CN112331949B - Method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries - Google Patents
Method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries Download PDFInfo
- Publication number
- CN112331949B CN112331949B CN202011259874.0A CN202011259874A CN112331949B CN 112331949 B CN112331949 B CN 112331949B CN 202011259874 A CN202011259874 A CN 202011259874A CN 112331949 B CN112331949 B CN 112331949B
- Authority
- CN
- China
- Prior art keywords
- lithium
- iron phosphate
- iron
- waste
- phosphate
- 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.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries, which comprises the following steps: soaking the waste ferric phosphate positive plate by using an organic solvent to obtain ferric phosphate lithium powder; soaking lithium iron phosphate powder into alkali liquor to obtain the aluminum-removed lithium iron phosphate powder; adding the aluminum-removed lithium iron phosphate powder into a mixed solution of sulfuric acid and hydrogen peroxide, and heating and leaching to obtain an acid leaching solution; adjusting the pH value of the pickle liquor to obtain crude iron phosphate; dissolving, precipitating and calcining the rough ferric phosphate to obtain battery-grade ferric phosphate; and (3) evaporating and concentrating the lithium-containing filtrate, and then adding an alkali solution to obtain a lithium carbonate precipitate, thereby obtaining the battery-grade lithium carbonate. The method has short process flow and simple reaction system; the method can fully utilize phosphorus, iron and lithium elements in the waste lithium iron phosphate to prepare the battery-grade iron phosphate and lithium carbonate products with high added values, does not generate iron-containing waste residues and phosphorus-containing wastewater, has high resource recovery rate and high product value, and is easy to realize industrial production.
Description
Technical Field
The invention relates to the technical field of lithium ion battery recovery, in particular to a method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries.
Background
In recent years, with the rapid development of the new energy automobile industry, the loading capacity of lithium ion power batteries is also increased dramatically year by year. The lithium iron phosphate power battery has excellent safety, stability and cyclicity, and is low in price, so that the lithium iron phosphate power battery is highly popular in the industries of electric automobiles, energy storage power stations and the like. The service life of the new energy automobile power battery is 5-8 years, and the new energy automobile power battery popularized earliest is about to meet 'retirement tide'. After the power battery is retired, a plurality of problems can be caused by improper disposal, on one hand, heavy metals and organic matters are contained in the retired power battery, and if the retired power battery is improperly disposed, environmental influence and potential safety hazard can be caused to the society; on the other hand, precious valuable resources are wasted, the retired power battery has obvious resource characteristics, and obvious economic benefits and environmental protection values are achieved for efficient recycling of the retired power battery.
At present, two major types of recovery methods for waste lithium iron phosphate batteries are mainly used, one is to regenerate lithium iron phosphate by using a solid phase method, and the other is to recover precious metal lithium, for example, patent document with publication number CN 104362408A discloses a recovery and reuse method for lithium iron phosphate waste. Due to the limitation of the powder source and the preparation process, the repaired and regenerated lithium iron phosphate cathode material is easily polluted by the outside, has low purity and poor electrochemical performance stability, and cannot meet the requirements of the current market on battery materials. Chinese patent publication No. CN 103280610 a discloses a method for recovering a positive plate of a lithium iron phosphate battery, in which the positive plate of the lithium iron phosphate battery is first dissolved with alkali, filtered, and the filter residue is dissolved with mixed acid, so that iron exists in the form of iron phosphate precipitate and reacts with impurities such as carbon black and lithium-containing solution, and the lithium-containing solution can be added with saturated sodium carbonate solution and precipitated to obtain lithium carbonate. In the recovery methods, the high-efficiency and high-value-added resource recovery of the lithium iron phosphate waste is not well realized, and the method has the advantages of complex process steps, multiple flow steps, high reagent consumption and high cost. Publication No. CN 106450547 a discloses a method for recovering iron phosphate and lithium carbonate from lithium iron phosphate waste. The method comprises the following steps: the method comprises the following steps of oxidizing roasting, pole piece cleaning, adding phosphoric acid, ball milling and activating, acid washing and separating iron phosphate, and precipitating lithium from filtrate to obtain a target lithium carbonate.
