CN113023703A - Method for recycling waste lithium iron phosphate powder - Google Patents
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- 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
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- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides a method for recovering waste lithium iron phosphate powder, which comprises the following steps: (1) leaching valuable ions: dissolving the waste lithium iron phosphate anode material by adopting a hydrochloric acid and additive system, and performing solid-liquid separation to obtain a leaching solution; (2) acid liquor concentration and circulation: decompressing and concentrating the metal ion leaching solution obtained in the step (1) to obtain a concentrated solution; (3) and (3) separating lithium iron: adjusting the pH value of the concentrated solution in the step (2), and performing solid-liquid separation to obtain a crude ferric phosphate solid and a lithium ion-containing solution; (4) and (3) iron phosphate refining: and (4) carrying out solid acid washing recrystallization on the crude ferric phosphate obtained in the step (3), drying, and calcining the powder to obtain the battery-grade ferric phosphate. The iron phosphate prepared in the whole recovery process has high purity, no secondary pollution is generated in the whole process, the process energy consumption is low, the recovery process is green and efficient, and the high added value recycling of the waste lithium iron phosphate batteries is realized.
Description
Technical Field
The invention relates to the field of lithium ion battery material recovery, in particular to a method for recovering waste lithium iron phosphate powder.
Background
With the rise of the new energy automobile industry and the guidance of national policies, new energy automobiles are in explosive growth. The yield of the electric automobile in 2025 is expected to reach 580 million vehicles, and the output value is expected to break through trillion yuan. Wherein in the whole electric automobile, the battery accounts for 1/3 of the cost of the whole automobile, the weight ratio is 1/4, and the electric automobile is rich in various energy metals and strategic elements. If the waste power battery is not treated properly, a plurality of contained metal elements not only can cause great harm to human health, but also can cause resource waste. The state issues a series of policies to carry out standardized guidance on recycling of power batteries, so that recycling and reusing of waste batteries are not slow.
At present, the lithium iron phosphate battery recovery method mainly comprises a dry high-temperature solid phase repair method and a hydrometallurgy recovery method. The dry high-temperature repair method comprises the steps of mechanically crushing the positive electrode material by a mechanical sorting method, removing the organic binder by high-temperature calcination, and separating the lithium iron phosphate powder from the aluminum foil to obtain the lithium iron phosphate positive electrode material, but the whole recovery process has weak pertinence to the waste battery, high energy consumption and serious environmental pollution caused by burning of organic solvents and the like in the battery. The hydrometallurgical recovery adopts acid-base solution as a medium to dissolve the waste lithium iron phosphate anode, and adopts the modes of precipitation, adsorption, ion exchange and the like to recover lithium carbonate and iron phosphate.
Chinese patent CN106684485A provides a method for recovering waste lithium iron phosphate anode material by acid leaching: and after the waste lithium iron phosphate anode material is subjected to acid leaching, adding an oxidant and adjusting the pH value to obtain the iron phosphate. The inorganic acid used in the process is not recycled, the purity of the subsequent generated iron phosphate product is low, further purification treatment is needed, the energy consumption of the whole recycling process is increased, and the economic value of the product is reduced.
Chinese patent CN103280610A discloses a method for recovering positive electrode of lithium iron phosphate battery, which adopts mixed acid leaching to dissolve, so that iron ions exist in the form of iron phosphate precipitate, then adopts acid leaching treatment, adds alkali solution to generate ferric hydroxide solid, and adds sodium carbonate to lithium-containing solution to generate lithium carbonate precipitate after solid-liquid separation. The processes do not realize the high-efficiency and high-value-added resource recovery of the lithium iron phosphate waste, and the generated ferric hydroxide material is difficult to separate solid and liquid, low in separation efficiency, complex in process steps, multiple in flow steps, large in reagent consumption, high in cost and poor in economical efficiency.
Therefore, the method for recycling the valuable metal elements has the advantages of high recovery efficiency of the valuable metal elements, simple process flow, high purity of the recycled iron phosphate product, no secondary pollution in the whole process, low process energy consumption, green and high efficiency in the recycling process, and the high added value recycling of the waste lithium iron phosphate batteries is realized.
