CN114941074A - Method for recovering valuable components of positive electrode material of waste lithium iron phosphate battery - Google Patents
Method for recovering valuable components of positive electrode material of waste lithium iron phosphate battery Download PDFInfo
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- CN114941074A CN114941074A CN202210576697.1A CN202210576697A CN114941074A CN 114941074 A CN114941074 A CN 114941074A CN 202210576697 A CN202210576697 A CN 202210576697A CN 114941074 A CN114941074 A CN 114941074A
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- lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering valuable components of a waste lithium iron phosphate battery positive electrode material, which comprises the following steps: pretreating waste lithium batteries to obtain lithium iron phosphate active substances and carbon powder; weighing carbon powder, lithium salt and lithium iron phosphate active substances according to a certain proportion, grinding and mixing uniformly, then putting into a crucible, then putting into a tubular furnace, and roasting for a period of time under the condition of inert gas to obtain a roasted product; treating the roasted product with ammonia water, filtering to obtain filtrate containing lithium and phosphorus and filter residue, adding carbonate into the filtrate to precipitate and recover lithium, and adding calcium salt to precipitate and recover phosphorus; and drying the filter residue, and then carrying out magnetic separation to obtain metal iron powder, wherein the residual carbon powder is recycled. The method can realize the high-efficiency recovery of lithium, phosphorus and iron elements in the waste lithium iron phosphate anode material and synchronously realize the utilization of cathode carbon powder.
Description
Technical Field
The invention relates to the technical field of waste battery recovery, in particular to a method for recovering valuable components of a positive electrode material of a waste lithium iron phosphate battery.
Background
The waste lithium battery mainly comprises a positive electrode material, a negative electrode material, a current collector, a diaphragm, electrolyte and the like, and can damage the ecological environment to different degrees if the waste lithium battery is not properly disposed or is exposed in the air for a long time. Meanwhile, the waste lithium battery material contains abundant valuable metal elements such as lithium, nickel, cobalt and the like, and has high recovery economic value. How to eliminate the pollution of the waste lithium battery from the source and realize the high-efficiency recovery and regeneration of the waste lithium battery is a hot problem influencing the world energy strategic pattern.
The waste lithium battery is recycled by mainly leaching metals in the anode material through inorganic acid, and then realizing metal separation and purification by means of multistage extraction or precipitation and the like, so that the resource recycling of the lithium battery is realized. The metal ion separation of the leachate in the wet recovery process has the problems of long recovery process, more raw material consumption, serious environmental pollution and the like, and the recovery efficiency is low because the lithium element is finally separated usually. In addition, the current method for recycling carbon powder in the waste lithium batteries is very lacking, and the carbon powder in the waste lithium batteries is usually stacked in a waste manner or used as fuel for treatment, so that the resource is greatly wasted.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for recovering valuable components of a waste lithium iron phosphate battery positive material, which can realize the high-efficiency recovery of lithium, phosphorus and iron elements in the waste lithium iron phosphate positive material and synchronously realize the utilization of negative carbon powder.
In order to achieve the technical effects, the invention provides the following technical scheme:
a method for recovering valuable components of a waste lithium iron phosphate battery positive electrode material comprises the following steps: (1) pretreating waste lithium batteries to obtain lithium iron phosphate active substances and carbon powder; (2) weighing carbon powder, lithium salt and lithium iron phosphate active substances according to a certain proportion, grinding and mixing uniformly, then putting into a crucible, then putting into a tubular furnace, and roasting for a period of time under the condition of inert gas to obtain a roasted product; (3) treating the roasted product with ammonia water, filtering to obtain filtrate containing lithium and phosphorus and filter residue, adding carbonate into the filtrate to precipitate and recover lithium, and adding calcium salt into the filtrate to precipitate and recover phosphorus; and drying the filter residue, and then carrying out magnetic separation to obtain metal iron powder, wherein the residual carbon powder is recycled.
