CN111908438B - Method for treating electrolyte of waste lithium ion battery - Google Patents
Method for treating electrolyte of waste lithium ion battery Download PDFInfo
- Publication number
- CN111908438B CN111908438B CN202010629142.XA CN202010629142A CN111908438B CN 111908438 B CN111908438 B CN 111908438B CN 202010629142 A CN202010629142 A CN 202010629142A CN 111908438 B CN111908438 B CN 111908438B
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- filter residue
- lithium
- ion battery
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 44
- 239000002699 waste material Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 13
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 13
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 230000001502 supplementing effect Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000010008 shearing Methods 0.000 claims description 18
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000004945 emulsification Methods 0.000 claims description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 239000011268 mixed slurry Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- -1 Lithium hexafluorophosphate Chemical compound 0.000 description 13
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 13
- 239000012535 impurity Substances 0.000 description 11
- 230000001804 emulsifying effect Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/308—Methods for converting an alkali metal orthophosphate into another one; Purification; Decolorasing; Dehydrating; Drying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
- Primary Cells (AREA)
Abstract
The invention provides a method for treating a waste lithium ion battery electrolyte, which comprises the following steps: (1) obtaining electrolyte from a waste lithium ion battery, mixing the electrolyte with a stabilizer, and sintering to obtain ash; (2) dissolving the ash with acid, adding an iron source, adjusting the pH value to 1-2, heating and reacting at 60-90 ℃ for 1-4h, and filtering to obtain first filter residue and lithium-containing filtrate; washing the first filter residue for multiple times to obtain high-purity iron phosphate; (3) supplementing phosphoric acid into the lithium-containing filtrate, adding ammonia water to adjust the pH value of the system to 8-12, heating at 70-100 ℃, and filtering to obtain second filter residue; and washing the second filter residue for multiple times to obtain high-purity lithium phosphate. The method is simple, reasonable and easy to operate, and environment-friendly.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of waste resources, in particular to a method for treating waste lithium ion battery electrolyte.
Background
Lithium ion batteries using lithium iron phosphate, ternary positive electrode materials (such as nickel cobalt lithium manganate) and the like as positive electrode materials are widely used as power batteries of electric tools such as electric vehicles and the like, and accordingly, the number of waste lithium ion batteries is increasing. Therefore, the method has double meanings of economic value and social benefit for effectively recycling and reusing the waste lithium ion battery.
At present, the method for recycling the waste lithium ion battery mainly aims at the anode material, and the recycling of the electrolyte is less. Lithium hexafluorophosphate is an important component of the current lithium ion battery electrolyte and accounts for about 43 percent of the total cost of the electrolyte. Therefore, the method is particularly important for recovering the waste lithium ion battery electrolyte containing lithium hexafluorophosphate. In the prior art, the recovery of lithium hexafluorophosphate in the electrolyte of the waste lithium ion battery is mainly carried out by rectification at high temperature and high pressure, but the lithium hexafluorophosphate has active properties, and the problems of high recovery difficulty, low purity of the recovered lithium hexafluorophosphate and the like exist.
Disclosure of Invention
In view of this, the present invention aims to provide a method for treating a waste lithium ion battery electrolyte, so as to solve the problems of high recycling difficulty, high recycling cost, and the like of the existing waste lithium ion battery electrolyte.
Specifically, the invention provides a method for treating a waste lithium ion battery electrolyte, which comprises the following steps:
(1) obtaining electrolyte from a waste lithium ion battery, mixing the electrolyte with a stabilizer, and sintering to obtain ash;
(2) dissolving the ash with acid, adding an iron source, adjusting the pH value to 1-2, heating and reacting at 60-90 ℃ for 1-4h, and filtering to obtain first filter residue and lithium-containing filtrate; washing the first filter residue for multiple times to obtain high-purity iron phosphate;
(3) supplementing phosphoric acid into the lithium-containing filtrate, adding ammonia water to adjust the pH value of the system to 8-12, heating at 70-100 ℃, and filtering to obtain second filter residue; and washing the second filter residue for multiple times to obtain high-purity lithium phosphate.
In the step (1), the obtaining of the electrolyte from the waste lithium ion battery includes: and disassembling the waste lithium ion battery, separating out the positive plate, the negative plate and the diaphragm, and placing the positive plate, the negative plate and the diaphragm in a centrifuge for centrifugation to obtain the electrolyte. Optionally, the rotation speed of the centrifugation is 1000-. For example, 1200-1800 rpm.
