CN102903985A - Method for recycling lithium carbonate from lithium iron phosphate waste material - Google Patents
Method for recycling lithium carbonate from lithium iron phosphate waste material Download PDFInfo
- Publication number
- CN102903985A CN102903985A CN2012104060159A CN201210406015A CN102903985A CN 102903985 A CN102903985 A CN 102903985A CN 2012104060159 A CN2012104060159 A CN 2012104060159A CN 201210406015 A CN201210406015 A CN 201210406015A CN 102903985 A CN102903985 A CN 102903985A
- Authority
- CN
- China
- Prior art keywords
- lifepo
- waste material
- lithium
- battery
- lithium carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to a method for recycling lithium carbonate from a lithium iron phosphate waste material, and belongs to the technical field of waste lithium oil battery recycling. The technical problem to be solved by the invention is that a method for recycling lithium carbonate from the lithium iron phosphate waste material is provided. The method provided by the invention comprises the following steps of: roasting the lithium iron phosphate waste material at 500-800 DEG C for 1-4 hours; adding sulfur into the roasted waste material and leaching, and filtering so as to obtain a mixed solution of lithium phosphate, iron phosphate and ferric sulfate; heating the mixed solution to 80-100 DEG C, and adjusting the pH value to 2-2.5, reacting for 1-4 hours, filtering, washing, and drying to obtain iron phosphate; adjusting the pH value of a filtrate obtained by filtering to be 6-7, adding calcium chloride and dephosphorizing, and filtering; and adjusting the pH value of the filtrate obtained by filtering to be 10-12 by sodium carbonate, reacting for 0.5-2 hours, filtering, washing, and drying so as to obtain battery grade lithium carbonate.
Description
Technical field
The present invention relates to from the LiFePO 4 waste material, reclaim the method for lithium carbonate, belong to waste and old lithium ion battery recovery and utilization technology field.
Background technology
Lithium ion battery is the green battery with a series of premium properties, comes out 10 for many years, is widely used.LiFePO 4 (LiFePO
4) material is owing to have characteristics such as high safety, high-environmental, low price, long-life, become the preferred material of generally acknowledged lithium-ion-power cell, and the lithium ion battery take LiFePO 4 as positive electrode the electrokinetic cell fields such as electric tool, electric bicycle, vehicle using motor, golf cart, ship model toy, mine lamp now have been widely used in.Car manufactures is also being tested use ferrousphosphate lithium material in startup power supply lithium ion battery (12V/24V 50Ah) repeatedly.Following this material also has development space in fields such as mobile communication base station, energy storage devices.
Along with the extensive use of lithium ion battery, will enter in a large number inefficacy, recovery stage.How to reclaim waste and old lithium ion battery and the resource recycling utilization has become social question of common concern.For the purpose of resource circulation utilization and industry sustainable development, tackling wherein, elemental lithium reclaims.
Lithium ion battery is comprised of shell and inner battery core.The shell of battery is stainless steel or nickel plating box hat, and the different models such as square and cylindrical are arranged.Inner battery core is rolled structure, is comprised of major parts such as positive pole, electrolyte and negative poles, and positive plate mainly is made of aluminium foil, organic binder bond and lithium salts (LiFePO 4); And negative plate is mainly Copper Foil and graphite, relatively single, the easy separation of the composition of negative material.The recycling of waste lithium ion cell anode material becomes the emphasis of people's research.Its recycling technology mainly is divided into following three classes:
(1) adopt the mode of roasting direct to reclaim LiFePO 4, such as, Chinese patent application 200710129898.2, the recovery method of lithium iron phosphate cathode material in a kind of lithium ion battery waste material, it toasts described waste material 2-5 hour under 450-600 ℃ under the atmosphere of inert gas, then mixes drying in the ethanolic solution with described powdered product adding soluble ferric iron salt, under the atmosphere of inert gas, at 300-500 ℃ of lower roasting 2-5 hour, reclaim and obtain lithium iron phosphate cathode material.Chinese patent application 200710076890.4, the comprehensive recovering process of the useless sheet of a kind of ferrous phosphate lithium battery anode comprises following steps: the anode material waste sheet Mechanical Crushing of collecting is fragmentated; Fragment is placed by the sintering furnace under vacuum atmosphere, inert gas and/or reducibility gas and/or the nitrogen protection, under 150-750 ℃ temperature, heat-treat; Adopt machinery to separate or the ultrasonic oscillation method fragment after the heat treatment, the aluminium foil matrix is separated from fragment, obtain the mixture of lithium iron phosphate cathode material, conductive agent and adhesive residue thing; With the mixture of lithium iron phosphate cathode material, conductive agent and adhesive residue thing, baking is 8-24 hour under 80-150 ℃ of temperature; With classification behind the mixture abrasive dust after the baking, the particle diameter of control powder is not more than 20 μ m, and D50 is controlled at 3-10 μ m, namely gets the ferrous lithium phosphate cathode reclaimed materials.
Although the method is simple, energy consumption is slightly high, and product alloy purity is lower, reclaims the LiFePO 4 that obtains, and is of low quality, can not use as cell positive material.
