method for recycling and preparing battery-grade iron phosphate | |
| CN113151680B (en) | Method for recycling waste lithium batteries | |
| CN115799696A (en) | Method for pretreating waste electrolyte after disassembling lithium ion battery and method for fully recovering lithium, fluorine and phosphorus in waste electrolyte | |
| CN115947323A (en) | Method for extracting lithium from waste lithium iron phosphate and preparing iron phosphate | |
| CN115074540A (en) | Comprehensive recovery method for valuable components of waste power battery | |
| CN114988381A (en) | Method for preparing iron phosphate by using waste lithium iron phosphate battery | |
| Yan et al. | A closed-loop process for high-value regeneration of spent LiFePO 4 cathodes after selective aluminium precipitation | |
| CN115676789B (en) | Preparation method for producing battery-grade ferric phosphate by adopting iron-based nickel-containing alloy | |
| WO2024021237A1 (en) | Recovery method for lithium iron phosphate |
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 |