CN115213023B - A method for improving the flotation separation efficiency of positive and negative electrode materials of waste lithium batteries - Google Patents
A method for improving the flotation separation efficiency of positive and negative electrode materials of waste lithium batteries Download PDFInfo
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- 238000005188 flotation Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000000926 separation method Methods 0.000 title claims abstract description 26
- 239000002699 waste material Substances 0.000 title claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 11
- 229910052744 lithium Inorganic materials 0.000 title claims description 11
- 239000007774 positive electrode material Substances 0.000 title abstract description 13
- 239000007773 negative electrode material Substances 0.000 title abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000011268 mixed slurry Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004945 emulsification Methods 0.000 claims abstract description 9
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000010405 anode material Substances 0.000 claims description 17
- 239000010406 cathode material Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002283 diesel fuel Substances 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 8
- 238000004513 sizing Methods 0.000 claims description 7
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000010624 camphor oil Substances 0.000 claims description 3
- 229960000411 camphor oil Drugs 0.000 claims description 3
- 239000010642 eucalyptus oil Substances 0.000 claims description 3
- 229940044949 eucalyptus oil Drugs 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 12
- 238000011282 treatment Methods 0.000 abstract description 6
- 239000006260 foam Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000010926 waste battery Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
- B03D1/025—Froth-flotation processes adapted for the flotation of fines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B1/00—Conditioning for facilitating separation by altering physical properties of the matter to be treated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B1/00—Conditioning for facilitating separation by altering physical properties of the matter to be treated
- B03B1/04—Conditioning for facilitating separation by altering physical properties of the matter to be treated by additives
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/005—Dispersants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/007—Modifying reagents for adjusting pH or conductivity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明公开了一种提高废旧磷酸铁锂电池正负极材料浮选分离效率的方法，包括以下步骤：将废旧磷酸铁锂电池正负极材料与水混合搅拌调浆后加入捕收剂再次搅拌，搅拌调浆后的料浆置于浮选机中，加入pH调节剂调节浆料pH、加入分散剂、添加起泡剂并进行浮选分离，得到正极磷酸铁锂粉和负极石墨粉。本发明进行了强搅拌调浆对正负极混合料浆进行处理，使正负极物料充分分散，避免后续浮选过程中造成过量细粒正极物料的泡沫夹带；加入的捕收剂柴油进行了超声乳化处理，使柴油分散更均匀，提高物料浮选分离效率，为后续电极材料的进一步提纯或再生修复创造条件，回收得到的正极磷酸铁锂粉、负极石墨粉回收率和品位高。
The present invention discloses a method for improving the flotation separation efficiency of the positive and negative electrode materials of waste lithium iron phosphate batteries, comprising the following steps: mixing the positive and negative electrode materials of waste lithium iron phosphate batteries with water, stirring and slurrying, adding a collector and stirring again, placing the slurry after stirring and slurrying in a flotation machine, adding a pH regulator to adjust the pH of the slurry, adding a dispersant, adding a foaming agent and flotation separation to obtain positive lithium iron phosphate powder and negative graphite powder. The present invention performs strong stirring and slurrying to treat the positive and negative electrode mixed slurry, so that the positive and negative electrode materials are fully dispersed, and the foam entrainment of excessive fine-grained positive electrode materials in the subsequent flotation process is avoided; the added collector diesel is subjected to ultrasonic emulsification treatment, so that the diesel is more evenly dispersed, the material flotation separation efficiency is improved, and conditions are created for further purification or regeneration and repair of subsequent electrode materials, and the recovered positive lithium iron phosphate powder and negative graphite powder have high recovery rate and grade.
Description
Technical Field
The invention belongs to the technical field of waste battery recycling, and particularly relates to a method for improving flotation separation efficiency of anode and cathode materials of waste lithium batteries.
