CN102903985B - Method for recycling lithium carbonate from lithium iron phosphate waste material - Google Patents
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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 reclaim the method for lithium carbonate from LiFePO 4 waste material, 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 having the features such as high safety, high-environmental, low price, long-life, become the preferred material of generally acknowledged lithium-ion-power cell, and take the lithium ion battery that LiFePO 4 is positive electrode, be now widely used in the electrokinetic cell fields such as electric tool, electric bicycle, vehicle using motor, golf cart, ship model toy, mine lamp.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 resource recycling utilization has become social question of common concern.For the object of resource circulation utilization and industry sustainable development, tackle wherein elemental lithium and reclaim.
Lithium ion battery is comprised of shell and inner battery core.The shell of battery is stainless steel or nickel plating box hat, has the different models such as square and cylindrical.Inner battery core is rolled structure, major parts such as positive pole, electrolyte and negative poles, consists of, and positive plate mainly consists of aluminium foil, organic binder bond and lithium salts (LiFePO 4); And negative plate is mainly Copper Foil and graphite, the composition of negative material is relatively single, easily separated.The recycling of waste lithium ion cell anode material becomes the emphasis of people's research.Its recycling technology is mainly 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 2-5 hour by described waste material under the atmosphere of inert gas at 450-600 ℃, then described powdered product is added in the ethanolic solution of soluble ferric iron salt and mixes, dry, under the atmosphere of inert gas at 300-500 ℃ roasting 2-5 hour, reclaim and to 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 in to the sintering furnace under vacuum atmosphere, inert gas and/or reducibility gas and/or nitrogen protection, at the temperature of 150-750 ℃, heat-treats; Fragment after heat treatment is adopted to mechanical separation or ultrasonic oscillation method, by the separation from fragment of aluminium foil matrix, obtain the mixture of lithium iron phosphate cathode material, conductive agent and adhesive residue thing; By the mixture of lithium iron phosphate cathode material, conductive agent and adhesive residue thing, at 80-150 ℃ of temperature, toast 8-24 hour; By classification after the mixture abrasive dust after baking, the particle diameter of controlling powder is not more than 20 μ m, and D50 is controlled at 3-10 μ m, obtains 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 obtaining, of low quality, can not use as cell positive material.
(2) ferrous lithium phosphate cathode sheet is just directly recycled after simple cleaning-drying.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 completely, battery is moved in the vacuum glove box that is filled with nitrogen protection, by mechanical force, open the cover plate of described battery, take out and be contained in the battery core in this battery case; Cover plate and battery case are shifted out to glove box, recycle after treatment polypropylene PP plastics, steel or the aluminium of described cover plate and battery case; Separated negative plate and barrier film in described vacuum glove box again, and positive plate; Wherein negative plate and barrier film are recycled after treatment; And positive plate is after cleaning, dry, screening, coordinate new negative plate making to become new ferrous phosphate lithium dynamical battery.
The possibility that this mode can realize is smoothly 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 organic solvent dissolution battery core fragment, by screening, realize ferrousphosphate lithium material separated with clean aluminium, Copper Foil, wherein aluminium, Copper Foil reclaim by melting; Utilize NaOH solution to remove aluminium foil bits remaining in ferrousphosphate lithium material, by heat treatment, remove graphite and remaining binding agent.After LiFePO 4 is dissolved with acid, utilize vulcanized sodium to remove copper ion wherein, and utilize NaOH solution or ammoniacal liquor to make iron in 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, finally add carbon source, in ball milling, inert atmosphere, calcining obtains new lithium iron phosphate cathode material.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), by after water-system waste lithium ion battery shearing-crushing, by deionized water, processed, dry rear electrode material and the conductive agent mixture of reclaiming sieves; 2) add inorganic acid to process dried electrode material and conductive agent mixture, filter 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 to stir, control pH value=3-7; Filter, be precipitated; 4) LiFePO step 3) being obtained
4thick product joins in aqueous sucrose solution and carries out ball milling, and drying and calcining obtains the LiFePO of regeneration
4material.