Therefore, how to search for a new method for recovering lithium iron phosphate so that phosphorus, iron and lithium elements can be recycled from high value-added resources, and the obtained iron phosphate product has stable quality and can meet the index requirements of battery-grade products becomes a new production process which is a technical problem to be solved in the field at present.
Disclosure of Invention
The invention provides a method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries, and solves the problems that the phosphorus, iron and lithium elements cannot be recycled in high value-added resources and the quality of an obtained iron phosphate product is unstable in the conventional lithium iron phosphate recovery process.
The technical scheme for realizing the invention is as follows:
a method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries comprises the following steps:
1) soaking the waste lithium iron phosphate positive plate by using an organic solvent, and recycling the organic solvent in a reduced pressure distillation mode to obtain lithium iron phosphate powder;
2) soaking the lithium iron phosphate powder into a sodium hydroxide solution, filtering and drying to obtain the aluminum-removed lithium iron phosphate powder;
3) adding the aluminum-removed lithium iron phosphate powder into a mixed solution of sulfuric acid and hydrogen peroxide, heating for leaching reaction, and filtering to obtain an acid leaching solution;
4) adjusting the pH value of the pickle liquor to precipitate iron and phosphorus elements in the form of iron phosphate, and filtering and separating to obtain crude iron phosphate and lithium-containing filtrate;
5) dissolving the rough ferric phosphate in an acid solution, adjusting the pH value to 2, filtering, washing and drying to obtain hydrated ferric phosphate, and calcining the hydrated ferric phosphate to obtain battery-grade ferric phosphate;
6) and (3) evaporating and concentrating the lithium-containing filtrate, adding a sodium carbonate solution, regulating the pH value to precipitate lithium element in the form of lithium carbonate, filtering, washing and drying to obtain the battery-grade lithium carbonate.
2. The method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries according to claim 1, characterized in that: the organic solvent in the step 1) is any one of dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone.
In the step 2), the pH value of the sodium hydroxide solution is 10-12, and the soaking time is 30-120 min.
The sulfuric acid concentration in the step 3) is 1-4 mol/L, the hydrogen peroxide accounts for 3vol% of the sulfuric acid, and the mass ratio of the lithium iron phosphate powder after aluminum removal to the sulfuric acid solution is 1: (5-10).
The heating temperature in the step 3) is 60-100 ℃, and the time is 1-5 h.
And adjusting the pH value to 1-2.5 in the step 4).
In the step 4), at least one of sodium hydroxide, ammonia water, sodium carbonate or sodium bicarbonate is used for adjusting the pH value.
The acid solution in the step 5) is one of sulfuric acid, nitric acid or hydrochloric acid, and the concentration is 0.5-2 mol/L.
In the step 5), the calcining temperature is 500-700 ℃, and the calcining time is 2-6 h.
And 6) adjusting the pH value to 10-11.
The invention has the beneficial effects that:
1) the invention can fully realize the recycling of high value-added resources of phosphorus, iron and lithium elements in the waste lithium iron phosphate, and prepare battery-grade iron phosphate and lithium carbonate products.
2) The method has simple process, can fully utilize phosphorus, iron and lithium resources, has high resource recovery rate, does not generate iron-containing waste residues and phosphorus-containing wastewater, and is easy to realize industrial production.
3) In the process for preparing battery-grade iron phosphate, the purity of the iron phosphate product can be fully ensured by the modes of soaking in alkali liquor for removing aluminum, and secondarily dissolving, removing impurities and precipitating, and the finally obtained iron phosphate product is superior to the standard requirements of 'iron phosphate for HG/T4701-supplement 2014 batteries' (iron phosphate), and can be used as a raw material for preparing lithium iron phosphate.