Background
The lithium ion battery is widely applied to the technical fields of new energy automobiles, energy storage and the like due to the advantages of high energy density, high working voltage, high cycle performance, long service life, small self-discharge, environmental friendliness and the like. With the rapid increase of economic level and the enhancement of environmental awareness, the power battery industry is rapidly developed, and the rapid increase of the installed amount of the power battery is required to bring about the rejection of a large amount of power batteries, which also brings about double pressure on environmental management and resource supply.
The lithium ion battery mainly comprises a lithium iron phosphate battery and a ternary battery. The lithium iron phosphate battery does not contain rare and noble metals such as cobalt, nickel, manganese and the like, and has the advantages of low price of raw materials for manufacturing the lithium iron phosphate battery, wide resource reserve, good stability in a high-temperature and high-heat environment and the like, so that the lithium iron phosphate battery is widely used. Lithium iron phosphate batteries generally consist of a positive current collector (aluminum foil plus positive active material (lithium iron phosphate (LiFePO 4)), a negative current collector (copper foil plus negative active material (carbon powder)), electrolyte, a diaphragm and other substances.
At present, pretreatment such as disassembly, discharge, pyrolysis, crushing, screening, reselection, color selection and the like is needed before the recovery of the waste power batteries so as to obtain valuable components such as copper foil, aluminum foil, anode and cathode mixed materials and the like. At present, most of research work is focused on the recovery of valuable metals in the anode material, but the recovery of graphite of the cathode material is ignored, so that the recovery of graphite not only can improve the resource utilization rate, but also can avoid environmental pollution. Because graphite has better natural hydrophobicity, separation and enrichment can be carried out by a flotation method. However, the separation efficiency of the anode and cathode materials is low due to the problems that the granularity of the anode and cathode mixture materials is fine and the fine graphite is easy to foam and entrain energy. Therefore, the development of an economical and efficient method for separating the anode material and the cathode material by flotation has important significance.
Disclosure of Invention
Aiming at the defect of low flotation separation efficiency of positive and negative electrode materials in the existing waste lithium batteries, the invention aims to provide a method for improving the flotation separation efficiency of the positive and negative electrode materials in the waste lithium batteries, which has the advantages of simple process, convenient operation, low production cost, cleanness and high efficiency.
In order to solve the technical problems, the technical scheme provided by the invention is that the method for improving the flotation separation efficiency of the anode and cathode materials in the waste lithium battery comprises the following steps:
(1) Mixing the anode and cathode materials of the waste lithium batteries with water, and stirring and pulping to obtain mixed slurry;
(2) Adding a collector into the mixed slurry obtained in the step (1) and stirring and mixing the slurry;
(3) Placing the slurry obtained after stirring and size mixing in the step (2) into a flotation machine, adding a pH regulator to regulate the pH of the slurry, adding a dispersing agent, adding a foaming agent and carrying out flotation separation to obtain lithium-containing positive electrode powder and negative electrode graphite powder.
Preferably, the mass concentration of the mixed slurry in the step (1) is 10% -50%.
Preferably, the stirring time of stirring and size mixing in the step (1) and the step (2) is 5-30 min, the stirrer for stirring and size mixing is an electromechanical stirrer or a magnetic stirrer, and the stirring rotating speed is 1500-10000 r/min. And the mixed slurry of the positive electrode and the negative electrode is treated by strong stirring and size mixing, so that the materials of the positive electrode and the negative electrode are fully dispersed, and the excessive foam entrainment of the fine-grained positive electrode materials in the subsequent flotation process is avoided.
Preferably, the collector in the step (2) is emulsified diesel oil obtained by ultrasonic emulsification of diesel oil and water, the dosage of the collector in each ton of mixed slurry is 80 g-200 g, the ultrasonic emulsification time is 3-30 min, the ultrasonic power of ultrasonic emulsification is 300-600 w, and the frequency of the ultrasonic power is 20-80 kHz. The added collector diesel oil is subjected to ultrasonic emulsification treatment, so that the diesel oil can be dispersed more uniformly, the material flotation separation efficiency and effect are improved, meanwhile, the dispersibility of the collector can be improved, the positive and negative electrode material flotation separation efficiency is improved, and conditions are created for further purification or regeneration repair of the subsequent electrode material.