The further technical scheme is that the pretreatment in the step (1) is to discharge and disassemble the waste lithium battery to obtain the lithium battery anode/cathode material; respectively carrying out pyrolysis treatment on the lithium battery anode/cathode material in a vacuum environment to obtain a lithium iron phosphate active substance and carbon powder.
The further technical scheme is that the pyrolysis temperature is 400-600 ℃, and the time is 60-90 min.
The further technical scheme is that the lithium salt is at least one of lithium hydroxide or lithium carbonate, the molar ratio of the lithium iron phosphate to the carbon powder is 1: 1-1: 4, and the addition amount of the lithium salt is 10-30% of the total mass of the lithium iron phosphate.
The further technical proposal is that the inert gas is at least one of nitrogen, argon and helium.
The further technical scheme is that in the step (2), the roasting temperature is 650-950 ℃, and the roasting time is 30-120 min.
The further technical scheme is that in the ammonia water treatment process in the step (3), the concentration of ammonia water is 5% -15%, the treatment time is 30-90 min, and the liquid-solid ratio of ammonia water to a roasted product is (3-9) ml:1 g.
The further technical scheme is that the drying temperature of the filter residue in the step (3) is 90-110 ℃, and the time is 4-8 hours.
Compared with the prior art, the invention has the following beneficial effects: the method realizes the full dissociation and high-efficiency recovery of three elements of phosphorus, iron and lithium in the lithium iron phosphate, and synchronously realizes the utilization of the cathode carbon powder; lithium salt is added to be used as an auxiliary agent to promote the reduction reaction, and simultaneously the lithium salt participates in the reaction to promote the sufficient dissociation and the respective recovery of the phosphorus element and the iron element; the recovery rate of lithium is higher, lithium is fully recovered, and the recovery rates of lithium, phosphorus and iron are all higher than 97%; the recovery process of the invention has no corrosive acid, does not discharge toxic gas into the environment and is more environment-friendly.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Discharging and disassembling the waste lithium iron phosphate battery to obtain a lithium battery positive/negative electrode material; and (3) pyrolyzing the lithium battery anode/cathode material at 400 ℃ for 90min in a vacuum environment to obtain the lithium iron phosphate active substance and carbon powder. Weighing carbon powder, a lithium iron phosphate active substance and lithium hydroxide according to the mol ratio of the lithium iron phosphate to the carbon powder of 1:1 and the addition amount of the lithium hydroxide of 10 percent of the lithium iron phosphate, grinding and mixing uniformly, putting into a crucible, putting into a tubular furnace, and roasting at 650 ℃ for 120min in a nitrogen environment to obtain a roasted product. Treating the roasted product in 5% ammonia water according to the liquid-solid ratio of 3ml/g for 90min, and filtering to obtain filtrate containing lithium and phosphorus and filter residue; adding sodium carbonate into the filtrate to precipitate and recover lithium, and adding lime water into the filtrate to precipitate and recover phosphorus; and drying the filter residue for 8 hours at 90 ℃, and then carrying out magnetic separation to obtain metal iron powder, wherein the residual carbon powder is recycled, and finally the recovery rate of lithium in the lithium iron phosphate positive active material is 97.2%, the recovery rate of phosphorus is 98.6%, and the recovery rate of iron is 97.4%.
Example 2
Discharging and disassembling the waste lithium iron phosphate battery to obtain a lithium battery positive/negative electrode material; carrying out pyrolysis treatment on the lithium battery anode/cathode material at 600 ℃ for 60min in a vacuum environment to obtain a lithium iron phosphate active substance and carbon powder. Weighing carbon powder, a lithium iron phosphate active substance and lithium carbonate according to the mol ratio of the lithium iron phosphate to the carbon powder of 1:4 and the addition amount of the lithium carbonate of 30 percent of the lithium iron phosphate, grinding and mixing uniformly, putting into a crucible, putting into a tubular furnace, and roasting for 30min at 950 ℃ in an argon environment to obtain a roasted product. Treating the roasted product in 15% ammonia water for 30min according to the liquid-solid ratio of 9ml/g, and filtering to obtain filtrate containing lithium and phosphorus and filter residue; adding sodium carbonate into the filtrate to precipitate and recover lithium, and adding lime water into the filtrate to precipitate and recover phosphorus; and drying the filter residue for 4 hours at 110 ℃, performing magnetic separation to obtain metal iron powder, recycling the residual carbon powder, and finally obtaining the lithium iron phosphate positive active material with the recovery rate of 99.1 percent, the phosphorus recovery rate of 98.9 percent and the iron recovery rate of 98.3 percent.