The electrolyte of the waste lithium ion battery contains lithium hexafluorophosphate. Optionally, the waste lithium ion battery includes a waste lithium iron phosphate battery, a waste ternary material battery, and the like.
The electrolyte of the waste lithium ion battery mainly comprises lithium hexafluorophosphate, an organic solvent (such as Dimethoxyethane (DME), Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC) and the like), and additives can be added. In the step (1), the electrolyte is sintered to remove organic substances such as DME, PC, EC, and DEC from the electrolyte and to make lithium hexafluorophosphate (LiPF) as a main component6) Sintering in the presence of the stabilizer to produce lithium fluoride and hexafluorophosphate.
Optionally, the stabilizer is selected from at least one of sodium fluoride and potassium fluoride. The presence of the stabilizer can avoid the volatilization loss of the phosphorus source in the electrolyte during the sintering process in the step (1).
Optionally, in the step (1), the sintering temperature is 500-.
Optionally, in the step (2), the acid for dissolving the ash includes at least one of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, and oxalic acid. Preferably, the acid is phosphoric acid to avoid the introduction of other anionic impurities.
In the step (2), after the ash is dissolved by adding acid, an iron source is added, and the heating reaction is carried out after the pH value is adjusted to 1-2, so as to accelerate the formation of iron phosphate precipitate. Alternatively, in the step (2), the temperature of the heating reaction may be 60 to 80 ℃ and 70 to 90 ℃. Alternatively, the temperature of the heating reaction is 65 to 85 ℃, preferably 70 to 80 ℃. The heating reaction time can be 1-3h, 2-4h or 1-2 h.
Optionally, in the step (2), the iron source may be at least one selected from iron sulfate, iron nitrate, iron oxide red, iron chloride, and iron carbonate.
In the step (2), the obtained first filter residue is washed by water, so that a small amount of Li adsorbed on the surface of the ferric phosphate precipitate can be removed+、PO4 3-、F-And dissolving the anions of the ash with acid to obtain the high-purity iron phosphate with extremely high purity. The obtained lithium-containing filtrate contains Li+、PO4 3-、F-And anions introduced by addition of acids other than phosphoric acid.
In the step (1), part of phosphorus is lost during the sintering process of the electrolyte, and phosphorus in the solution is consumed during the formation of iron phosphate in the step (2), so that in the step (3) of the present application, a proper amount of phosphoric acid needs to be supplemented as a phosphorus source. Optionally, in the step (3), the adding amount of the phosphoric acid is 1/3-1/4 of the molar amount of lithium element in the lithium-containing filtrate.
Alternatively, in the step (3), the temperature of the heat treatment may be 70 to 90 ℃. For example 80-90 deg.c.
Optionally, in the step (3), the time of the heat treatment may be 2 to 4 hours.
In step (3) of the application, the obtained second filter residue is washed with water, and anions of a small amount of acid for dissolving ash, which are adsorbed on the surface of the lithium phosphate precipitate and coated in the lithium phosphate, can be removed.
In the invention, the first filter residue and the second filter residue are washed by a shearing emulsifying pump, so that better impurity removal and purification effects can be realized, namely impurity ions adsorbed on the surface of the corresponding filter residue or coated in the filter residue can be well removed. The method has the advantages that the shearing emulsifying pump is adopted for washing, impurities in the water-containing slurry of each filter residue can be fully released, the method has the characteristics of large treatment capacity, no dispersed shearing dead angle, mass and automatic production and suitability for industrial production.
Specifically, the water washing with the shear emulsification pump comprises: placing the slurry of each filter residue and water into a feeding pipe of a shearing emulsification pump, and sucking the mixed slurry into a working cavity for homogenization treatment under the pressure difference between the feeding pipe and the working cavity where a rotor of the shearing emulsification pump is located, wherein the rotating speed of the rotor of the shearing emulsification pump is 1000-2935rpm, and the pressure difference is 0.1-0.2 MPa. Optionally, the rotor speed of the shear emulsification pump is 1500-2900rpm, preferably 2000-2900 rpm. Wherein, the pressure of a working cavity where a rotor of the shearing emulsifying pump is positioned is less than the pressure in the feeding pipe.