Preferably, the water-oil ratio of the emulsified diesel oil in the step (2) is 1:1-1:3.
Preferably, in the step (3), the dispersing agent is one or a combination of more than one of sodium silicate, sodium hexametaphosphate, sodium tripolyphosphate and sodium pyrophosphate, and the dosage of the dispersing agent in each ton of slurry after stirring and size mixing is 10-1000 g.
Preferably, in the step (3), the pH of the slurry is adjusted to 8-10, and in the step (3), the pH regulator is one or a combination of several of sodium carbonate, sodium hydroxide, hydrochloric acid or sulfuric acid.
Preferably, the foaming agent in the step (3) is one or a combination of more of eucalyptus oil, no. 2 oil, camphor oil or MIBC, and the dosage of the foaming agent in each ton of slurry after stirring and size mixing is 10-50 g.
Preferably, the flotation machine in the step (3) is an XFD type single-tank flotation machine.
Preferably, in the flotation separation operation in the step (3), the rotating speed of the flotation machine is 1500-2500 r/min, and the aeration amount is 0.2-0.8 m 3/min.
Compared with the prior art, the invention has the beneficial effects that:
1. The invention adopts the dosing sequence of the collector-pH regulator-dispersant-foaming agent, and adopts the flotation separation dosing sequence of the pH regulator-dispersant-collector-foaming agent in the prior art.
2. The invention processes the anode and cathode mixed slurry by strong stirring and size mixing, the stirring rotation speed is 1500-10000 r/min, so that anode and cathode materials are fully dispersed, foam entrainment of excessive fine-grained anode materials in the subsequent flotation process is avoided, the added collector diesel is subjected to ultrasonic emulsification treatment, so that the diesel is more uniformly dispersed, the material flotation separation efficiency and effect are improved, the dispersibility of the collector is improved, the anode and cathode material flotation separation efficiency is improved, and conditions are created for further purification or regeneration repair of the subsequent electrode materials.
3. The method provided by the invention has the advantages that the separation of the anode material and the cathode material is high, the recovery rate and grade of the recovered anode lithium iron phosphate powder and cathode graphite powder are high, the recovery rate and grade of the anode lithium iron phosphate powder are respectively up to 98.21% and 97.59%, and the recovery rate and grade of the cathode graphite powder are respectively up to 99.86% and 98.89%.
4. The method provided by the invention has the advantages of simple process, convenient operation, cleanness, high efficiency, low production cost and easy industrialized production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flow chart of a flotation separation process of anode and cathode materials of a waste lithium iron phosphate battery.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
The method for carrying out flotation separation on the anode and cathode materials of the waste batteries is used for treating the waste lithium iron phosphate batteries, and the process flow is shown in figure 1 and comprises the following steps:
(1) Placing 500g of anode and cathode mixed materials of the waste lithium iron phosphate battery into a beaker, mixing the mixed materials with water to a constant volume of 1000mL to obtain mixed slurry, and stirring and sizing by using an electromechanical stirrer, wherein the stirring speed is 3000r/min, and the stirring time is 20min;
(2) Emulsifying diesel oil according to the conditions of water-oil ratio of 1:1, ultrasonic power, frequency and time of 400w, 20kH and 5min respectively, adding mixed slurry according to the emulsified diesel oil with the dosage of 100g/t as a collector after the treatment, and stirring and sizing;
(3) Placing the stirred slurry into a 1.5L XFD type single-tank flotation machine, adding sodium hydroxide to adjust the pH of the slurry to 10, mixing the slurry for 3min, adding sodium hexametaphosphate with the dosage of 100g/t, mixing the slurry for 3min, adding eucalyptus oil with the dosage of 30g/t, mixing the slurry for 1min, carrying out flotation operation, wherein the flotation time is 5min, the rotation speed of the flotation machine is 2000r/min, the aeration quantity is 0.4m 3/min, the obtained concentrate product is negative electrode material graphite, and the tailing product is positive electrode material lithium iron phosphate.