Example 3
Discharging and disassembling the waste lithium iron phosphate battery to obtain a lithium battery positive/negative electrode material; and (3) pyrolyzing the lithium battery anode/cathode material at 550 ℃ for 90min in a vacuum environment to obtain the lithium iron phosphate active substance and carbon powder. Weighing carbon powder, a lithium iron phosphate active substance and lithium hydroxide according to the mol ratio of the lithium iron phosphate to the carbon powder of 1:3 and the addition amount of the lithium hydroxide of 15 percent of the lithium iron phosphate, grinding and mixing uniformly, then putting the mixture into a crucible, putting the crucible into a tubular furnace, and roasting the crucible in a nitrogen environment at 850 ℃ for 75min to obtain a roasted product. Treating the roasted product in 10% ammonia water for 45min according to the liquid-solid ratio of 6ml/g, and filtering to obtain filtrate containing lithium and phosphorus and filter residue; adding sodium carbonate into the filtrate to precipitate and recover lithium, and adding lime water into the filtrate to precipitate and recover phosphorus; and drying the filter residue for 6 hours at 100 ℃, performing magnetic separation to obtain metal iron powder, recycling the residual carbon powder, and finally obtaining the lithium iron phosphate positive active material with the recovery rate of 98.5 percent, the phosphorus recovery rate of 97.6 percent and the iron recovery rate of 97.9 percent.
Although the invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be the only preferred embodiments of the invention, it is not intended that the invention be limited thereto, since many other modifications and embodiments will be apparent to those skilled in the art and will be within the spirit and scope of the principles of this disclosure.
Claims (8)
1. A method for recovering valuable components of a positive electrode material of a waste lithium iron phosphate battery is characterized by comprising the following steps: (1) pretreating waste lithium batteries to obtain lithium iron phosphate active substances and carbon powder; (2) weighing carbon powder, lithium salt and lithium iron phosphate active substances according to a certain proportion, grinding and mixing uniformly, then putting into a crucible, then putting into a tubular furnace, and roasting for a period of time under the condition of inert gas to obtain a roasted product; (3) treating the roasted product with ammonia water, filtering to obtain filtrate containing lithium and phosphorus and filter residue, adding carbonate into the filtrate to precipitate and recover lithium, and adding calcium salt into the filtrate to precipitate and recover phosphorus; and drying the filter residue, and then carrying out magnetic separation to obtain metal iron powder, wherein the residual carbon powder is recycled.
2. The method for recycling valuable components of the positive electrode material of the waste lithium iron phosphate batteries according to claim 1, wherein the pretreatment in the step (1) is to discharge and disassemble the waste lithium batteries to obtain the positive/negative electrode material of the lithium batteries; respectively carrying out pyrolysis treatment on the lithium battery anode/cathode material in a vacuum environment to obtain a lithium iron phosphate active substance and carbon powder.
3. The method for recycling valuable components of the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 2, wherein the pyrolysis temperature is 400-600 ℃ and the time is 60-90 min.
4. The method for recovering valuable components of the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 1, wherein the lithium salt is at least one of lithium hydroxide or lithium carbonate, the molar ratio of the lithium iron phosphate to the carbon powder is 1: 1-1: 4, and the addition amount of the lithium salt is 10% -30% of the total mass of the lithium iron phosphate.
5. The method for recovering valuable components of the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 1, wherein the inert gas is at least one selected from nitrogen, argon and helium.