Drawings
In order to more clearly illustrate the embodiments of the present invention 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 invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Fig. 2 is an XRD characterization of the battery grade iron phosphate obtained in example 1 and a spectrum of iron phosphate standard card 29-0715.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1
The method for recovering phosphorus, iron and lithium from the waste lithium iron phosphate batteries comprises the following steps:
(1) stripping a current collector and an active material from the waste iron phosphate positive plate by using N, N-dimethylacetamide to obtain iron phosphate lithium powder, and recycling the N, N-dimethylacetamide in a reduced pressure distillation mode;
(2) soaking the lithium iron phosphate powder in a sodium hydroxide solution with the pH value of 11 for 60min to obtain the aluminum-removed lithium iron phosphate powder;
(3) adding the aluminum-removed lithium iron phosphate powder into a mixed solution of 3mol/L sulfuric acid and 3vol% hydrogen peroxide according to the mass ratio of the lithium iron phosphate powder to the sulfuric acid of 1:10, and heating at 90 ℃ for 2 hours to carry out leaching reaction to obtain an acid leaching solution;
(4) adjusting the pH value of the acid leaching solution to 2 by using sodium carbonate to precipitate iron and phosphorus elements in the form of iron phosphate to obtain crude iron phosphate and lithium-containing filtrate;
(5) dissolving the crude ferric phosphate in 1mol/L sulfuric acid solution, adjusting the pH value to 2, filtering, washing and drying to obtain hydrated ferric phosphate, and calcining the hydrated ferric phosphate at 600 ℃ for 4 hours to obtain battery-grade ferric phosphate;
(6) and (3) evaporating and concentrating the lithium-containing filtrate, adding a sodium carbonate solution, adjusting the pH value to 11 to enable lithium element to be precipitated in the form of lithium carbonate, and filtering, washing and drying to obtain the battery-grade lithium carbonate.
The process flow diagram of an embodiment of the invention is shown in fig. 1. Fig. 2 is an XRD characterization of the battery-grade iron phosphate prepared in this example, and the XRD spectrum of the battery-grade iron phosphate prepared in this example is consistent with the spectrum of the standard card 29-0715 of iron phosphate, and the diffraction peak is sharp and the characteristic peak is obvious, which indicates that the battery-grade iron phosphate is pure-phase FePO4And has good crystallinity, belonging to an orthorhombic system.
Table 1 shows the concentrations of metal ions in the pickle liquor obtained by leaching with acid and an oxidant, which indicates that the content of impurity ion elements is high; table 2 shows the product quality of the battery-grade iron phosphate prepared in this example, and the iron phosphate obtained by the present invention patent meets the standard requirements of "iron phosphate for HG/T4701-.
TABLE 1 concentration of each metal ion in the pickle liquor obtained by acid and oxidant leaching
TABLE 2 product quality of Battery grade iron phosphate and Standard requirements of "iron phosphate for HG/T4701-
Note: the percentages are given in table 2.
Example 2
The method for recovering phosphorus, iron and lithium from the waste lithium iron phosphate batteries comprises the following steps:
(1) stripping a current collector and an active material from the waste iron phosphate positive plate by using dimethyl sulfoxide to obtain iron phosphate lithium powder, and recycling the dimethyl sulfoxide in a reduced pressure distillation mode;
(2) soaking the lithium iron phosphate powder in a sodium hydroxide solution with the pH value of 10 for 120min to obtain the aluminum-removed lithium iron phosphate powder;
(3) adding the dealuminized lithium iron phosphate powder into a mixed solution of 4mol/L sulfuric acid and 3vol% hydrogen peroxide according to the mass ratio of the lithium iron phosphate powder to the sulfuric acid of 1:5, and heating for 5 hours at 60 ℃ to perform leaching reaction to obtain an acid leaching solution;
(4) adjusting the pH value of the pickle liquor to 1 by ammonia water, so that iron and phosphorus elements are precipitated in the form of iron phosphate to obtain crude iron phosphate and lithium-containing filtrate;
(5) dissolving the crude iron phosphate in a 2mol/L sulfuric acid solution, adjusting the pH value to 2, filtering, washing and drying to obtain hydrated iron phosphate, and calcining the hydrated iron phosphate at 700 ℃ for 2 hours to obtain battery-grade iron phosphate;
(6) and (3) evaporating and concentrating the lithium-containing filtrate, adding a sodium carbonate solution, adjusting the pH value to 12 to enable lithium element to be precipitated in the form of lithium carbonate, and filtering, washing and drying to obtain the battery-grade lithium carbonate.