Disclosure of Invention
The invention provides a method for recovering waste lithium iron phosphate powder, which reduces the acidity of a leaching solution through a concentration process, reduces the using amount of a reagent when the pH value of a solution is adjusted to generate iron phosphate precipitate in a subsequent process, can recycle and leach dilute hydrochloric acid obtained through the concentration process, has high purity of iron phosphate solid obtained through repeated dissolution and crystallization, effectively reduces the recovery cost while fully utilizing valuable elements in a waste lithium iron phosphate positive electrode material, and realizes green and high-added-value recovery and utilization of waste lithium iron phosphate batteries.
The technical scheme for realizing the invention is as follows:
a method for recycling waste lithium iron phosphate powder comprises the following steps:
(1) leaching valuable ions: dissolving the waste lithium iron phosphate anode material by adopting a hydrochloric acid and additive system, and performing solid-liquid separation to obtain leachate containing metal ions of phosphorus, iron and lithium;
(2) acid liquor concentration and circulation: decompressing and concentrating the metal ion leaching solution obtained in the step (1) to obtain a concentrated solution, wherein hydrochloric acid solution prepared by absorbing and regenerating hydrogen chloride gas is recycled;
(3) and (3) separating lithium iron: adjusting the pH of the concentrated solution in the step (2) to obtain a solution containing ferric phosphate solid and lithium ions, and performing solid-liquid separation to obtain crude ferric phosphate solid and a solution containing lithium ions;
(4) and (3) iron phosphate refining: and (4) carrying out solid acid washing recrystallization on the crude ferric phosphate obtained in the step (3), drying, and calcining the powder to obtain the battery-grade ferric phosphate.
The additive in the step (1) is one of hydrogen peroxide, sodium thiosulfate or sodium sulfite, and the addition amount of the hydrochloric acid and the additive in the additive system is 1-5 wt%.
The reduced pressure concentration method in the step (2) is reduced pressure distillation.
The vacuum degree of the reduced pressure distillation is 0.01-0.1 MPa, and the temperature is controlled at 20-90 ℃.
And (3) absorbing and regenerating the hydrogen chloride gas generated in the pressure reduction concentration process in the step (2) in a gas recovery device, wherein the absorbent of the gas absorption tower is water, and the generated hydrogen chloride gas is recovered in the concentration process to obtain a dilute hydrochloric acid solution for leaching, dissolving and recycling.
And in the step (3), one or a combination of at least two of water and a soda reagent is adopted to adjust the pH value to 1.5-4.
And (4) carrying out recrystallization washing operation by adopting the dilute hydrochloric acid solution and the deionized water absorbed and regenerated in the step (2), wherein the pickling solution is concentrated and circulated to an absorption device for reuse.
And (4) after acid washing and recrystallization in the step (4), repeating the operation treatment of the step (2) and the step (3) for 1-5 times.
The preferred drying mode of the ferric phosphate solid is one or the combination of at least two of forced air drying, vacuum drying or freeze drying.
The preferred calcining atmosphere of the iron phosphate solid is one of air and oxygen.
And (4) calcining the dried powder at 550-750 ℃ for 2-10 h.
And (3) adding carbonate (sodium carbonate, ammonium carbonate and potassium carbonate) into the lithium ion-containing solution in the step (3) to obtain a lithium carbonate material.
The invention has the beneficial effects that: according to the invention, through the concentration process, on one hand, the acidity of the leachate is reduced, the subsequent alkali consumption is reduced, on the other hand, the recovered dilute hydrochloric acid can be used for leaching and recycling, and the ferric phosphate solid obtained through repeated dissolution and crystallization has high purity, so that the recovery cost is effectively reduced while valuable elements in the waste lithium iron phosphate anode material are fully utilized. The iron phosphate prepared in the whole recovery process has high purity, no secondary pollution is generated in the whole process, the process energy consumption is low, the recovery process is green and efficient, and the high added value recycling of the waste lithium iron phosphate batteries is realized.
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 schematic flow chart of a process for recovering waste lithium iron phosphate powder to generate battery-grade iron phosphate according to the embodiment of the present invention.