6. The method for recovering valuable components of the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 1, wherein the roasting temperature in the step (2) is 650-950 ℃, and the roasting time is 30-120 min.
7. The method for recovering valuable components of the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 1, wherein the concentration of ammonia water in the ammonia water treatment process in the step (3) is 5% -15%, the treatment time is 30-90 min, and the liquid-solid ratio of ammonia water to a roasted product is (3-9) ml:1 g.
8. The method for recovering valuable components of the positive electrode material of the waste lithium iron phosphate battery as claimed in claim 1, wherein the drying temperature of the filter residue in the step (3) is 90-110 ℃, and the time is 4-8 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210576697.1A CN114941074A (en) | 2022-05-25 | 2022-05-25 | Method for recovering valuable components of positive electrode material of waste lithium iron phosphate battery |
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| CN202210576697.1A CN114941074A (en) | 2022-05-25 | 2022-05-25 | Method for recovering valuable components of positive electrode material of waste lithium iron phosphate battery |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108110357A (en) * | 2017-12-14 | 2018-06-01 | 眉山顺应动力电池材料有限公司 | A kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate |
| CN109811125A (en) * | 2019-01-21 | 2019-05-28 | 湖南邦普循环科技有限公司 | The method of ferrorphosphorus and lithium compound is recycled from waste lithium iron phosphate material |
| CN111170343A (en) * | 2019-12-23 | 2020-05-19 | 北京矿冶科技集团有限公司 | Method for recovering and producing lithium hydroxide from waste lithium ion battery |
| CN112111651A (en) * | 2020-09-21 | 2020-12-22 | 天齐锂业（江苏）有限公司 | Pyrogenic process recovery process of waste lithium ion battery powder |
| CN113562717A (en) * | 2021-07-28 | 2021-10-29 | 中南大学 | Method for recycling and regenerating waste lithium iron phosphate batteries at low temperature |
| CN114229812A (en) * | 2021-12-20 | 2022-03-25 | 中北大学 | Method for extracting iron and phosphorus from lithium iron phosphate waste |
| CN114394610A (en) * | 2021-12-20 | 2022-04-26 | 格林美股份有限公司 | Recovery method of waste lithium iron phosphate battery |
-
2022
- 2022-05-25 CN CN202210576697.1A patent/CN114941074A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108110357A (en) * | 2017-12-14 | 2018-06-01 | 眉山顺应动力电池材料有限公司 | A kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate |
| CN109811125A (en) * | 2019-01-21 | 2019-05-28 | 湖南邦普循环科技有限公司 | The method of ferrorphosphorus and lithium compound is recycled from waste lithium iron phosphate material |
| CN111170343A (en) * | 2019-12-23 | 2020-05-19 | 北京矿冶科技集团有限公司 | Method for recovering and producing lithium hydroxide from waste lithium ion battery |
| CN112111651A (en) * | 2020-09-21 | 2020-12-22 | 天齐锂业（江苏）有限公司 | Pyrogenic process recovery process of waste lithium ion battery powder |
| CN113562717A (en) * | 2021-07-28 | 2021-10-29 | 中南大学 | Method for recycling and regenerating waste lithium iron phosphate batteries at low temperature |
| CN114229812A (en) * | 2021-12-20 | 2022-03-25 | 中北大学 | Method for extracting iron and phosphorus from lithium iron phosphate waste |
| CN114394610A (en) * | 2021-12-20 | 2022-04-26 | 格林美股份有限公司 | Recovery method of waste lithium iron phosphate battery |
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Effective date of registration: 20230306 Address after: No. 678, Huaihe East Road, Huaiyin District, Huai'an City, Jiangsu Province, 223300 Applicant after: Jiangsu Gerun New Material Co.,Ltd. Address before: No. 6-1, Hanzhuang Road, Huangqiao Economic Development Zone, Taixing City, Taizhou City, Jiangsu Province, 225400 Applicant before: Jiangsu Green New Material Technology Co.,Ltd. |
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