If said method impurity removal obtains 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, can not meet 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 is to provide a kind of method that reclaims lithium carbonate from LiFePO 4 waste material.
The method that the present invention reclaims lithium carbonate from LiFePO 4 waste material comprises the steps:
A, roasting: LiFePO 4 waste material is in 500～800 ℃ of roasting 1～4h; Wherein, can conventional baking furnace as: in rotary kiln, carry out roasting;
B, leaching: the material after roasting adds sulfuric acid leaching, during leaching, pH value is controlled at 0.5～1, 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, filtration, washing, the dry ferric phosphate that obtains;
D, removal of impurities: the filtrate that c step is filtered gained regulates pH value 6～7, adds calcium chloride dephosphorization, filters;
E, precipitation lithium carbonate: the filtrate that d step is filtered gained regulates pH value to 10～12 with sodium carbonate, reaction 0.5～2h, filtration, washing, the dry battery-level lithium carbonate that obtains.
Wherein, LiFePO 4 waste material in said method can be the LiFePO 4 waste material producing in the LiFePO 4 waste material that produces in LiFePO 4 production process or battery production process, also can adopt following methods to reclaim obtains: old and useless battery is disassembled battery after discharging completely, separated negative plate and barrier film, and positive plate, positive plate is heated to 300-400 ℃ of heat treatment 1～4h, 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 LiFePO 4 waste material; Or reclaim and obtain LiFePO 4 waste material in the useless positive plate that employing said method produces from Production Process of Lithium Battery or inferior positive plate; Or the LiFePO 4 waste material producing in the positive plate production process for lithium battery.
Further, in said method, preferably 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 one in 1-METHYLPYRROLIDONE (NMP), DMA (DMA), dimethyl formamide (DMF).Organic solvent soaks the binding agent dissolving wherein, and sheet metal is reclaimed in screening, can collect and obtain LiFePO 4 waste material after screening.
In roasting process, thing phase conversion reaction can occur, the iron in 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 material caking.As preferred scheme, sintering temperature is advisable with 500～800 ℃.Calcination formula is:
6LiFePO
4+3O
2＝4FePO
4+2Li
3PO
4+Fe
2O
3
Wherein, in b step, the material after roasting adds Ore Leaching can add sulfuric acid, hydrochloric acid etc., because hydrochloric acid is volatile, considers operational environment, and the material after 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, in above-mentioned c, e step, temperature of washing water is preferably controlled at 40～100 ℃.
Beneficial effect of the present invention: the present inventor, from another one angle, provides a kind of brand-new method, the low-cost LiFePO 4 waste material of recycling, is become ferric phosphate 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.
Accompanying drawing explanation
Fig. 1 is the flow chart of one of embodiment of LiFePO 4 recovery process of the present invention.
Fig. 2 is two flow chart of the embodiment of LiFePO 4 recovery process of the present invention.
Embodiment
The method that the present invention reclaims lithium carbonate from LiFePO 4 waste material comprises the steps:
A, roasting: LiFePO 4 waste material is in 500～800 ℃ of roasting 1～4h; Wherein, can conventional baking furnace as: in rotary kiln, carry out roasting;
B, leaching: the material after roasting adds sulfuric acid leaching, during leaching, pH value is controlled at 0.5～1, 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, filtration, washing, the dry ferric phosphate that obtains;
D, removal of impurities: the filtrate that c step is filtered gained regulates pH value 6～7, adds calcium chloride dephosphorization, filters;
E, precipitation lithium carbonate: the filtrate that d step is filtered gained regulates pH value to 10～12 with sodium carbonate, reaction 0.5～2h, filtration, washing, the dry battery-level lithium carbonate that obtains.
Wherein, LiFePO 4 waste material in said method can be the LiFePO 4 waste material producing in the LiFePO 4 waste material that produces in LiFePO 4 production process or battery production process, also can adopt following methods to reclaim obtains: old and useless battery is disassembled battery after discharging completely, separated negative plate and barrier film, and positive plate, positive plate is heated to 300-400 ℃ of heat treatment 1～4h, 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 LiFePO 4 waste material; Or reclaim and obtain LiFePO 4 waste material in the useless positive plate that employing said method produces from Production Process of Lithium Battery or inferior positive plate; Or the LiFePO 4 waste material producing in the positive plate production process for lithium battery.