Figure 2 is an XRD pattern of the iron phosphate recovered in example 1.
Figure 3 is an SEM image of the recovered iron phosphate from example 1.
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 without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A process method for generating battery-grade iron phosphate by recycling waste lithium iron phosphate powder comprises the following specific production steps:
(1) adding 10g of black powder material into 100ml of mixed solution of hydrochloric acid and hydrogen peroxide according to the solid-to-liquid ratio of 100g/L, wherein the volume of the hydrochloric acid is 86.7ml, the volume of the hydrogen peroxide is 13.3ml, the leaching temperature is 40 ℃, the leaching time is 1h, and filtering after dissolution to obtain metal ion leachate containing phosphorus, iron and lithium;
(2) concentrating the leachate obtained in the step (1) by adopting a reduced pressure distillation method, collecting evaporated hydrogen chloride gas by adopting a gas recovery tower device by using water as an absorbent, regenerating the obtained dilute hydrochloric acid solution, and recycling the dilute hydrochloric acid solution for subsequent leaching and dissolving cycles, wherein the leachate containing phosphorus, iron and lithium ions is obtained by concentrating, the vacuum degree in the reduced pressure distillation process is 0.1Mpa, and the temperature is controlled at 80 ℃;
(3) adjusting the pH value of the concentrated solution containing phosphorus, iron and lithium ions obtained in the step (2) to 2.0 by using a soda solution to generate an iron phosphate precipitate, carrying out solid-liquid separation after the precipitate is precipitated, filtering to obtain a crude iron phosphate solid, and filtering to obtain an acidic lithium ion-containing solution;
(4) carrying out repeated dissolution leaching 2 times on the crude ferric phosphate solid obtained in the step (3) by adopting the leaching, recovery, concentration and regeneration treatment in the step (2) to obtain a hydrochloric acid solution, carrying out recrystallization purification treatment, washing the obtained ferric phosphate solid for a plurality of times by adopting pure water until the supernatant is neutral, and drying by air blowing at 120 ℃ to obtain ferric phosphate powder containing crystal water; calcining the dried powder for 5 hours at 650 ℃ in a tubular furnace in air atmosphere to obtain a battery-grade iron phosphate material;
(5) adding sodium carbonate into the acidic lithium ion-containing solution by a traditional method to generate precipitate, and filtering to obtain the lithium carbonate material.
Fig. 1 is an overall process route diagram of the present invention, fig. 2 is an XRD spectrum of the recovered battery-grade iron phosphate solid, fig. 3 is an SEM spectrum of the recovered battery-grade iron phosphate solid, and ICP test results of the sample after dissolution leaching and secondary dissolution crystallization treatment of the lithium iron phosphate black powder material are shown in table 1.
Example 2
A process method for generating battery-grade iron phosphate by recycling waste lithium iron phosphate powder comprises the following specific production steps:
(1) adding 10g of black powder material into 100ml of mixed solution of hydrochloric acid and sodium thiosulfate according to the solid-to-liquid ratio of 100g/L, wherein the volume of the hydrochloric acid is 96.7ml, the volume of the sodium thiosulfate solution is 3.3ml, the leaching temperature is 60 ℃, the leaching time is 0.5h, and filtering after dissolution to obtain a leaching solution containing metal ions of phosphorus, iron and lithium;
(2) concentrating the obtained leachate by adopting a reduced pressure distillation method, collecting evaporated hydrogen chloride gas by adopting a gas recovery tower device by using water as an absorbent, regenerating the obtained dilute hydrochloric acid solution, and then repeatedly using the dilute hydrochloric acid solution for subsequent leaching and dissolving cycles, and concentrating to obtain leachate containing phosphorus, iron and lithium ions, wherein the vacuum degree in the reduced pressure distillation process is 0.01Mpa, and the temperature is controlled at 20 ℃;
(3) adjusting the pH value of the concentrated solution containing phosphorus, iron and lithium ions obtained in the step (2) to 1.5 by adopting a pure water solution to generate an iron phosphate precipitate, carrying out solid-liquid separation after the precipitate is precipitated, filtering to obtain a crude iron phosphate solid, and filtering to obtain an acidic lithium ion-containing solution;
(4) repeatedly dissolving and leaching the crude ferric phosphate solid obtained in the step (3) by using a hydrochloric acid solution obtained by leaching, recovering, concentrating and regenerating treatment in the step (2) for 1 time, recrystallizing and purifying, washing the obtained ferric phosphate solid by using pure water for a plurality of times until the supernatant is neutral, and drying by blowing at 120 ℃ to obtain ferric phosphate powder containing crystal water; calcining the dried powder for 5 hours in a tube furnace at 650 ℃ in an oxygen atmosphere to obtain a battery-grade iron phosphate material;
(5) adding ammonia carbonate into the acidic lithium ion-containing solution by a traditional method to generate precipitate, and filtering to obtain the lithium carbonate material.