Example 3
The method for recovering phosphorus, iron and lithium from the waste lithium iron phosphate batteries comprises the following steps:
(1) stripping a current collector and an active material from a waste iron phosphate positive plate by using N, N-dimethylformamide to obtain iron phosphate lithium powder, and recycling the N, N-dimethylformamide in a reduced pressure distillation mode;
(2) soaking the lithium iron phosphate powder in a sodium hydroxide solution with the pH value of 10.5 for 30min to obtain the aluminum-removed lithium iron phosphate powder;
(3) adding the dealuminized lithium iron phosphate powder into a mixed solution of 1mol/L sulfuric acid and 3vol% hydrogen peroxide according to the mass ratio of the lithium iron phosphate powder to the sulfuric acid of 1:6, and heating for 1h at 100 ℃ to perform leaching reaction to obtain an acid leaching solution;
(4) adjusting the pH value of the pickle liquor to 2.5 by using ammonium carbonate to precipitate iron and phosphorus elements in the form of iron phosphate to obtain crude iron phosphate and lithium-containing filtrate;
(5) dissolving the rough ferric phosphate in a 0.5mol/L sulfuric acid solution, adjusting the pH value to 2, filtering, washing and drying to obtain hydrated ferric phosphate, and calcining the hydrated ferric phosphate at 500 ℃ for 6 hours to obtain battery-grade ferric phosphate;
(6) and (3) evaporating and concentrating the lithium-containing filtrate, adding a sodium carbonate solution, adjusting the pH value to 10 to enable lithium element to be precipitated in the form of lithium carbonate, and filtering, washing and drying to obtain the battery-grade lithium carbonate.
Example 4
The method for recovering phosphorus, iron and lithium from the waste lithium iron phosphate batteries comprises the following steps:
(1) stripping a current collector and an active material from the waste iron phosphate positive plate by using N, N-dimethylacetamide to obtain lithium iron phosphate powder N, N-dimethylacetamide, and recycling the lithium iron phosphate powder N, N-dimethylacetamide in a reduced pressure distillation mode;
(2) soaking lithium iron phosphate powder into a sodium hydroxide solution with the pH value of 11 for 30min to obtain the aluminum-removed lithium iron phosphate powder;
(3) adding the dealuminized lithium iron phosphate powder into a mixed solution of 4mol/L sulfuric acid and 3vol% hydrogen peroxide according to the mass ratio of the lithium iron phosphate powder to the sulfuric acid of 1:6, and heating for 4 hours at 80 ℃ to perform leaching reaction to obtain an acid leaching solution;
(4) regulating the pH value of the acid leaching solution to 1.9 by using urea to precipitate iron and phosphorus elements in the form of iron phosphate to obtain crude iron phosphate and lithium-containing filtrate;
(5) dissolving the crude ferric phosphate in 1.5mol/L sulfuric acid solution, adjusting the pH value to 2, filtering, washing and drying to obtain hydrated ferric phosphate, and calcining the hydrated ferric phosphate at 700 ℃ for 3 hours to obtain battery-grade ferric phosphate;
(6) and (3) evaporating and concentrating the lithium-containing filtrate, adding a sodium carbonate solution, adjusting the pH value to 11.5 to precipitate lithium element in the form of lithium carbonate, and filtering, washing and drying to obtain the battery-grade lithium carbonate.