(2) will just directly recycle behind the simple cleaning-drying of ferrous lithium phosphate cathode sheet process.Such as, Chinese patent application 200980100912.3, a kind of recoverying and utilizing method of waste and old ferrous phosphate lithium dynamical battery, after first described waste and old ferrous phosphate lithium battery being discharged fully, battery is moved in the vacuum glove box that is filled with nitrogen protection, open the cover plate of described battery with mechanical force, take out the battery core that is contained in this battery case; Cover plate and battery case are shifted out glove box, recycle after treatment polypropylene PP plastics, steel or the aluminium of described cover plate and battery case; In described vacuum glove box, separate again negative plate and barrier film, and positive plate; Wherein negative plate and barrier film are recycled after treatment; And positive plate cooperates new negative plate making to become new ferrous phosphate lithium dynamical battery after cleaning, dry, screening.
The possibility that this mode can realize smoothly is not high.
(3) adopt the mode of sour molten precipitation to reclaim LiFePO 4.Such as Chinese patent application, 201010148325.6, a kind of waste and old ferrous phosphate lithium battery comprehensive recovering process, the method is utilized the binding agent on the organic solvent dissolution battery core fragment, by screening, realize that ferrousphosphate lithium material separates with clean aluminium, Copper Foil, wherein aluminium, Copper Foil reclaim by melting; Utilize NaOH solution to remove aluminium foil bits remaining in the ferrousphosphate lithium material, remove graphite and remaining binding agent by heat treatment.After LiFePO 4 usefulness acid dissolving, utilize vulcanized sodium to remove copper ion wherein, and utilize NaOH solution or ammoniacal liquor to make iron in the solution, lithium, phosphonium ion generate sediment, and in sediment, add source of iron, lithium source or P source compound to adjust the mol ratio of iron, lithium, phosphorus, add at last carbon source, calcining obtains new lithium iron phosphate cathode material in ball milling, inert atmosphere.Chinese patent application 201010253859.5, a kind of water-system waste lithium-ion-power cell reclaims the method for preparing LiFePO 4, concrete steps are as follows: 1) with behind the water-system waste lithium ion battery shearing-crushing, processed by deionized water, dry rear electrode material and the conductive agent mixture of reclaiming sieves; 2) dried electrode material and conductive agent mixture adding inorganic acid are processed, filtered and obtain Li
+, Fe
2+, PO
4 3-Acid solution; 3) to containing Li
+, Fe
2+, PO
4 3-Acid solution in add lithium salts or molysite, add ascorbic acid and stir, control pH value=3-7; Filter, be precipitated; 4) LiFePO that step 3) is obtained
4Thick product joins and carries out ball milling, the LiFePO that drying and calcining obtains regenerating in the aqueous sucrose solution
4Material.
If the said method impurity removal gets totally, in theory should be feasible.But because the quality of raw material alters a great deal, homogeneity of product is difficult to be guaranteed, and can not satisfy the needs that LiFePO 4 is reclaimed in industrialized production.
Therefore, at present the research of the recycling of waste lithium ion cell anode material is remained the hot issue of social common concern.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method that reclaims lithium carbonate from the LiFePO 4 waste material.
The present invention reclaims lithium carbonate from the LiFePO 4 waste material method comprises the steps:
A, roasting: the LiFePO 4 waste material is in 500～800 ℃ of roasting 1～4h; Wherein, can the baking furnace of routine as: carry out roasting in the rotary kiln;
B, leaching: the material after the roasting adds sulfuric acid leaching, and the pH value is controlled at 0.5～1 during leaching, filters the mixed solution that obtains lithium phosphate, ferric phosphate and ferric sulfate;
C, precipitate phosphoric acid iron: b step gained mixed solution is heated to 80～100 ℃, and regulates pH value to 2～2.5, reaction 1～4h, and filtration, washing, drying obtain ferric phosphate;
D, removal of impurities: the c step is filtered the filtrate of gained and is regulated pH value 6～7, adds the calcium chloride dephosphorization, filters;
E, precipitation lithium carbonate: the d step is filtered the filtrate of gained and is regulated pH value to 10～12 with sodium carbonate, reaction 0.5～2h, and filtration, washing, drying obtain battery-level lithium carbonate.
Wherein, LiFePO 4 waste material in the said method can be the LiFePO 4 waste material that produces in the LiFePO 4 waste material that produces in the LiFePO 4 production process or the battery production process, also can adopt following methods to reclaim obtains: old and useless battery is disassembled battery after discharging fully, separate negative plate and barrier film, and positive plate, positive plate is heated to 300-400 ℃ of heat treatment 1～4h, the matrix aluminium foil is separated with positive electrode, and the mixture that obtains lithium iron phosphate cathode material, conductive agent and adhesive residue thing is the LiFePO 4 waste material; Perhaps adopt to reclaim in useless positive plate that said method produces from Production Process of Lithium Battery or the inferior positive plate and obtain the LiFePO 4 waste material; It perhaps is the LiFePO 4 waste material that produces in the positive plate production process of lithium battery.