Example 3
A process method for generating battery-grade iron phosphate by recycling waste lithium iron phosphate powder comprises the following specific production steps:
(1) adding 10g of black powder material into 100ml of mixed solution of hydrochloric acid and sodium sulfite according to the solid-to-liquid ratio of 100g/L, wherein the concentration of the hydrochloric acid is 2.5mol/L, the volume of the hydrochloric acid is 86.7ml, the volume of the sodium sulfite is 13.3ml, the leaching temperature is 20 ℃, the leaching time is 4h, and filtering after dissolution is carried out to obtain metal ion leachate containing phosphorus, iron and lithium;
(2) concentrating the obtained leachate by adopting a reduced pressure distillation method, collecting evaporated hydrogen chloride gas by adopting a gas recovery tower device by using water as an absorbent, regenerating the obtained dilute hydrochloric acid solution, and then recycling the dilute hydrochloric acid solution for subsequent leaching and dissolving cycles, and concentrating to obtain leachate containing phosphorus, iron and lithium ions, wherein the vacuum degree in the reduced pressure distillation process is 0.08Mpa, and the temperature is controlled at 90 ℃;
(3) adjusting the pH value of the concentrated solution containing phosphorus, iron and lithium ions obtained in the step (2) to 4.0 by using an alkali solution to generate an iron phosphate precipitate, carrying out solid-liquid separation after the precipitate is precipitated, filtering to obtain a crude iron phosphate solid, and filtering to obtain an acidic lithium ion-containing solution;
(4) carrying out repeated dissolution leaching 5 times on the crude ferric phosphate solid obtained in the step (3) by adopting the leaching, recovery, concentration and regeneration treatment in the step (2) to obtain a hydrochloric acid solution, carrying out recrystallization purification treatment, washing the obtained ferric phosphate solid for a plurality of times by adopting pure water until the supernatant is neutral, and drying by air blowing at 120 ℃ to obtain ferric phosphate powder containing crystal water; calcining the dried powder for 10 hours at 550 ℃ in a tube furnace in air atmosphere to obtain a battery-grade iron phosphate material;
(5) adding sodium carbonate into the acidic lithium ion-containing solution by a traditional method to generate precipitate, and filtering to obtain the lithium carbonate material.
Example 4
A process method for generating battery-grade iron phosphate by recycling waste lithium iron phosphate powder comprises the following specific production steps:
(1) adding 10g of black powder material into 100ml of mixed solution of hydrochloric acid and hydrogen peroxide according to the solid-to-liquid ratio of 100g/L, wherein the volume of the hydrochloric acid is 86.7ml, the volume of the hydrogen peroxide is 13.3ml, the leaching temperature is 50 ℃, the leaching time is 2.5h, and filtering after dissolution to obtain a leaching solution containing metal ions of phosphorus, iron and lithium;
(2) concentrating the obtained leachate by adopting a reduced pressure distillation method, collecting evaporated hydrogen chloride gas by adopting a gas recovery tower device by using water as an absorbent, regenerating the obtained dilute hydrochloric acid solution, and then recycling the dilute hydrochloric acid solution for subsequent leaching and dissolving cycles, and concentrating to obtain leachate containing phosphorus, iron and lithium ions, wherein the vacuum degree in the reduced pressure distillation process is 0.08Mpa, and the temperature is controlled at 40 ℃;
(3) adjusting the pH value of the concentrated solution containing phosphorus, iron and lithium ions obtained in the step (2) to 2.0 by using an alkali solution to generate an iron phosphate precipitate, carrying out solid-liquid separation after the precipitate is precipitated, filtering to obtain a crude iron phosphate solid, and filtering to obtain an acidic lithium ion-containing solution;
(4) repeatedly dissolving and leaching the crude ferric phosphate solid obtained in the step (3) by using a hydrochloric acid solution obtained by leaching, recovering and concentrating in the step (2) for 3 times, recrystallizing and purifying, washing the obtained ferric phosphate solid for a plurality of times by using pure water until the supernatant is neutral, and drying by blowing at 120 ℃ to obtain ferric phosphate powder containing crystal water; calcining the dried powder for 2 hours at 750 ℃ in a tubular furnace in air atmosphere to obtain a battery-grade iron phosphate material;
(5) the lithium ion-containing solution is precipitated by adding potassium carbonate, and filtered to obtain a lithium carbonate material.