Example 5
The method for recovering phosphorus, iron and lithium from the waste lithium iron phosphate batteries comprises the following steps:
(1) stripping a current collector and an active material from the waste iron phosphate positive plate by using N-methylpyrrolidone to obtain lithium iron phosphate powder N-methylpyrrolidone, and recycling the lithium iron phosphate powder N-methylpyrrolidone in a reduced pressure distillation mode;
(2) soaking the lithium iron phosphate powder into a sodium hydroxide solution with the pH value of 10 for 50min to obtain the aluminum-removed lithium iron phosphate powder;
(3) adding the dealuminized lithium iron phosphate powder into a mixed solution of 2mol/L sulfuric acid and 3vol% hydrogen peroxide according to the mass ratio of the lithium iron phosphate powder to the sulfuric acid of 1:8, and heating for 3 hours at 80 ℃ to perform leaching reaction to obtain an acid leaching solution;
(4) adjusting the pH value of the acid leaching solution to 2 by using sodium hydroxide to precipitate iron and phosphorus elements in the form of iron phosphate to obtain crude iron phosphate and lithium-containing filtrate;
(5) dissolving the crude ferric phosphate in 1.5mol/L sulfuric acid solution, adjusting the pH value to 2, filtering, washing and drying to obtain hydrated ferric phosphate, and calcining the hydrated ferric phosphate at 600 ℃ for 3 hours to obtain battery-grade ferric phosphate;
(6) and (3) evaporating and concentrating the lithium-containing filtrate, adding a sodium carbonate solution, adjusting the pH value to 11 to enable lithium element to be precipitated in the form of lithium carbonate, and filtering, washing and drying to obtain the battery-grade lithium carbonate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries is characterized by comprising the following steps:
1) soaking the waste lithium iron phosphate positive plate by using an organic solvent, and distilling under reduced pressure to obtain lithium iron phosphate powder;
2) soaking the lithium iron phosphate powder into a sodium hydroxide solution, filtering and drying to obtain the aluminum-removed lithium iron phosphate powder;
3) adding the aluminum-removed lithium iron phosphate powder into a mixed solution of sulfuric acid and hydrogen peroxide, heating for leaching reaction, and filtering to obtain an acid leaching solution;
4) adjusting pH of the pickle liquor to 2 with sodium carbonate or sodium bicarbonate to precipitate iron and phosphorus in the form of iron phosphate, filtering, separating to obtain crude iron phosphate and filtrate containing lithium
5) Dissolving the rough ferric phosphate in an acid solution, adjusting the pH value to 2, filtering, washing and drying to obtain hydrated ferric phosphate, and calcining the hydrated ferric phosphate to obtain battery-grade ferric phosphate; the acid solution is one of sulfuric acid, nitric acid or hydrochloric acid, and the concentration is 0.5-2 mol/L;
6) and (3) evaporating and concentrating the lithium-containing filtrate, adding a sodium carbonate solution, adjusting the pH value to precipitate lithium element in the form of lithium carbonate, filtering, washing and drying to obtain the battery-grade lithium carbonate.
2. The method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries according to claim 1, characterized in that: the organic solvent in the step 1) is any one of dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone.
3. The method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries according to claim 1, characterized in that: in the step 2), the pH value of the sodium hydroxide solution is 10-12, and the soaking time is 30-120 min.
4. The method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries according to claim 1, characterized in that: the sulfuric acid concentration in the step 3) is 1-4 mol/L, the hydrogen peroxide accounts for 3vol% of the sulfuric acid, and the mass ratio of the lithium iron phosphate powder after aluminum removal to the sulfuric acid solution is 1: (5-10).
5. The method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries according to claim 1, characterized in that: the heating temperature in the step 3) is 60-100 ℃, and the time is 1-5 h.
6. The method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries according to claim 1, wherein the method comprises the following steps: in the step 5), the calcining temperature is 500-700 ℃, and the calcining time is 2-6 h.