Further, in said method, preferably 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 one in 1-METHYLPYRROLIDONE (NMP), DMA (DMA), dimethyl formamide (DMF).Organic solvent soaks the binding agent dissolving wherein, and sheet metal is reclaimed in screening, can collect and obtain LiFePO 4 waste material after screening.
In roasting process, thing phase conversion reaction can occur, the iron in 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 material caking.As preferred scheme, sintering temperature is advisable with 500～800 ℃.Calcination formula is:
6LiFePO
4+3O
2＝4FePO
4+2Li
3PO
4+Fe
2O
3
Wherein, in b step, the material after roasting adds Ore Leaching can add sulfuric acid, hydrochloric acid etc., because hydrochloric acid is volatile, considers operational environment, and the material after 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, in above-mentioned c, e step, temperature of washing water is preferably controlled at 40～100 ℃.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among 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 after 300-400 ℃ of roasting 1～4h of ferrous lithium phosphate cathode sheet, pulverize.
C. anodal aluminium flake is reclaimed in screening, obtains LiFePO 4 waste material.
D. LiFePO 4 waste material 500-800 ℃ of roasting 1～4h.
E. after roasting, material adds 93%～98% sulfuric acid leaching, filters and obtains ferric phosphate, lithium phosphate, ferric sulfate mixed solution.
F. lithium phosphate, ferric phosphate, ferric sulfate mixed solution are heated to 80-100 ℃, and regulate pH value to 2-2.5, reaction 1-4 hour, filtration, washing, the dry ferric phosphate that obtains.
G.f step filtrate regulates pH value 6-7,, add calcium chloride to remove a small amount of foreign matter of phosphor.
The filtrate that h.g step obtains regulates pH value to 10-12 with sodium carbonate, reaction 0.5-2 hour, filtration, washing, the dry battery-level lithium carbonate that obtains.In LiFePO 4 waste material, the lithium rate of recovery reaches more than 80%.
Wherein, step a-h is applicable to old and useless battery and reclaims, for the LiFePO 4 waste material producing in the LiFePO 4 waste material producing in LiFePO 4 production process or 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; By 400 ℃ of roasting 1h of ferrous lithium phosphate cathode sheet, after pulverizing, anodal aluminium flake is reclaimed in screening; LiFePO 4 waste material 100kg, lithium content 3.5%.
800 ℃ of roastings of LiFePO 4 waste material 1 hour, then add water and size mixing, and add 98% concentrated sulfuric acid to regulate 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, then through 40 ℃ of water washings, the dry ferric phosphate that obtains; Filtrate regulates pH value to 6, adds 100g calcium chloride, then filtering and impurity removing; After removal of impurities, filtrate regulates pH value to 12 with sodium carbonate, reacts 0.5 hour, filters and obtains Crude lithium Carbonate, through 40 ℃ of water washings, the dry lithium carbonate 15.12kg that obtains.The purity of gained ferric phosphate and lithium carbonate is respectively as shown in table 1,2, and lithium carbonate quality meets YS/T 582-2006 LITHIUM BATTERY standard-required.
Table 1
Table 2
After testing, in LiFePO 4 waste material, the lithium rate of recovery is 81.55%.
Embodiment 2 adopts the inventive method comprehensive reutilization LiFePO 4 waste material
The LiFePO 4 waste material 100kg producing in the production process of power taking pond, lithium content 3.52%.600 ℃ of roastings of LiFePO 4 waste material 2 hours, then add water and size mixing, and add 98% concentrated sulfuric acid to regulate 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, then through 60 ℃ of water washings, the dry ferric phosphate that obtains; Filtrate regulates pH value to 7, adds calcium chloride 100g, then filtering and impurity removing; After removal of impurities, filtrate regulates pH value to 11 with sodium carbonate, reacts 1 hour, filters and obtains Crude lithium Carbonate, through 60 ℃ of water washings, the dry lithium carbonate 15.4kg that obtains.Respectively as shown in Table 3, 4, lithium carbonate quality meets YS/T 582-2006 battery-level lithium carbonate standard-required to the purity of gained ferric phosphate and lithium carbonate.