Further, preferred machinery separation, the separation of ultrasonic oscillation method or the organic solvent of adopting soaks matrix separation aluminium foil and positive electrode in the said method; Wherein, described organic solvent is at least a in 1-METHYLPYRROLIDONE (NMP), DMA (DMA), the dimethyl formamide (DMF).Organic solvent soaks dissolving binding agent wherein, and sheet metal is reclaimed in screening, can collect after the screening and obtain the LiFePO 4 waste material.
In the roasting process phase conversion reaction can occur, the iron in the LiFePO 4 changes trivalent into by divalence.
Sintering temperature is crossed low reaction and can not be carried out, but temperature is also unsuitable too high, prevents the material caking.As preferred scheme, sintering temperature is advisable with 500～800 ℃.The calcination formula is:
6LiFePO
4+3O
2＝4FePO
4+2Li
3PO
4+Fe
2O
3
Wherein, in the b step, the material after the roasting adds Ore Leaching can add sulfuric acid, hydrochloric acid etc., because hydrochloric acid is volatile, considers operational environment, and the material after the roasting preferably adds sulfuric acid leaching.Further, described sulfuric acid concentration is preferably 93～98wt%.
Further, in order to obtain high-purity phosphoric acid iron and lithium carbonate, temperature of washing water preferably is controlled at 40～100 ℃ in above-mentioned c, the e step.
Beneficial effect of the present invention: the present inventor provides a kind of brand-new method from the another one angle, and the low-cost LiFePO 4 waste material of recycling becomes ferric phosphate with it and lithium carbonate reclaims respectively.Solved ferrous phosphate lithium dynamical battery resource recycling problem, for trouble and worry is removed in the development of electric automobile.
Description of drawings
Fig. 1 is the flow chart of one of embodiment of LiFePO 4 recovery technique of the present invention.
Fig. 2 is two flow chart of the LiFePO 4 of the present invention embodiment that reclaims technique.
Embodiment
The present invention reclaims lithium carbonate from the LiFePO 4 waste material method comprises the steps:
A, roasting: the LiFePO 4 waste material is in 500～800 ℃ of roasting 1～4h; Wherein, can the baking furnace of routine as: carry out roasting in the rotary kiln;
B, leaching: the material after the roasting adds sulfuric acid leaching, and the pH value is controlled at 0.5～1 during leaching, filters the mixed solution that obtains lithium phosphate, ferric phosphate and ferric sulfate;
C, precipitate phosphoric acid iron: b step gained mixed solution is heated to 80～100 ℃, and regulates pH value to 2～2.5, reaction 1～4h, and filtration, washing, drying obtain ferric phosphate;
D, removal of impurities: the c step is filtered the filtrate of gained and is regulated pH value 6～7, adds the calcium chloride dephosphorization, filters;
E, precipitation lithium carbonate: the d step is filtered the filtrate of gained and is regulated pH value to 10～12 with sodium carbonate, reaction 0.5～2h, and filtration, washing, drying obtain battery-level lithium carbonate.
Wherein, LiFePO 4 waste material in the said method can be the LiFePO 4 waste material that produces in the LiFePO 4 waste material that produces in the LiFePO 4 production process or the battery production process, also can adopt following methods to reclaim obtains: old and useless battery is disassembled battery after discharging fully, separate negative plate and barrier film, and positive plate, positive plate is heated to 300-400 ℃ of heat treatment 1～4h, the matrix aluminium foil is separated with positive electrode, and the mixture that obtains lithium iron phosphate cathode material, conductive agent and adhesive residue thing is the LiFePO 4 waste material; Perhaps adopt to reclaim in useless positive plate that said method produces from Production Process of Lithium Battery or the inferior positive plate and obtain the LiFePO 4 waste material; It perhaps is the LiFePO 4 waste material that produces in the positive plate production process of lithium battery.
Further, preferred machinery separation, the separation of ultrasonic oscillation method or the organic solvent of adopting soaks matrix separation aluminium foil and positive electrode in the said method; Wherein, described organic solvent is at least a in 1-METHYLPYRROLIDONE (NMP), DMA (DMA), the dimethyl formamide (DMF).Organic solvent soaks dissolving binding agent wherein, and sheet metal is reclaimed in screening, can collect after the screening and obtain the LiFePO 4 waste material.
In the roasting process phase conversion reaction can occur, the iron in the LiFePO 4 changes trivalent into by divalence.
Sintering temperature is crossed low reaction and can not be carried out, but temperature is also unsuitable too high, prevents the material caking.As preferred scheme, sintering temperature is advisable with 500～800 ℃.The calcination formula is:
6LiFePO
4+3O
2＝4FePO
4+2Li
3PO
4+Fe
2O
3
Wherein, in the b step, the material after the roasting adds Ore Leaching can add sulfuric acid, hydrochloric acid etc., because hydrochloric acid is volatile, considers operational environment, and the material after the roasting preferably adds sulfuric acid leaching.Further, described sulfuric acid concentration is preferably 93～98wt%.
Further, in order to obtain high-purity phosphoric acid iron and lithium carbonate, temperature of washing water preferably is controlled at 40～100 ℃ in above-mentioned c, the e step.
Below in conjunction with embodiment the specific embodiment of the present invention is further described, does not therefore limit the present invention among the described scope of embodiments.