The treatment method provided by the invention is simple and safe in process, and can convert phosphorus and lithium elements in the electrolyte of the waste lithium iron phosphate battery into high-purity ferric phosphate and lithium phosphate products through the design of the steps of ring-and-ring buckling, so that the problems of high recovery difficulty, high recovery cost and the like of the electrolyte of the existing waste lithium iron phosphate battery are solved. The treatment method is simple, reasonable and easy to operate, low in cost, environment-friendly and capable of being applied industrially.
Detailed Description
The following are exemplary embodiments of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations are also regarded as the protection scope of the present invention.
The present invention will be further illustrated by the following specific examples.
Example 1
A method for treating electrolyte of a waste lithium iron phosphate battery comprises the following steps:
(1) removing the shell of the waste lithium iron phosphate battery, disassembling and separating out a positive plate, a negative plate and a diaphragm, placing the positive plate, the negative plate and the diaphragm in a centrifuge for centrifugation (the centrifugation speed is 1500rpm), and separating to obtain electrolyte; taking 150mL of the electrolyte, adding 0.1mol of sodium fluoride, sintering at 700 ℃ for 1.5h, and collecting ash;
(2) dissolving the ash by adding 40mL of 30 wt% nitric acid, adding 24g of ferric nitrate, adding ammonia water to adjust the pH value of the solution to 2, heating and reacting at 76 ℃ for 2 hours, and filtering to obtain first filter residue and lithium-containing filtrate;
and (3) washing the first filter residue by using a shearing emulsion pump to obtain high-purity iron phosphate (the purity is as high as 99.95%, and the content of impurity ions is only 15ppm), wherein the process comprises the following steps: preparing the first filter residue and water into mixed slurry, placing the mixed slurry into a feeding pipe of a shearing emulsifying pump, controlling the pressure difference between the feeding pipe and a working cavity where a rotor of the shearing emulsifying pump is located to be 0.2MPa, sucking the mixed slurry into the working cavity containing the rotor under the pressure difference, performing homogenization treatment at the rotor rotating speed of 2900rpm, filtering the homogenized material, collecting solid matters, and repeating the operation for 2 times to obtain high-purity iron phosphate;
(3) adding 10mL of 85% phosphoric acid into the lithium-containing filtrate, adding ammonia water to adjust the pH value of the system to 10, heating at 90 ℃ for 2 hours, and filtering to obtain second filter residue;
and (3) washing the second filter residue for multiple times by using a shearing emulsifying pump in a similar manner to the step (2) to obtain high-purity lithium phosphate (the purity is 98.53%, and the impurity ion content is only 30 ppm).
Example 2
A method for treating electrolyte of a waste lithium iron phosphate battery comprises the following steps:
(1) removing the shell of the waste lithium iron phosphate battery, disassembling and separating out a positive plate, a negative plate and a diaphragm, placing the positive plate, the negative plate and the diaphragm in a centrifuge for centrifugation (the centrifugation speed is 1200rpm), and separating to obtain electrolyte; taking 80mL of the electrolyte, adding 0.05mol of sodium fluoride, sintering at 600 ℃ for 2h, and collecting ash;
(2) dissolving the ash by adding 30mL of 50 wt% sulfuric acid, adding 35g of ferric sulfate, adding ammonia water to adjust the pH value of the solution to 1, heating the solution at 60 ℃ for reaction for 1h, and filtering the solution to obtain first filter residue and lithium-containing filtrate; washing the first filter residue for multiple times by using a shearing emulsion pump to obtain high-purity iron phosphate (the purity is as high as 99.82%, and the content of impurity ions is only 10 ppm);
(3) adding 18mL of 60 wt% phosphoric acid into the lithium-containing filtrate, adding ammonia water to adjust the pH of the system to 8, heating at 80 ℃ for 4 hours, and filtering to obtain second filter residue; and (4) washing the second filter residue for multiple times by using a shearing emulsifying pump to obtain high-purity lithium phosphate (the purity is 98.17%, and the content of impurity ions is only 36 ppm).