And finally, the cathode graphite powder with the recovery rate and the grade of 98.31 percent and 97.86 percent respectively can be obtained through detection.
Example 2:
The method for carrying out flotation separation on the anode and cathode materials of the waste batteries is used for treating the waste lithium iron phosphate batteries, and the process flow is shown in figure 1 and comprises the following steps:
(1) Placing 500g of anode and cathode mixed materials of the waste lithium iron phosphate battery into a beaker, mixing the mixed materials with water to a constant volume of 1000mL to obtain mixed slurry, and stirring and sizing by using an electromechanical stirrer, wherein the stirring speed is 4000r/min, and the stirring time is 18min;
(2) Emulsifying diesel oil according to the conditions of water-oil ratio of 1:1.25, ultrasonic power, frequency and time of 350w, 30kH and 6min respectively, adding mixed slurry according to the use amount of 90g/t of the emulsified diesel oil as a collector after the treatment, and stirring and sizing;
(3) Placing the stirred slurry into a 1.5LXFD single-tank flotation machine, adding sodium hydroxide to adjust the pH of the slurry to 10, mixing the slurry for 3min, adding water glass with the dosage of 100g/t, mixing the slurry for 3min, adding 25g/t of camphor oil, mixing the slurry for 1min, performing flotation operation, wherein the flotation time is 5min, the rotation speed of the flotation machine is 2000r/min, the aeration quantity is 0.4m 3/min, the obtained concentrate product is negative electrode material graphite, and the tailing product is positive electrode material lithium iron phosphate.
And finally, the cathode graphite powder with the recovery rate and grade of 98.21 percent and 97.59 percent respectively and the recovery rate and grade of 99.86 percent and 98.89 percent respectively can be obtained through detection.
Example 3:
The method for carrying out flotation separation on the anode and cathode materials of the waste batteries is used for treating the waste lithium iron phosphate batteries, and the process flow is shown in figure 1 and comprises the following steps:
(1) Placing 500g of anode and cathode mixed materials of the waste lithium iron phosphate battery into a beaker, mixing the mixed materials with water to a constant volume of 1000mL to obtain mixed slurry, and stirring and sizing the mixed slurry by using an electromechanical stirrer, wherein the stirring speed is 4500r/min, and the stirring time is 16min;
(2) Emulsifying diesel oil according to the conditions of water-oil ratio of 1:1.5, ultrasonic power, frequency and time of 400w, 40kH and 8min respectively, adding mixed slurry according to the use amount of 80g/t of the emulsified diesel oil as a collector after the treatment, and stirring and sizing;
(3) Placing the stirred slurry into a 1.5LXFD single-tank flotation machine, adding sodium hydroxide to adjust the pH of the slurry to 10 and mixing the slurry for 3min, adding sodium pyrophosphate with the dosage of 120g/t to mix the slurry for 3min, adding 25g/t of No. 2 oil and mixing the slurry for 1min, performing flotation operation, wherein the flotation time is 5min, the rotation speed of the flotation machine is 2000r/min, the aeration quantity is 0.4m 3/min, the obtained concentrate product is negative electrode material graphite, and the tailing product is positive electrode material lithium iron phosphate.
And finally, the cathode graphite powder with the recovery rate and grade of 98.32% and 97.56% respectively and 99.81% and 98.76% respectively can be obtained through detection.