Following examples are implemented by following execution mode:
A. waste and old ferrous phosphate lithium battery remaining capacity is discharged, then disassemble battery, take out positive plate.
B. will pulverize behind 300-400 ℃ of roasting 1～4h of ferrous lithium phosphate cathode sheet.
C. anodal aluminium flake is reclaimed in screening, gets the LiFePO 4 waste material.
D. LiFePO 4 waste material 500-800 ℃ of roasting 1～4h.
E. material adds 93%～98% sulfuric acid leaching after the roasting, filters to obtain ferric phosphate, lithium phosphate, ferric sulfate mixed solution.
F. lithium phosphate, ferric phosphate, ferric sulfate mixed solution are heated to 80-100 ℃, and regulate the pH value to 2-2.5, react 1-4 hour, and filtration, washing, drying obtain ferric phosphate.
G.f step filtrate is regulated pH value 6-7,, add calcium chloride and remove a small amount of foreign matter of phosphor.
The filtrate that the h.g step obtains is regulated the pH value to 10-12 with sodium carbonate, reacts 0.5-2 hour, and filtration, washing, drying obtain battery-level lithium carbonate.The lithium rate of recovery reaches more than 80% in the LiFePO 4 waste material.
Wherein, step a-h is applicable to old and useless battery and reclaims, for the LiFePO 4 waste material that produces in the LiFePO 4 waste material that produces in the LiFePO 4 production process or the battery production process, directly from steps d.
Embodiment 1 adopts the inventive method comprehensive reutilization LiFePO 4 waste material
Waste and old ferrous phosphate lithium dynamical battery remaining capacity is discharged, disassemble battery, take out positive plate, battery case is pressed the classification such as aluminum hull, box hat, plastics and is reclaimed; With 400 ℃ of roasting 1h of ferrous lithium phosphate cathode sheet, anodal aluminium flake is reclaimed in screening after pulverizing; LiFePO 4 waste material 100kg, lithium content 3.5%.
Then 800 ℃ of roastings of LiFePO 4 waste material 1 hour add water and size mixing, and add 98% concentrated sulfuric acid adjusting pH value to 0.5, filter and obtain ferric phosphate, lithium phosphate, ferric sulfate mixed solution; Mixed solution is heated to 80 ℃, adds alkali and regulate pH value to 2.0, reaction 4h filters and obtains raw phosphoric acid iron, obtains ferric phosphate through 40 ℃ of water washings, dryings again; Filtrate is regulated pH value to 6, adds 100g calcium chloride, then filtering and impurity removing; The removal of impurities rear filtrate is regulated pH value to 12 with sodium carbonate, reacts 0.5 hour, filters and obtains Crude lithium Carbonate, obtains lithium carbonate 15.12kg through 40 ℃ of water washings, dryings.Shown in table 1,2, the lithium carbonate quality satisfies YS/T 582-2006 LITHIUM BATTERY standard-required to the purity of gained ferric phosphate and lithium carbonate respectively.
Table 1
Table 2
After testing, the lithium rate of recovery is 81.55% in the LiFePO 4 waste material.
Embodiment 2 adopts the inventive method comprehensive reutilization LiFePO 4 waste material
The LiFePO 4 waste material 100kg that produces in the production process of power taking pond, lithium content 3.52%.Then 600 ℃ of roastings of LiFePO 4 waste material 2 hours add water and size mixing, and add 98% concentrated sulfuric acid adjusting pH value to 0.8, filter and obtain ferric phosphate, lithium phosphate, ferric sulfate mixed solution; Mixed solution is heated to 90 ℃, adds alkali and regulate pH value to 2.3, reaction 2h filters and obtains raw phosphoric acid iron, obtains ferric phosphate through 60 ℃ of water washings, dryings again; Filtrate is regulated pH value to 7, adds calcium chloride 100g, then filtering and impurity removing; The removal of impurities rear filtrate is regulated pH value to 11 with sodium carbonate, reacts 1 hour, filters and obtains Crude lithium Carbonate, obtains lithium carbonate 15.4kg through 60 ℃ of water washings, dryings.Shown in table 3,4, the lithium carbonate quality satisfies YS/T 582-2006 battery-level lithium carbonate standard-required to the purity of gained ferric phosphate and lithium carbonate respectively.
Table 3
Table 4
After testing, the lithium rate of recovery is 83.21% in the LiFePO 4 waste material.
Embodiment 3 adopts the inventive method comprehensive reutilization LiFePO 4 waste material
Get the LiFePO 4 waste material 100kg that produces in the LiFePO 4 production process, lithium content 4.38%.Then 500 ℃ of roastings of LiFePO 4 waste material 4 hours add water and size mixing, and add 98% concentrated sulfuric acid adjusting pH value to 1, filter and obtain ferric phosphate, lithium phosphate, ferric sulfate mixed solution; Mixed solution is heated to 100 ℃, adds alkali and regulate pH value to 2.5, reaction 1h filters and obtains raw phosphoric acid iron, obtains ferric phosphate through 80 ℃ of water washings, dryings again; Filtrate is regulated pH value to 6, adds 100g calcium chloride, then filtering and impurity removing; The removal of impurities rear filtrate is regulated pH value to 10 with sodium carbonate, reacts 2 hours, filters and obtains Crude lithium Carbonate, obtains lithium carbonate 15.2kg through 100 ℃ of water washings, dryings.Shown in table 5,6, the lithium carbonate quality satisfies YS/T 582-2006 battery-level lithium carbonate standard-required to the purity of gained ferric phosphate and lithium carbonate respectively.