Example 3
A method for treating electrolyte of a waste lithium iron phosphate battery comprises the following steps:
(1) removing the shell of the waste lithium iron phosphate battery, disassembling and separating out a positive plate, a negative plate and a diaphragm, placing the positive plate, the negative plate and the diaphragm in a centrifuge for centrifugation (the centrifugation speed is 2000rpm), and separating to obtain electrolyte; taking 100mL of the electrolyte, adding 0.1mol of potassium fluoride, sintering at 800 ℃ for 1h, and collecting ash;
(2) dissolving the ash by adding 40mL of 30 wt% phosphoric acid, adding 40g of iron oxide red, adding ammonia water to adjust the pH value of the solution to 1.5, heating to react for 3 hours at 80 ℃, and filtering to obtain first filter residue and lithium-containing filtrate; washing the first filter residue for multiple times by using a shearing emulsion pump to obtain high-purity iron phosphate (the purity is as high as 99.96%, and the content of impurity ions is only 7 ppm);
(3) supplementing 25mL of 30 wt% phosphoric acid into the lithium-containing filtrate, adding ammonia water to adjust the pH of the system to 12, heating at 70 ℃ for 3 hours, and filtering to obtain second filter residue; and (4) washing the second filter residue for multiple times by using a shearing emulsifying pump to obtain high-purity lithium phosphate (the purity is 98.33%, and the content of impurity ions is only 32 ppm).
Comparative example 1
A method for treating electrolyte of a waste lithium iron phosphate battery comprises the following steps:
(1) extracting waste electrolyte of waste lithium iron phosphate batteries in the manner of example 1, putting 50mL of waste electrolyte in a rectification device, recovering an organic solvent under the conditions of high temperature and high pressure (10kPa, 100 ℃), and obtaining a residue after rectification as a crude product of lithium hexafluorophosphate;
(2) and (3) taking 5g of the crude lithium hexafluorophosphate, adding 10mL of hydrofluoric acid for dissolving, and recrystallizing at-10 ℃ for 10h to obtain the lithium hexafluorophosphate.
As a result, it was found that the purity of lithium hexafluorophosphate obtained in comparative example 1 was low, only 80%, and it could not be used as it was, and a complicated impurity removal work was required.
Compared with the prior art, the method for treating the electrolyte of the waste lithium iron phosphate battery has the advantages that dangerous operation of high temperature and high pressure is not needed, the safety is high, the product containing P and Fe (high-purity iron phosphate) and the product containing P and Li (high-purity lithium phosphate) with extremely high purity can be obtained through simple operation, and the products can be directly used.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A method for treating electrolyte of a waste lithium ion battery is characterized by comprising the following steps:
(1) obtaining electrolyte from a waste lithium ion battery, mixing the electrolyte with a stabilizer, and sintering to obtain ash; wherein the stabilizer is selected from at least one of sodium fluoride and potassium fluoride;
(2) dissolving the ash with acid, adding an iron source, adjusting the pH value to 1-2, heating and reacting at 60-90 ℃ for 1-4h, and filtering to obtain first filter residue and lithium-containing filtrate; washing the first filter residue for multiple times to obtain high-purity iron phosphate;
(3) supplementing phosphoric acid into the lithium-containing filtrate, adding ammonia water to adjust the pH value of the system to 8-12, heating at 70-100 ℃, and filtering to obtain second filter residue; and washing the second filter residue for multiple times to obtain high-purity lithium phosphate.
2. The process of claim 1, wherein the step (1) of obtaining the electrolyte from the used lithium ion battery comprises: and disassembling the waste lithium ion battery, separating the positive plate, the negative plate and the diaphragm, and placing the battery in a centrifuge for centrifugation to obtain the electrolyte.
3. The treatment method according to claim 1, wherein in the step (2), the iron source is at least one selected from the group consisting of iron sulfate, iron nitrate, iron oxide red, iron chloride and iron carbonate.
4. The treatment method according to claim 1, wherein in the step (2), the acid for dissolving the ash includes at least one of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, and oxalic acid.
5. The process of claim 1, wherein in step (2), the heating reaction is carried out at 60 to 80 ℃.
6. The process according to claim 1, wherein in the step (3), the heat treatment is carried out at 70 to 90 ℃ for 2 to 4 hours.
7. The process of claim 1, wherein in step (3), the phosphoric acid is added in an amount of 1/3-1/4 based on the molar amount of lithium in the lithium-containing filtrate.
8. The process according to any one of claims 1 to 7, wherein the washing of the first and second filter residue with water is carried out using a shear emulsification pump.