7. The method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries according to claim 1, characterized in that: and 6) adjusting the pH value to 10-11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011259874.0A CN112331949B (en) | 2020-11-12 | 2020-11-12 | Method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011259874.0A CN112331949B (en) | 2020-11-12 | 2020-11-12 | Method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112331949A CN112331949A (en) | 2021-02-05 |
| CN112331949B true CN112331949B (en) | 2022-06-07 |
Family
ID=74317478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011259874.0A Active CN112331949B (en) | 2020-11-12 | 2020-11-12 | Method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112331949B (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112838289B (en) * | 2021-02-24 | 2022-02-01 | 武汉工程大学 | Method for recovering lithium and ferrous phosphate from lithium iron phosphate positive electrode material |
| CN113023703A (en) * | 2021-03-24 | 2021-06-25 | 郑州中科新兴产业技术研究院 | Method for recycling waste lithium iron phosphate powder |
| CN113120876B (en) * | 2021-03-30 | 2022-06-10 | 中国石油大学(北京) | Method for preparing lithium iron phosphate material by regenerating and recycling waste lithium iron phosphate pole pieces |
| CN113430322A (en) * | 2021-06-07 | 2021-09-24 | 中国恩菲工程技术有限公司 | Method for recovering phosphorus and iron in waste lithium iron phosphate battery |
| CN113336211A (en) * | 2021-06-18 | 2021-09-03 | 湖北融通高科先进材料有限公司 | Method for preparing ferrous phosphate and lithium phosphate by recycling lithium iron phosphate material |
| CN113501510A (en) * | 2021-07-13 | 2021-10-15 | 郑州中科新兴产业技术研究院 | Method for recycling and regenerating anode material of waste lithium iron phosphate battery |
| CN113322380B (en) * | 2021-08-02 | 2021-11-30 | 清大国华环境集团股份有限公司 | Recycling treatment method of power lithium battery |
| CN113809423A (en) * | 2021-08-03 | 2021-12-17 | 广东邦普循环科技有限公司 | Comprehensive utilization method of waste lithium iron phosphate battery |
| CN113603119B (en) * | 2021-08-03 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for recovering lithium from waste lithium iron phosphate material |
| CN113666397A (en) * | 2021-08-21 | 2021-11-19 | 福州大学 | Method for economically recycling lithium from waste lithium iron phosphate material by acid process |
| CN113793994B (en) * | 2021-08-24 | 2023-04-07 | 西安交通大学 | Method for recycling waste lithium iron phosphate batteries |
| CN113912036B (en) * | 2021-10-15 | 2023-09-08 | 合肥国轩电池材料有限公司 | Method for recycling and preparing lithium iron phosphate from retired lithium iron battery |
| CN114195112A (en) * | 2021-11-03 | 2022-03-18 | 格林美股份有限公司 | Recovery method of waste lithium iron phosphate battery |
| CN113880064B (en) * | 2021-11-09 | 2023-08-01 | 株洲冶炼集团股份有限公司 | Method for treating high-impurity lithium iron phosphate waste powder by low-consumption phosphoric acid |
| CN114229812B (en) * | 2021-12-20 | 2023-03-24 | 中北大学 | Method for extracting iron and phosphorus from lithium iron phosphate waste |
| CN114349030B (en) * | 2021-12-23 | 2024-04-12 | 湖北锂宝新材料科技发展有限公司 | Comprehensive wet recycling method for waste lithium iron phosphate positive plate |
| CN114408888B (en) * | 2021-12-23 | 2023-09-19 | 广东臻鼎环境科技有限公司 | Method for preparing battery grade ferric phosphate powder by using aluminum-containing waste acid liquid |
| CN115241556A (en) * | 2022-08-11 | 2022-10-25 | 天津理工大学 | Lithium iron phosphate black powder treatment method |
| CN115159492A (en) * | 2022-08-16 | 2022-10-11 | 雅安天蓝新材料科技有限公司 | Resource treatment method for waste batteries |
| CN115072688B (en) * | 2022-08-18 | 2022-11-08 | 矿冶科技集团有限公司 | Method for recycling all components of waste lithium iron phosphate battery |
| CN115504446B (en) * | 2022-09-22 | 2023-06-27 | 河南鑫再生新材料科技有限公司 | Method for green recovery of lithium iron phosphate positive electrode material |