Table 5
Table 6
After testing, the lithium rate of recovery is 82.31% in the LiFePO 4 waste material.
Claims (5)
1. from the LiFePO 4 waste material, reclaim the method for lithium carbonate, it is characterized in that comprising the steps:
A, roasting: the LiFePO 4 waste material is in 500～800 ℃ of roasting 1～4h;
B, leaching: the material after the roasting adds sulfuric acid leaching, and the pH value is controlled at 0.5～1 during leaching, filters the mixed solution that obtains lithium phosphate, ferric phosphate and ferric sulfate;
C, precipitate phosphoric acid iron: b step gained mixed solution is heated to 80～100 ℃, and regulates pH value to 2～2.5, reaction 1～4h, and filtration, washing, drying obtain ferric phosphate;
D, removal of impurities: the c step is filtered the filtrate of gained and is regulated pH value 6～7, adds the calcium chloride dephosphorization, filters;
E, precipitation lithium carbonate: the d step is filtered the filtrate of gained and is regulated pH value to 10～12 with sodium carbonate, reaction 0.5～2h, and filtration, washing, drying obtain battery-level lithium carbonate.
2. the method that from the LiFePO 4 waste material, reclaims lithium carbonate according to claim 1, it is characterized in that: described LiFePO 4 waste material is the LiFePO 4 waste material that produces in the LiFePO 4 waste material that produces in the LiFePO 4 production process or the battery production process, or adopt the following methods recovery to obtain: old and useless battery is disassembled battery after discharging fully, separate negative plate and barrier film, and positive plate, positive plate is heated to 300-400 ℃ of heat treatment 1～4h, the matrix aluminium foil is separated with positive electrode, obtain lithium iron phosphate cathode material, the mixture of conductive agent and adhesive residue thing is the LiFePO 4 waste material;
Perhaps adopt to reclaim in useless positive plate that said method produces from Production Process of Lithium Battery or the inferior positive plate and obtain the LiFePO 4 waste material;
It perhaps is the LiFePO 4 waste material that produces in the positive plate production process of lithium battery.
3. the method that reclaims lithium carbonate from the LiFePO 4 waste material according to claim 2 is characterized in that: adopt machinery separation, the separation of ultrasonic oscillation method or organic solvent to soak matrix separation aluminium foil and positive electrode; Wherein, described organic solvent is at least a in 1-METHYLPYRROLIDONE (NMP), DMA (DMA), the dimethyl formamide (DMF).
4. each described method that reclaims lithium carbonate from the LiFePO 4 waste material according to claim 1～3, it is characterized in that: in the b step, described sulfuric acid concentration is 93～98wt%.
5. each described method that reclaims lithium carbonate from the LiFePO 4 waste material according to claim 1～4 is characterized in that: the water temperature in c, the e step during washing is 40～100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210406015.9A CN102903985B (en) | 2012-10-22 | 2012-10-22 | Method for recycling lithium carbonate from lithium iron phosphate waste material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210406015.9A CN102903985B (en) | 2012-10-22 | 2012-10-22 | Method for recycling lithium carbonate from lithium iron phosphate waste material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102903985A true CN102903985A (en) | 2013-01-30 |
| CN102903985B CN102903985B (en) | 2014-09-24 |
Family
ID=47576121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210406015.9A Active CN102903985B (en) | 2012-10-22 | 2012-10-22 | Method for recycling lithium carbonate from lithium iron phosphate waste material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102903985B (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103259063A (en) * | 2013-05-13 | 2013-08-21 | 宁夏东方钽业股份有限公司 | Method for recycling transition metal from waste lithium ion battery positive pole material or precursor thereof containing at least one of Mn and Co |
| CN103474719A (en) * | 2013-08-30 | 2013-12-25 | 国家电网公司 | Method for recycling positive electrode of LiFePO4 battery |
| CN104338441A (en) * | 2014-10-17 | 2015-02-11 | 南京格洛特环境工程股份有限公司 | Treatment process of lithium precipitation mother solution |
| 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 |
| CN106129519A (en) * | 2016-08-25 | 2016-11-16 | 合肥国轩高科动力能源有限公司 | The method that ferric phosphate lithium cell prepares lithium carbonate is scrapped in a kind of employing |
| CN106450547A (en) * | 2016-10-19 | 2017-02-22 | 荆门市格林美新材料有限公司 | Method for recycling iron phosphate and lithium carbonate from lithium iron phosphate waste |