9. The process of claim 8, wherein said washing with a shear emulsion pump comprises: placing the slurry of each filter residue and water into a feeding pipe of a shearing emulsification pump, and sucking the mixed slurry into a working cavity for homogenization treatment under the pressure difference between the feeding pipe and the working cavity where a rotor of the shearing emulsification pump is located, wherein the rotating speed of the rotor of the shearing emulsification pump is 1000-2935rpm, and the pressure difference is 0.1-0.2 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010629142.XA CN111908438B (en) | 2020-07-02 | 2020-07-02 | Method for treating electrolyte of waste lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010629142.XA CN111908438B (en) | 2020-07-02 | 2020-07-02 | Method for treating electrolyte of waste lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111908438A CN111908438A (en) | 2020-11-10 |
| CN111908438B true CN111908438B (en) | 2021-11-02 |
Family
ID=73227301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010629142.XA Active CN111908438B (en) | 2020-07-02 | 2020-07-02 | Method for treating electrolyte of waste lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111908438B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2721467B2 (en) * | 1993-02-25 | 1998-03-04 | キヤノン株式会社 | Lithium battery material recovery method |
| JP2002343337A (en) * | 2001-05-21 | 2002-11-29 | Ngk Insulators Ltd | Injection / discharge method of electrolyte for lithium secondary battery |
| CN105958150B (en) * | 2016-06-30 | 2019-07-12 | 普定县银丰农业科技发展有限公司 | A kind of method of comprehensive utilization of waste and old lithium ion battery |
| CN108923092A (en) * | 2018-06-29 | 2018-11-30 | 惠州市宙邦化工有限公司 | A kind of waste and old lithium ionic cell electrolyte processing method |
| CN109585963B (en) * | 2018-11-30 | 2021-12-21 | 先进储能材料国家工程研究中心有限责任公司 | Method for recycling and treating waste lithium ion battery electrolyte |
| CN110176646B (en) * | 2019-05-20 | 2020-07-24 | 代辉 | Recovery processing method of waste lithium ion battery electrolyte |
| CN110534834A (en) * | 2019-09-11 | 2019-12-03 | 新中天环保股份有限公司 | The recovery method of electrolyte in a kind of waste and old lithium ion battery |
-
2020
- 2020-07-02 CN CN202010629142.XA patent/CN111908438B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111908438A (en) | 2020-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115432681B (en) | Regeneration process of waste lithium iron phosphate battery anode material | |
| CN109449523B (en) | Comprehensive recovery method for waste lithium ion battery | |
| CN108075202B (en) | Comprehensive recovery method of lithium iron phosphate anode material | |
| CN113443640B (en) | Method for preparing battery-grade lithium carbonate and battery-grade iron phosphate by using waste positive and negative electrode powder of lithium iron phosphate battery | |
| CN107739830A (en) | A kind of recovery method of positive material of waste lithium iron phosphate | |
| CN109179359A (en) | A method of extracting lithium and ferric phosphate from LiFePO4 waste material | |
| JP2012121780A (en) | Method for manufacturing lithium oxide | |
| JP2012106874A (en) | Method for purifying lithium hydroxide | |
| CN115149140B (en) | Method for recovering iron and lithium from waste lithium iron phosphate batteries | |
| CN115261605A (en) | Recovery method of lithium iron phosphate | |
| CN108155434A (en) | A kind of method that lithium is recycled in the waste electrolyte from lithium ion battery | |
| CN105907983A (en) | Method of extracting lithium from furnace slag generated from pyrogenic process recovery of lithium battery | |
| CN111924815A (en) | Method for recovering anode material of waste lithium iron phosphate battery | |
| CN119220819B (en) | A recycling method for extracting lithium, copper and aluminum from waste lithium iron phosphate batteries | |
| CN109004307A (en) | The recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery | |
| CN111924816A (en) | Method for recovering electrolyte of waste lithium ion battery | |
| CN119040637A (en) | Selective leaching method of black powder of lithium iron phosphate battery and method for recycling battery grade lithium carbonate | |
| CN117448577A (en) | Process for recycling lithium sulfate and ferric phosphate based on waste lithium iron phosphate battery | |
| CN111908438B (en) | Method for treating electrolyte of waste lithium ion battery | |
| CN117776130B (en) | Method for producing lithium phosphate by using waste lithium iron phosphate battery | |
| CN116854062B (en) | A method for efficient recycling of lithium extraction waste residue | |
| CN115637326B (en) | A method for co-disposing of waste phosphoric acid etching solution and retired LiFePO4 power batteries | |
| CN111170359A (en) | Device and process for preparing red lead from desulfurized lead | |
| JP5983526B2 (en) | Recovery method for heavy rare earth elements | |
| CN110304666B (en) | Method for recovering valuable elements from waste lithium ion battery anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |