CN117577991B - Wet recovery method of poor positive electrode material, positive electrode material and lithium iron phosphate battery - Google Patents
Wet recovery method of poor positive electrode material, positive electrode material and lithium iron phosphate battery Download PDFInfo
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- CN117577991B CN117577991B CN202410058596.4A CN202410058596A CN117577991B CN 117577991 B CN117577991 B CN 117577991B CN 202410058596 A CN202410058596 A CN 202410058596A CN 117577991 B CN117577991 B CN 117577991B
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- phosphate battery
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 82
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 73
- 238000011084 recovery Methods 0.000 title claims description 22
- 239000000463 material Substances 0.000 claims abstract description 89
- 239000010405 anode material Substances 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 239000011888 foil Substances 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 31
- 238000004064 recycling Methods 0.000 claims abstract description 21
- 238000012216 screening Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 34
- 239000002033 PVDF binder Substances 0.000 abstract description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 19
- 230000002950 deficient Effects 0.000 abstract description 14
- 238000000197 pyrolysis Methods 0.000 abstract description 12
- 239000013543 active substance Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000001681 protective effect Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 description 14
- 208000005156 Dehydration Diseases 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/35—Shredding, crushing or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/15—Electronic waste
- B09B2101/16—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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to a wet recycling method of a poor anode material, the anode material and a lithium iron phosphate battery, wherein the poor materials are integrally soaked by a solvent; removing part of the solvent to a preset content by adopting a roller; wet crushing to a preset size; drying the wet crushed material; the dried material is subjected to bar pin type scattering treatment; separating the scattered materials; crushing the separated polar powder; and (5) screening and demagnetizing the crushed pole powder. The defective products of the anode materials of the lithium iron phosphate battery are fully utilized, and the waste of resources is avoided; the lithium iron phosphate anode material in the defective products is recovered by adopting a wet method, active substances and aluminum foils are separated by adopting the wet method, and the polyvinylidene fluoride does not generate pyrolysis reaction; and the drying process does not need protective gas, the disposal cost is low, the surface of the positive electrode material with the activity destroyed by the decomposition of polyvinylidene fluoride can be avoided, and the recovered positive electrode material is ensured to maintain the original electrochemical performance as much as possible.
Description
Technical Field
The application relates to the field of recovery of defective products of lithium ion batteries, in particular to a wet recovery method of a defective positive electrode material, a positive electrode material and a lithium iron phosphate battery, namely a wet recovery method of a defective lithium iron phosphate battery positive electrode material, a regenerated defective lithium iron phosphate battery positive electrode material and a regenerated lithium iron phosphate battery.
Background
The lithium iron phosphate battery is a lithium ion battery which uses lithium iron phosphate (LiFePO 4, LFP) as a positive electrode material and carbon as a negative electrode material, has the advantages of long cycle life, good safety performance, small self-discharge rate and no memory effect, and has been widely used. In the production process, especially in the process upgrading improvement, defective products inevitably exist in the lithium iron phosphate battery, and the problem of resource waste of a large amount of lithium iron phosphate battery materials, especially cathode materials, is also brought.
The application publication No. CN115939553A discloses a dry-wet mixed physical recycling method of leftover materials of a positive plate of a lithium iron phosphate battery, which comprises the steps of shearing a lithium iron phosphate pole piece into a proper size, rolling and stirring, flushing dust removal by using air flow, and removing broken pole piece fragments; drying the pole piece; placing a drain net in the deionized water tank; the materials are conveyed to the upper part of a leakage net, high pressure bubbling is carried out from the two sides of the upper part of the leakage net, the pole piece is impacted, rolled and stirred, and active substances are separated from aluminum foils on the pole piece; grinding the separated active substances, and breaking the active substances to fall under a grid; collecting the aluminum foil suspended in water above the leakage net; collecting the active substances from the bottom of the tank, and dehydrating, drying and calcining without oxygen; classifying and crushing the calcined active substances into tiny particles by using an airflow crusher; carrying out dry powder demagnetization on the active substances; and carrying out air classification on the particles of the demagnetized active material dry powder, and removing ultra-coarse particles and part of ultra-fine particles, thereby obtaining fine powder of the lithium iron phosphate positive electrode material with moderate carbon content.
However, the recovery method disclosed in the above patent document is only used for treating the scraps, and needs to be performed under the protection of a protective gas, and because the calcination and pyrolysis temperatures are high, part F can react with the positive electrode material in the decomposition process of polyvinylidene fluoride (Poly-VINYLIDENE FLUORIDE, PVDF, also called polyvinylidene fluoride) in the binder of the positive electrode material, so that the electrochemical performance is degraded, and thus it is difficult to recover the positive electrode material meeting the requirements.
Disclosure of Invention
Accordingly, it is necessary to provide a wet recovery method for a poor lithium iron phosphate battery positive electrode material, a regenerated poor lithium iron phosphate battery positive electrode material, and a lithium iron phosphate battery.
In one embodiment, a wet recovery method of a poor lithium iron phosphate battery positive electrode material includes the steps of:
S200, integrally soaking bad materials by adopting a solvent;
S300, removing part of the solvent from the soaked material to a preset content by adopting a roller;
S400, carrying out wet crushing on the material from which part of the solvent is removed to a preset size;
S500, drying the wet crushed material;
S600, carrying out bar pin type scattering treatment on the dried material;
S700, separating the scattered materials;
s800, crushing the separated pole powder;
S900, screening and demagnetizing the crushed pole powder.