| CN106495190A (en) * | 2016-09-12 | 2017-03-15 | 天津科技大学 | A kind of calcining of abraum salt containing lithium recovery method |
| JP2017052997A (en) * | 2015-09-09 | 2017-03-16 | 太平洋セメント株式会社 | Lithium extraction method |
| CN106684486A (en) * | 2016-12-28 | 2017-05-17 | 天津先众新能源科技股份有限公司 | Method for extracting lithium from waste lithium iron phosphate |
| CN106785166A (en) * | 2016-12-12 | 2017-05-31 | 江西赣锋锂业股份有限公司 | The method that lithium prepares battery-level lithium carbonate is reclaimed in a kind of old and useless battery from LiFePO 4 |
| CN106997973A (en) * | 2017-05-12 | 2017-08-01 | 湖南省正源储能材料与器件研究所 | The phosphatic method of ferric phosphate and lithium is prepared in a kind of anode material from waste lithium iron phosphate |
| CN107720716A (en) * | 2017-11-21 | 2018-02-23 | 成都开飞高能化学工业有限公司 | The technique for preparing battery-level lithium carbonate and ferric phosphate from crude product lithium phosphate recovery lithium phosphorus |
| 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 |
| CN108336442A (en) * | 2018-03-01 | 2018-07-27 | 中国科学院过程工程研究所 | A method of detaching aluminium foil and anode waste from lithium ion battery positive plate |
| CN108394919A (en) * | 2018-02-02 | 2018-08-14 | 东北石油大学 | Application of the complexing of metal ion agent in waste lithium iron phosphate battery removal process |
| CN108767353A (en) * | 2018-05-25 | 2018-11-06 | 北京矿冶科技集团有限公司 | The method for producing rich lithium net liquid from waste lithium ion cell anode active material |
| WO2018209164A1 (en) * | 2017-05-11 | 2018-11-15 | Worcester Polytechnic Institute | Method and apparatus for recycling lithium iron phosphate batteries |
| CN109689573A (en) * | 2016-09-05 | 2019-04-26 | 株式会社Posco | The preparation method of lithium chloride and the preparation method of lithium carbonate |
| CN110649342A (en) * | 2018-06-26 | 2020-01-03 | 中天储能科技有限公司 | Method for recycling positive active material of waste lithium iron phosphate battery |
| US10741890B2 (en) | 2012-04-04 | 2020-08-11 | Worcester Polytechnic Institute | Method and apparatus for recycling lithium iron phosphate batteries |
| CN113104866A (en) * | 2021-03-30 | 2021-07-13 | 中国石油大学(北京) | Method for preparing battery-grade lithium carbonate from lithium iron phosphate waste |
| CN113285135A (en) * | 2021-05-07 | 2021-08-20 | 宁夏百川新材料有限公司 | Method for recycling multiple components of waste lithium iron phosphate battery |
| CN113621802A (en) * | 2020-05-07 | 2021-11-09 | 贵州中伟资源循环产业发展有限公司 | Method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole piece |
| CN115072748A (en) * | 2022-06-09 | 2022-09-20 | 江西春鹏锂业有限责任公司 | Clean production method and production system of battery-grade lithium carbonate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555030A (en) * | 2009-05-04 | 2009-10-14 | 佛山市邦普镍钴技术有限公司 | Method for recovering and recycling waste lithium ion battery cathode material |
| CN101723343A (en) * | 2009-12-24 | 2010-06-09 | 四川大学 | Method for reducing influences of impurity elements in ferrophosphorus on LixFeyPzO4 |
| CN101759174A (en) * | 2009-12-18 | 2010-06-30 | 四川大学 | Process for reducing impacts on LixFeyPzO4 caused by impurity elements in ferrophosphorus |
| CN102170036A (en) * | 2010-02-26 | 2011-08-31 | 比亚迪股份有限公司 | Recycling method of lithium iron phosphate cathode materials |
| CN102208706A (en) * | 2011-05-04 | 2011-10-05 | 合肥国轩高科动力能源有限公司 | Recycling treatment method of waste and old lithium iron phosphate battery anode materials |
| KR20120015658A (en) * | 2010-08-12 | 2012-02-22 | 재단법인 포항산업과학연구원 | Method for recovering with high purity lithium, lithium carbonate, lithium hydroxide and synthetic method of cathod material for lithium secondary battery from sea water |
| CN103370829A (en) * | 2011-02-15 | 2013-10-23 | 住友化学株式会社 | Method of recovering active material from scrap battery material |
-
2012
- 2012-10-22 CN CN201210406015.9A patent/CN102903985B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555030A (en) * | 2009-05-04 | 2009-10-14 | 佛山市邦普镍钴技术有限公司 | Method for recovering and recycling waste lithium ion battery cathode material |
| CN101759174A (en) * | 2009-12-18 | 2010-06-30 | 四川大学 | Process for reducing impacts on LixFeyPzO4 caused by impurity elements in ferrophosphorus |
| CN101723343A (en) * | 2009-12-24 | 2010-06-09 | 四川大学 | Method for reducing influences of impurity elements in ferrophosphorus on LixFeyPzO4 |
| CN102170036A (en) * | 2010-02-26 | 2011-08-31 | 比亚迪股份有限公司 | Recycling method of lithium iron phosphate cathode materials |
| KR20120015658A (en) * | 2010-08-12 | 2012-02-22 | 재단법인 포항산업과학연구원 | Method for recovering with high purity lithium, lithium carbonate, lithium hydroxide and synthetic method of cathod material for lithium secondary battery from sea water |