Example 5
A process method for generating battery-grade iron phosphate by recycling waste lithium iron phosphate powder comprises the following specific production steps:
(1) adding 10g of black powder material into 100ml of mixed solution of hydrochloric acid and hydrogen peroxide according to the solid-to-liquid ratio of 100g/L, wherein the volume of the hydrochloric acid is 86.7ml, the volume of the hydrogen peroxide is 13.3ml, the leaching temperature is 40 ℃, the leaching time is 2 hours, and filtering after dissolution to obtain metal ion leachate containing phosphorus, iron and lithium;
(2) concentrating the obtained leachate by adopting a reduced pressure distillation method, collecting evaporated hydrogen chloride gas by adopting a gas recovery tower device by using water as an absorbent, regenerating the obtained dilute hydrochloric acid solution, and then recycling the dilute hydrochloric acid solution for subsequent leaching and dissolving cycles, and concentrating to obtain leachate containing phosphorus, iron and lithium ions, wherein the vacuum degree in the reduced pressure distillation process is 0.08Mpa, and the temperature is controlled at 60 ℃;
(3) adjusting the pH value of the concentrated solution containing phosphorus, iron and lithium ions obtained in the step (2) to 2.5 by using an alkali solution to generate an iron phosphate precipitate, carrying out solid-liquid separation after the precipitate is precipitated, filtering to obtain a crude iron phosphate solid, and filtering to obtain an acidic lithium ion-containing solution;
(4) repeatedly dissolving and leaching the crude ferric phosphate solid obtained in the step (3) by using a hydrochloric acid solution obtained by leaching, recovering, concentrating and regenerating treatment in the step (2) for 3 times, recrystallizing and purifying, washing the obtained ferric phosphate solid by using pure water for a plurality of times until the supernatant is neutral, and drying by blowing at 120 ℃ to obtain ferric phosphate powder containing crystal water; calcining the dried powder for 2 hours at 650 ℃ in a tubular furnace in air atmosphere to obtain a battery-grade iron phosphate material;
(5) adding sodium carbonate into the acidic lithium ion-containing solution by a traditional method to generate precipitate, and filtering to obtain the lithium carbonate material.
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 (10)
1. A method for recycling waste lithium iron phosphate powder is characterized by comprising the following steps:
(1) leaching valuable ions: dissolving the waste lithium iron phosphate anode material by adopting a hydrochloric acid and additive system to obtain a metal ion leaching solution;
(2) acid liquor concentration and circulation: decompressing and concentrating the metal ion leaching solution obtained in the step (1) to obtain a concentrated solution;
(3) and (3) separating lithium iron: adjusting the pH value of the concentrated solution in the step (2), and performing solid-liquid separation to obtain a crude ferric phosphate solid and a lithium ion-containing solution;
(4) and (3) iron phosphate refining: and (4) carrying out solid acid washing recrystallization on the crude ferric phosphate obtained in the step (3), drying, and calcining the powder to obtain the battery-grade ferric phosphate.
2. The method for recycling waste lithium iron phosphate powder according to claim 1, characterized in that: the additive in the step (1) is one of hydrogen peroxide, sodium thiosulfate or sodium sulfite, and the addition amount of the hydrochloric acid and the additive in the additive system is 1-5 wt%.
3. The method for recycling waste lithium iron phosphate powder according to claim 1, characterized in that: the reduced pressure concentration method in the step (2) is reduced pressure distillation.
4. The method for recycling waste lithium iron phosphate powder according to claim 3, characterized in that: the vacuum degree of the reduced pressure distillation is 0.01-0.1 MPa, and the temperature is controlled at 20-90 ℃.
5. The method for recycling waste lithium iron phosphate powder according to claim 1, characterized in that: and (3) collecting hydrogen chloride gas generated in the pressure reduction concentration process in the step (2) by using water as an absorbent, and regenerating the obtained dilute hydrochloric acid solution for subsequent leaching and dissolving cycle and reuse.
6. The method for recycling waste lithium iron phosphate powder according to claim 1, characterized in that: and (4) adjusting the pH value to 1.5-4 in the step (3).
7. The method for recycling waste lithium iron phosphate powder according to claim 5, characterized in that: and (4) carrying out recrystallization washing operation by adopting the dilute hydrochloric acid solution and the deionized water absorbed and regenerated in the step (2), wherein the pickling solution is concentrated and circulated to an absorption device for reuse.
8. The method for recycling waste lithium iron phosphate powder according to claim 1, characterized in that: and (4) after acid washing and recrystallization in the step (4), repeating the operation treatment of the step (2) and the step (3) for 1-5 times.
9. The method for recycling waste lithium iron phosphate powder according to claim 1, characterized in that: and (4) calcining the dried powder at 550-750 ℃ for 2-10 h.
10. The method for recycling waste lithium iron phosphate powder according to any one of claims 1 to 9, characterized in that: and (3) adding carbonate into the lithium ion-containing solution in the step (3) to obtain a lithium carbonate material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912033A (en) * | 2021-10-15 | 2022-01-11 | 浙江天能新材料有限公司 | Method for recycling anode and cathode mixed powder of waste lithium iron phosphate battery with pre-positioned lithium extraction |
| CN114477118A (en) * | 2022-02-15 | 2022-05-13 | 合肥国轩循环科技有限公司 | Comprehensive treatment method for waste lithium iron phosphate battery positive electrode powder |
| CN115448335A (en) * | 2022-10-26 | 2022-12-09 | 埃索凯循环能源科技(广西)有限公司 | Recycling method of waste manganese iron phosphate lithium battery |
| CN115611250A (en) * | 2021-07-16 | 2023-01-17 | 中国科学院过程工程研究所 | Method for recovering high-purity iron phosphate from waste lithium iron phosphate anode powder |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009263222A (en) * | 2008-03-31 | 2009-11-12 | Toda Kogyo Corp | Method for producing lithium iron phosphate powder, olivine-structured lithium iron phosphate powder, cathode sheet using the lithium iron phosphate powder and non-aqueous solvent secondary battery |
| CN102403554A (en) * | 2011-11-10 | 2012-04-04 | 大连交通大学 | Method for recycling waste lithium iron phosphate ion battery anode material |
| CN102891345A (en) * | 2012-10-22 | 2013-01-23 | 四川天齐锂业股份有限公司 | Method for recycling lithium chloride from waste lithium iron phosphate |
| CN103086341A (en) * | 2013-02-04 | 2013-05-08 | 瓮福（集团）有限责任公司 | Method for preparing battery-grade iron phosphate by using ferrophosphorus |
| CN106629646A (en) * | 2016-11-28 | 2017-05-10 | 荆门市格林美新材料有限公司 | Resource recovery method of lithium iron phosphate waste materials |
| CN106916956A (en) * | 2017-03-31 | 2017-07-04 | 广东佳纳能源科技有限公司 | A kind of method that solventing-out process reclaims valuable metal and recycling in LiFePO4 waste material |