| CN115385316B (en) * | 2022-09-23 | 2023-05-26 | 清华四川能源互联网研究院 | Recovery process of lithium iron phosphate |
| CN115744943A (en) * | 2022-11-29 | 2023-03-07 | 长沙道尚循环科技有限公司 | Method for recycling lithium iron phosphate battery |
| CN115784188A (en) * | 2023-02-07 | 2023-03-14 | 锂源(深圳)科学研究有限公司 | Method for recycling and preparing battery-grade iron phosphate |
| CN116397110B (en) * | 2023-05-26 | 2023-10-31 | 科立鑫(珠海)新能源有限公司 | Method for recycling lithium from waste lithium iron phosphate battery |
| CN116864851B (en) * | 2023-09-05 | 2023-11-21 | 赣州市力道新能源有限公司 | Process for deeply removing phosphorus from retired battery recovery feed liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101847763A (en) * | 2010-04-09 | 2010-09-29 | 奇瑞汽车股份有限公司 | Comprehensive recovering method of waste lithium iron phosphate battery |
| CN104953200A (en) * | 2015-06-30 | 2015-09-30 | 哈尔滨工业大学 | Method for recycling battery-grade iron phosphate in lithium iron phosphate battery and preparing lithium iron phosphate positive material by utilizing waste lithium ion phosphate battery |
| CN107352524A (en) * | 2017-08-03 | 2017-11-17 | 清华大学 | A kind of recovery method of waste lithium iron phosphate positive electrode |
| CN110233306A (en) * | 2019-07-09 | 2019-09-13 | 郑州中科新兴产业技术研究院 | A kind of method of waste and old lithium ion battery recycling ternary anode material precursor |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2979756B1 (en) * | 2011-09-07 | 2013-10-04 | Commissariat Energie Atomique | PROCESS FOR RECYCLING LITHIUM BATTERIES AND / OR ELECTRODES OF SUCH BATTERIES |
| CN103280610B (en) * | 2013-03-29 | 2015-11-11 | 江西省电力科学研究院 | A kind of positive pole waste tablet from ferric phosphate lithium cell recovery method |
| CN106684485B (en) * | 2016-12-19 | 2020-04-21 | 天齐锂业股份有限公司 | Method for recycling waste lithium iron phosphate anode material by acid leaching method |
| CN107069132A (en) * | 2016-12-19 | 2017-08-18 | 天齐锂业股份有限公司 | A kind of method for reclaiming waste lithium iron phosphate positive electrode |
| CN108899601B (en) * | 2018-06-11 | 2020-01-14 | 衢州华友钴新材料有限公司 | Method for recovering lithium and iron from lithium iron phosphate |
| CN109179358B (en) * | 2018-11-08 | 2020-06-09 | 广东省稀有金属研究所 | Method for preparing battery-grade iron phosphate from waste lithium iron phosphate batteries |
| CN109775678B (en) * | 2019-04-01 | 2022-05-10 | 中钢集团南京新材料研究院有限公司 | Method for preparing battery-grade iron phosphate and industrial-grade lithium phosphate from waste lithium iron phosphate batteries |
| CN110342483B (en) * | 2019-06-04 | 2020-11-03 | 湖南雅城新材料有限公司 | Method for preparing battery-grade iron phosphate by using lithium phosphate waste |
| CN111285341A (en) * | 2020-02-21 | 2020-06-16 | 北京蒙京石墨新材料科技研究院有限公司 | Method for extracting battery-grade iron phosphate from waste lithium iron phosphate batteries |
| CN111411366B (en) * | 2020-04-26 | 2021-07-02 | 华中科技大学 | Method for recovering metal ions in lithium iron phosphate waste through solid-phase electrolysis |
| CN111646447B (en) * | 2020-06-17 | 2021-12-14 | 中国科学院宁波材料技术与工程研究所 | Method for recovering iron phosphate from iron-phosphorus slag after lithium extraction of lithium iron phosphate lithium battery |
-
2020
- 2020-11-12 CN CN202011259874.0A patent/CN112331949B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101847763A (en) * | 2010-04-09 | 2010-09-29 | 奇瑞汽车股份有限公司 | Comprehensive recovering method of waste lithium iron phosphate battery |
| CN104953200A (en) * | 2015-06-30 | 2015-09-30 | 哈尔滨工业大学 | Method for recycling battery-grade iron phosphate in lithium iron phosphate battery and preparing lithium iron phosphate positive material by utilizing waste lithium ion phosphate battery |
| CN107352524A (en) * | 2017-08-03 | 2017-11-17 | 清华大学 | A kind of recovery method of waste lithium iron phosphate positive electrode |