| CN103370829A (en) * | 2011-02-15 | 2013-10-23 | 住友化学株式会社 | Method of recovering active material from scrap battery material |
| CN102208706A (en) * | 2011-05-04 | 2011-10-05 | 合肥国轩高科动力能源有限公司 | Recycling treatment method of waste and old lithium iron phosphate battery anode materials |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10741890B2 (en) | 2012-04-04 | 2020-08-11 | Worcester Polytechnic Institute | Method and apparatus for recycling lithium iron phosphate batteries |
| CN103259063A (en) * | 2013-05-13 | 2013-08-21 | 宁夏东方钽业股份有限公司 | Method for recycling transition metal from waste lithium ion battery positive pole material or precursor thereof containing at least one of Mn and Co |
| CN103259063B (en) * | 2013-05-13 | 2016-01-13 | 宁夏东方钽业股份有限公司 | The method of transition metal is reclaimed from the waste and old anode material for lithium-ion batteries containing at least one Co and Mn or its presoma |
| CN103474719A (en) * | 2013-08-30 | 2013-12-25 | 国家电网公司 | Method for recycling positive electrode of LiFePO4 battery |
| CN103474719B (en) * | 2013-08-30 | 2015-08-19 | 国家电网公司 | A kind of for LiFePO 4the recovery method of anode |
| CN104338441A (en) * | 2014-10-17 | 2015-02-11 | 南京格洛特环境工程股份有限公司 | Treatment process of lithium precipitation mother solution |
| 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 |
| CN104953200B (en) * | 2015-06-30 | 2017-06-23 | 哈尔滨工业大学 | Battery-grade iron phosphate and the method that lithium iron phosphate positive material is prepared using waste lithium iron phosphate battery are reclaimed in ferric phosphate lithium cell |
| JP2017052997A (en) * | 2015-09-09 | 2017-03-16 | 太平洋セメント株式会社 | Lithium extraction method |
| CN106129519A (en) * | 2016-08-25 | 2016-11-16 | 合肥国轩高科动力能源有限公司 | The method that ferric phosphate lithium cell prepares lithium carbonate is scrapped in a kind of employing |
| CN109689573A (en) * | 2016-09-05 | 2019-04-26 | 株式会社Posco | The preparation method of lithium chloride and the preparation method of lithium carbonate |
| CN106495190B (en) * | 2016-09-12 | 2018-03-09 | 天津科技大学 | A kind of calcining of abraum salt containing lithium recovery method |
| CN106495190A (en) * | 2016-09-12 | 2017-03-15 | 天津科技大学 | A kind of calcining of abraum salt containing lithium recovery method |
| CN106450547B (en) * | 2016-10-19 | 2020-03-27 | 荆门市格林美新材料有限公司 | Method for recovering iron phosphate and lithium carbonate from lithium iron phosphate waste |
| CN106450547A (en) * | 2016-10-19 | 2017-02-22 | 荆门市格林美新材料有限公司 | Method for recycling iron phosphate and lithium carbonate from lithium iron phosphate waste |
| CN106785166A (en) * | 2016-12-12 | 2017-05-31 | 江西赣锋锂业股份有限公司 | The method that lithium prepares battery-level lithium carbonate is reclaimed in a kind of old and useless battery from LiFePO 4 |
| CN106785166B (en) * | 2016-12-12 | 2019-02-12 | 江西赣锋锂业股份有限公司 | A method of lithium, which is recycled, from LiFePO 4 old and useless battery prepares battery-level lithium carbonate |
| CN106684486A (en) * | 2016-12-28 | 2017-05-17 | 天津先众新能源科技股份有限公司 | Method for extracting lithium from waste lithium iron phosphate |
| WO2018209164A1 (en) * | 2017-05-11 | 2018-11-15 | Worcester Polytechnic Institute | Method and apparatus for recycling lithium iron phosphate batteries |
| CN106997973A (en) * | 2017-05-12 | 2017-08-01 | 湖南省正源储能材料与器件研究所 | The phosphatic method of ferric phosphate and lithium is prepared in a kind of anode material from waste lithium iron phosphate |
| CN107720716A (en) * | 2017-11-21 | 2018-02-23 | 成都开飞高能化学工业有限公司 | The technique for preparing battery-level lithium carbonate and ferric phosphate from crude product lithium phosphate recovery lithium phosphorus |
| 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 |
| CN108394919A (en) * | 2018-02-02 | 2018-08-14 | 东北石油大学 | Application of the complexing of metal ion agent in waste lithium iron phosphate battery removal process |
| CN108336442A (en) * | 2018-03-01 | 2018-07-27 | 中国科学院过程工程研究所 | A method of detaching aluminium foil and anode waste from lithium ion battery positive plate |
| CN108767353A (en) * | 2018-05-25 | 2018-11-06 | 北京矿冶科技集团有限公司 | The method for producing rich lithium net liquid from waste lithium ion cell anode active material |
| CN110649342A (en) * | 2018-06-26 | 2020-01-03 | 中天储能科技有限公司 | Method for recycling positive active material of waste lithium iron phosphate battery |
| CN110649342B (en) * | 2018-06-26 | 2022-08-12 | 中天储能科技有限公司 | Method for recycling positive active material of waste lithium iron phosphate battery |
| CN113621802A (en) * | 2020-05-07 | 2021-11-09 | 贵州中伟资源循环产业发展有限公司 | Method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole piece |
| CN113104866A (en) * | 2021-03-30 | 2021-07-13 | 中国石油大学(北京) | Method for preparing battery-grade lithium carbonate from lithium iron phosphate waste |