Claims (9)
1. The method for improving the flotation separation efficiency of the anode and cathode materials of the waste lithium batteries is characterized by comprising the following steps of:
(1) Mixing the anode and cathode materials of the waste lithium batteries with water, and stirring and sizing to obtain mixed slurry, wherein the stirring speed is 3000-10000 r/min;
(2) Adding a collector into the mixed slurry obtained in the step (1) and stirring and mixing the mixed slurry, wherein the collector is emulsified diesel oil obtained by ultrasonic emulsification of diesel oil and water, the dosage of the collector in each ton of mixed slurry is 80-200 g, the ultrasonic emulsification time is 3-30 min, the ultrasonic power of ultrasonic emulsification is 300-600 w, and the frequency of the ultrasonic power is 20-80 kHz;
(3) Placing the slurry obtained after stirring and size mixing in the step (2) into a flotation machine, adding a pH regulator to regulate the pH of the slurry, adding a dispersing agent, adding a foaming agent and carrying out flotation separation to obtain lithium-containing positive electrode powder and negative electrode graphite powder.
2. The method according to claim 1, wherein the mass concentration of the mixed slurry in the step (1) is 10% -50%.
3. The method of claim 1, wherein the stirring and size mixing time in the step (1) and the step (2) is 5-30 min, and the stirrer for stirring and size mixing is an electromechanical stirrer or a magnetic stirrer.
4. The method of claim 1, wherein the emulsified diesel oil in step (2) has a water to oil ratio of 1:1 to 1:3.
5. The method of claim 1, wherein in the step (3), the dispersing agent is one or a combination of several of sodium silicate, sodium hexametaphosphate, sodium tripolyphosphate and sodium pyrophosphate, and the amount of the dispersing agent in each ton of slurry after stirring and size mixing is 10-1000 g.
6. The method of claim 1, wherein in the step (3), the pH of the slurry is adjusted to 8-10, and in the step (3), the pH adjuster is one or a combination of several of sodium carbonate, sodium hydroxide, hydrochloric acid or sulfuric acid.
7. The method of claim 1, wherein the foaming agent in the step (3) is one or a combination of a plurality of eucalyptus oil, 2# oil, camphor oil or MIBC, and the amount of the foaming agent in each ton of slurry after stirring and pulping is 10-50 g.
8. The method of claim 1, wherein the flotation machine of step (3) is an XFD single cell flotation machine.
9. The method according to any one of claims 1 to 8, wherein in the flotation separation operation in step (3), the rotation speed of the flotation machine is 1500-2500 r/min, and the aeration amount is 0.2-0.8 m 3/min.
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| CN115784268B (en) * | 2022-11-28 | 2025-08-05 | 武汉瑞科美新能源有限责任公司 | A method for jointly recovering lithium and graphite from positive and negative electrode black powder |
| JP2024103899A (en) * | 2023-01-23 | 2024-08-02 | Ｊｆｅスチール株式会社 | Graphite Refining Method |
| CN115863822A (en) * | 2023-02-09 | 2023-03-28 | 湖南五创循环科技股份有限公司 | Method for efficiently separating and recovering valuable substances in waste lithium battery electrode powder |
| CN115893355A (en) * | 2023-02-15 | 2023-04-04 | 中钢天源股份有限公司 | A method for recovering iron phosphate and carbon from iron phosphorus slag after lithium extraction |
| CN116140073A (en) * | 2023-02-23 | 2023-05-23 | 湖南五创循环科技股份有限公司 | Method for carrying out flotation separation on anode and cathode mixed materials of waste lithium iron phosphate battery |
| CN116441061B (en) * | 2023-05-05 | 2025-06-24 | 江西飞宇新能源科技有限公司 | A method for improving the grade of lithium mica concentrate |
| CN117163954A (en) * | 2023-09-05 | 2023-12-05 | 荆门市格林美新材料有限公司 | Separation and purification method of negative graphite in waste lithium iron phosphate battery |
| CN118676463B (en) * | 2024-06-01 | 2025-11-07 | 福州大学 | Method for separating anode and cathode materials of waste lithium battery through floatation |
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