| CN110233306A (en) * | 2019-07-09 | 2019-09-13 | 郑州中科新兴产业技术研究院 | A kind of method of waste and old lithium ion battery recycling ternary anode material precursor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112331949A (en) | 2021-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112331949B (en) | Method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries | |
| CN108832215B (en) | Method for selectively recovering lithium ion battery anode material | |
| CN113501510A (en) | Method for recycling and regenerating anode material of waste lithium iron phosphate battery | |
| CN107267759A (en) | A kind of comprehensive recovering process of anode material for lithium-ion batteries | |
| CN110669933B (en) | Method for removing fluorine in nickel-cobalt-manganese solution | |
| CN110474123B (en) | Comprehensive recovery method of waste lithium iron phosphate battery positive electrode material | |
| CN109179359A (en) | A method of extracting lithium and ferric phosphate from LiFePO4 waste material | |
| CN111082043A (en) | Recycling method of waste nickel cobalt lithium manganate ternary battery positive electrode material | |
| CN103035977A (en) | Method for separating and recovering lithium from waste lithium ion battery | |
| CN109167118B (en) | Comprehensive utilization method of lithium iron phosphate battery electrode material | |
| CN111697282B (en) | Method for extracting lithium from dilute solution recovered from waste battery positive electrode material | |
| CN115432681B (en) | Regeneration process of waste lithium iron phosphate battery anode material | |
| CN111961839A (en) | Method for synchronously leaching valuable metals from positive and negative electrode active materials of waste lithium ion batteries and removing impurities | |
| US20240088468A1 (en) | Method for extracting lithium from waste lithium battery | |
| CN114717419A (en) | Method for separating and recovering nickel, cobalt, manganese and lithium from waste ternary lithium battery | |
| CN114317968A (en) | Recycling method and application of waste lithium iron phosphate battery | |
| CN113415793A (en) | Method for preparing high-purity iron phosphate from lithium iron phosphate battery waste | |
| US20220384868A1 (en) | Battery-level ni-co-mn mixed solution and preparation method for battery-level mn solution | |
| CN111041218A (en) | Comprehensive extraction method for metals in waste lithium ion batteries | |
| CN113603120A (en) | Method for recovering battery-grade lithium from waste lithium iron phosphate through short-process acid leaching | |
| CN115072688B (en) | Method for recycling all components of waste lithium iron phosphate battery | |
| CN115799696A (en) | Method for pretreating waste electrolyte after disassembling lithium ion battery and method for fully recovering lithium, fluorine and phosphorus in waste electrolyte | |
| CN114852983A (en) | Method for extracting battery-grade iron phosphate from byproduct ferrophosphorus waste residue of recovered waste lithium battery | |
| CN113373321B (en) | Method for recycling lithium element from scrapped lithium iron phosphate battery by wet method | |
| CN117625996A (en) | Method for recycling lithium from lithium iron phosphate battery positive electrode waste powder |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230720 Address after: Room 1125, 10th Floor, Building 1, No. 6 Danling Street, Haidian District, Beijing 100086 Patentee after: Zhongke Xingfa Medical Technology Co.,Ltd. Address before: 10 / F, block a, Newton international, Yangjin Road, Jinshui District, Zhengzhou City, Henan Province Patentee before: ZHENGZHOU INSTITUTE OF EMERGING INDUSTRIAL TECHNOLOGY Patentee before: Institute of Process Engineering, Chinese Academy of Sciences |
|
| TR01 | Transfer of patent right |