| CN113104866B (en) * | 2021-03-30 | 2021-11-09 | 中国石油大学(北京) | Method for preparing battery-grade lithium carbonate from lithium iron phosphate waste |
| CN113285135A (en) * | 2021-05-07 | 2021-08-20 | 宁夏百川新材料有限公司 | Method for recycling multiple components of waste lithium iron phosphate battery |
| CN115072748A (en) * | 2022-06-09 | 2022-09-20 | 江西春鹏锂业有限责任公司 | Clean production method and production system of battery-grade lithium carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102903985B (en) | 2014-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102903985B (en) | Method for recycling lithium carbonate from lithium iron phosphate waste material | |
| CN102891345B (en) | Method for recycling lithium chloride from waste lithium iron phosphate | |
| Jo et al. | Efficient recycling of valuable resources from discarded lithium-ion batteries | |
| CN102910607B (en) | Comprehensive recycling method for lithium iron phosphate cathode material | |
| CN102916236B (en) | Comprehensive recycling method for lithium iron phosphate positive plates | |
| CN106910889B (en) | A method of regenerating positive active material from waste lithium iron phosphate battery | |
| CN110581323B (en) | In-situ regeneration method of waste lithium iron phosphate battery positive electrode material | |
| CN107196007B (en) | Lithium battery recycling method | |
| CN110343864B (en) | Method for recovering lithium and cobalt in waste electrode material by microwave roasting assistance | |
| CN108075203B (en) | Method for recycling valuable metal components in waste lithium ion battery material | |
| CN106450547B (en) | Method for recovering iron phosphate and lithium carbonate from lithium iron phosphate waste | |
| CN102676827B (en) | Method for recovering valuable metal from nickel cobalt lithium manganate batteries and positive pole materials | |
| CN104466292B (en) | The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material | |
| CN110620278B (en) | Method for recovering anode material of waste lithium iron phosphate battery | |
| CN109449523A (en) | A kind of comprehensive recovering process of waste and old lithium ion battery | |
| CN102881960B (en) | Method for recycling lithium hydrate from lithium iron phosphate waste | |
| CN101847763A (en) | Comprehensive recovering method of waste lithium iron phosphate battery | |
| WO2014154152A1 (en) | Method for recycling nickel-cobalt-manganese ternary anode material | |
| CN104485493B (en) | The reparative regeneration method of lithium cobaltate cathode active material in used Li ion cell | |
| CN110092398B (en) | Resource utilization method for waste lithium ion battery roasting tail gas | |
| CN111924819B (en) | Method for recycling waste disassembled lithium iron phosphate cathode material | |
| CN109167118B (en) | Comprehensive utilization method of lithium iron phosphate battery electrode material | |
| CN105977569A (en) | Method for preparing lithium iron ii phosphate from lithium iron ii phosphate waste | |
| WO2014154154A1 (en) | Method of recycling lithium manganese battery anode material | |
| JP2012121780A (en) | Method for manufacturing lithium oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 629200 Shehong County, Suining City, Taihe Town, north of the city of Qi Qi lithium Limited by Share Ltd Patentee after: Tianqi Lithium Co., Ltd. Address before: North of the city of Suining city in 629200 Sichuan Taihe County of Shehong province Tianqi lithium New Material Industrial Park Patentee before: Sichuan Tianqi Lithium Industries.Inc. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191017 Address after: 629200, Suining County, Sichuan City, Shehong Province Taihe Town, North Qi Li lithium Limited by Share Ltd Co-patentee after: Tianqi lithium industry (Jiangsu) Co., Ltd. Patentee after: Tianqi Lithium Industry Co., Ltd. Co-patentee after: Tianqi Lithium Industry (Shehong) Co., Ltd. Address before: 629200, Suining County, Sichuan City, Shehong Province Taihe Town, North Qi Li lithium Limited by Share Ltd Patentee before: Tianqi Lithium Industry Co., Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 215634, 5, Dongxin Road, Yangzi International Chemical Industry Park, Suzhou, Jiangsu, Zhangjiagang Co-patentee after: Tianqi Lithium Industry Co., Ltd. Patentee after: Tianqi lithium industry (Jiangsu) Co., Ltd. Co-patentee after: Tianqi Lithium Industry (Shehong) Co., Ltd. Address before: 629200, Suining County, Sichuan City, Shehong Province Taihe Town, North Qi Li lithium Limited by Share Ltd Co-patentee before: Tianqi lithium industry (Jiangsu) Co., Ltd. Patentee before: Tianqi Lithium Industry Co., Ltd. Co-patentee before: Tianqi Lithium Industry (Shehong) Co., Ltd. |