Table 3
Table 4
After testing, in LiFePO 4 waste material, the lithium rate of recovery is 83.21%.
Embodiment 3 adopts the inventive method comprehensive reutilization LiFePO 4 waste material
Get the LiFePO 4 waste material 100kg producing in LiFePO 4 production process, lithium content 4.38%.500 ℃ of roastings of LiFePO 4 waste material 4 hours, then add water and size mixing, and add 98% concentrated sulfuric acid to regulate 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, then through 80 ℃ of water washings, the dry ferric phosphate that obtains; Filtrate regulates pH value to 6, adds 100g calcium chloride, then filtering and impurity removing; After removal of impurities, filtrate regulates pH value to 10 with sodium carbonate, reacts 2 hours, filters and obtains Crude lithium Carbonate, through 100 ℃ of water washings, the dry lithium carbonate 15.2kg that obtains.Respectively as shown in Table 5,6, lithium carbonate quality meets YS/T 582-2006 battery-level lithium carbonate standard-required to the purity of gained ferric phosphate and lithium carbonate.
Table 5
Table 6
After testing, in LiFePO 4 waste material, the lithium rate of recovery is 82.31%.
Claims (6)
1. from LiFePO 4 waste material, reclaim the method for lithium carbonate, it is characterized in that comprising the steps:
A, roasting: LiFePO 4 waste material is in 500～800 ℃ of roasting 1～4h;
B, leaching: the material after roasting adds sulfuric acid leaching, during leaching, pH value is controlled at 0.5～1, 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, filtration, washing, the dry ferric phosphate that obtains;
D, removal of impurities: the filtrate that c step is filtered gained regulates pH value 6～7, adds calcium chloride dephosphorization, filters;
E, precipitation lithium carbonate: the filtrate that d step is filtered gained regulates pH value to 10～12 with sodium carbonate, reaction 0.5～2h, filtration, washing, the dry battery-level lithium carbonate that obtains.
2. the method that reclaims lithium carbonate from LiFePO 4 waste material according to claim 1, it is characterized in that: described LiFePO 4 waste material is the LiFePO 4 waste material producing in the LiFePO 4 waste material that produces in LiFePO 4 production process or battery production process, or adopt following methods recovery to obtain: old and useless battery is disassembled battery after discharging completely, separated negative plate and barrier film, and positive plate, positive plate is heated to 300-400 ℃ of heat treatment 1～4h, matrix aluminium foil is separated with positive electrode, obtain lithium iron phosphate cathode material, the mixture of conductive agent and adhesive residue thing is LiFePO 4 waste material,
Or reclaim and obtain LiFePO 4 waste material in the useless positive plate that employing said method produces from Production Process of Lithium Battery or inferior positive plate;
Or the LiFePO 4 waste material producing in the positive plate production process for lithium battery.
3. the method that reclaims lithium carbonate from 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 one in 1-METHYLPYRROLIDONE (NMP), DMA (DMA), dimethyl formamide (DMF).
4. according to the method for lithium carbonate that reclaims from LiFePO 4 waste material described in claim 1～3 any one, it is characterized in that: in b step, described sulfuric acid concentration is 93～98wt%.
5. according to the method for lithium carbonate that reclaims from LiFePO 4 waste material described in claim 1～3 any one, it is characterized in that: the water temperature while washing in c, e step is 40～100 ℃.
6. the method that reclaims lithium carbonate from LiFePO 4 waste material according to claim 4, is characterized in that: the water temperature while washing in c, e step is 40～100 ℃.
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| 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 |
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| CN103370829A (en) * | 2011-02-15 | 2013-10-23 | 住友化学株式会社 | Method for recovering active material from battery waste |
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