| CN109250696A (en) * | 2017-07-12 | 2019-01-22 | 深圳佳彬科技有限公司 | A method of recycling nano ferric phosphate from ferric phosphate lithium cell |
| CN109950651A (en) * | 2019-04-03 | 2019-06-28 | 中南大学 | A kind of integrated conduct method of waste lithium iron phosphate battery recycling carbon |
| CN111333046A (en) * | 2020-03-26 | 2020-06-26 | 中国科学院过程工程研究所 | Resource recovery method and system for waste lithium iron phosphate anode based on hydrochloric acid circulation |
| CN111924817A (en) * | 2020-07-24 | 2020-11-13 | 中南大学 | Method for comprehensively utilizing waste lithium iron phosphate anode material |
| CN112331949A (en) * | 2020-11-12 | 2021-02-05 | 郑州中科新兴产业技术研究院 | Method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries |
-
2021
- 2021-03-24 CN CN202110312242.4A patent/CN113023703A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009263222A (en) * | 2008-03-31 | 2009-11-12 | Toda Kogyo Corp | Method for producing lithium iron phosphate powder, olivine-structured lithium iron phosphate powder, cathode sheet using the lithium iron phosphate powder and non-aqueous solvent secondary battery |
| CN102403554A (en) * | 2011-11-10 | 2012-04-04 | 大连交通大学 | Method for recycling waste lithium iron phosphate ion battery anode material |
| CN102891345A (en) * | 2012-10-22 | 2013-01-23 | 四川天齐锂业股份有限公司 | Method for recycling lithium chloride from waste lithium iron phosphate |
| CN103086341A (en) * | 2013-02-04 | 2013-05-08 | 瓮福（集团）有限责任公司 | Method for preparing battery-grade iron phosphate by using ferrophosphorus |
| CN106629646A (en) * | 2016-11-28 | 2017-05-10 | 荆门市格林美新材料有限公司 | Resource recovery method of lithium iron phosphate waste materials |
| CN106916956A (en) * | 2017-03-31 | 2017-07-04 | 广东佳纳能源科技有限公司 | A kind of method that solventing-out process reclaims valuable metal and recycling in LiFePO4 waste material |
| CN109250696A (en) * | 2017-07-12 | 2019-01-22 | 深圳佳彬科技有限公司 | A method of recycling nano ferric phosphate from ferric phosphate lithium cell |
| CN109950651A (en) * | 2019-04-03 | 2019-06-28 | 中南大学 | A kind of integrated conduct method of waste lithium iron phosphate battery recycling carbon |
| CN111333046A (en) * | 2020-03-26 | 2020-06-26 | 中国科学院过程工程研究所 | Resource recovery method and system for waste lithium iron phosphate anode based on hydrochloric acid circulation |
| CN111924817A (en) * | 2020-07-24 | 2020-11-13 | 中南大学 | Method for comprehensively utilizing waste lithium iron phosphate anode material |
| CN112331949A (en) * | 2020-11-12 | 2021-02-05 | 郑州中科新兴产业技术研究院 | Method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries |
Non-Patent Citations (1)
| Title |
|---|
| В.И.沙尔科夫: "《水解生产》", 31 January 1959, 轻工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611250A (en) * | 2021-07-16 | 2023-01-17 | 中国科学院过程工程研究所 | Method for recovering high-purity iron phosphate from waste lithium iron phosphate anode powder |
| CN115611250B (en) * | 2021-07-16 | 2024-04-02 | 中国科学院过程工程研究所 | Method for recycling high-purity ferric phosphate from waste lithium iron phosphate positive electrode powder |
| CN113912033A (en) * | 2021-10-15 | 2022-01-11 | 浙江天能新材料有限公司 | Method for recycling anode and cathode mixed powder of waste lithium iron phosphate battery with pre-positioned lithium extraction |
| CN114477118A (en) * | 2022-02-15 | 2022-05-13 | 合肥国轩循环科技有限公司 | Comprehensive treatment method for waste lithium iron phosphate battery positive electrode powder |
| CN115448335A (en) * | 2022-10-26 | 2022-12-09 | 埃索凯循环能源科技(广西)有限公司 | Recycling method of waste manganese iron phosphate lithium battery |
| CN115448335B (en) * | 2022-10-26 | 2024-01-23 | 埃索凯循环能源科技(广西)有限公司 | Recycling method of waste lithium iron manganese phosphate battery |
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