According to the wet recycling method of the poor lithium iron phosphate battery anode material, wet recycling and regeneration are realized on the poor lithium iron phosphate battery anode material, so that on one hand, the poor product of the lithium iron phosphate battery anode material is fully utilized, and the waste of resources is avoided; on the other hand, the wet method is adopted to recycle the lithium iron phosphate anode material in the defective products, and the wet method is adopted to separate active substances and aluminum foils, so that the polyvinylidene fluoride does not generate pyrolysis reaction; and the drying process does not need protective gas, the disposal cost is low, the surface of the positive electrode material with the activity destroyed by the decomposition of polyvinylidene fluoride can be avoided, and the recovered positive electrode material is ensured to maintain the original electrochemical performance as much as possible.
In one embodiment, before step S200, the method further includes the steps of: s100, for bad materials, water and ethanol are adopted for cleaning at least once in turn.
In one embodiment, in step S200, the poor materials are immersed in the solvent as a whole at normal temperature and pressure.
In one embodiment, in step S200, the solvent is water.
In one embodiment, in step S200, a lithium hydroxide solution or a lithium carbonate solution is added in an amount of 0.01mol/L to 0.03mol/L according to a preset time-quantity curve during the soaking.
In one embodiment, in step S200, the soaking liquid-solid ratio is 2:1 to 10:1, the soaking time is not more than 10 hours, and the soaking temperature is not more than 100 ℃.
In one embodiment, in step S300, the water content of the dehydrated material is not higher than 60%.
In one embodiment, in step S600, a pin breaker is used to perform pin breaking, where the pin breaker has a working speed of 20m/S to 80m/S and a working time of 2S to 30S.
In one embodiment, a regenerated poor lithium iron phosphate battery positive electrode material is produced using the wet recovery method of the poor lithium iron phosphate battery positive electrode material of any of the embodiments.
In one embodiment, a lithium iron phosphate battery includes the regenerated poor lithium iron phosphate battery positive electrode material of any of the embodiments.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments or the conventional techniques of the present application, the drawings required for the descriptions of the embodiments or the conventional techniques will be briefly described below, and it is apparent that the drawings in the following descriptions are only some embodiments of the present application, and other drawings may be obtained according to the drawings without inventive effort for those skilled in the art.
Fig. 1 is a schematic flow chart of an embodiment of a method for repairing a positive electrode material of a lithium iron phosphate battery according to the present application.
Fig. 2 is a schematic flow chart of another embodiment of a method for repairing a positive electrode material of a lithium iron phosphate battery according to the present application.
Fig. 3 is a schematic diagram of a cathode material recovered in example 1 of the method for repairing a cathode material of a lithium iron phosphate battery according to the present application.
FIG. 4 is a schematic diagram of the recovered aluminum foil of example 1.
Fig. 5 is a schematic diagram showing the results of the charge-discharge cycle performance test of example 1.
Fig. 6 is a schematic diagram of the results of the specific capacity-cycle test of example 1.
Fig. 7 is a graph showing the results of the median voltage-cycle test of example 1.
Fig. 8 is a schematic diagram showing the results of the charge-discharge cycle performance test of comparative example 1 using the conventional pyrolysis method.
FIG. 9 is a schematic diagram of the results of the specific capacity-cycle test of comparative example 1.
Fig. 10 is a graph showing the results of the median voltage-cycle test of comparative example 1.
Fig. 11 is a schematic diagram showing the charge-discharge cycle performance test results of example 2 of the method for repairing a lithium iron phosphate battery positive electrode material according to the present application.
Fig. 12 is a schematic diagram showing the results of the specific capacity-cycle test of fig. 2.
Fig. 13 is a graph showing the results of the median voltage-cycle test of fig. 2.
Detailed Description
In order that the above objects, features and advantages of the application will be readily understood, a more particular description of the application will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. The present application may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the application, whereby the application is not limited to the specific embodiments disclosed below.
It will be understood that when an element is referred to as being "mounted" or "disposed" on another element, it can be directly on the other element or intervening elements may also be present. When a component is considered to be "connected" to another component, it can be directly connected to the other component or intervening components may also be present. The terms "vertical", "horizontal", "upper", "lower", "left", "right" and the like are used in the description of the present application for the purpose of illustration only and do not represent the only embodiment.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present application, unless expressly stated or limited otherwise, a first feature "up" or "down" on a second feature may be that the first feature is in direct contact with the second feature, or that the first feature and the second feature are in indirect contact through intermedial media. Moreover, a first feature "above," "over" and "on" a second feature may be a first feature directly above or obliquely above the second feature, or simply indicate that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely under the second feature, or simply indicating that the first feature is less level than the second feature.
Unless defined otherwise, all technical and scientific terms used in the specification of the present application have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used in the description of the present application includes any and all combinations of one or more of the associated listed items.
The application discloses a wet recycling method of a poor lithium iron phosphate battery positive electrode material, a regenerated poor lithium iron phosphate battery positive electrode material and a lithium iron phosphate battery, which comprise part of or all of the technical characteristics of the following embodiments; that is, the method for repairing the lithium iron phosphate battery cathode material includes the following partial steps or all the steps. In one embodiment of the present application, a method for repairing a positive electrode material of a lithium iron phosphate battery is shown in fig. 1, and includes the steps of: s200, integrally soaking bad materials by adopting a solvent; s300, removing part of the solvent from the soaked material to a preset content by adopting a roller; s400, carrying out wet crushing on the material from which part of the solvent is removed to a preset size; s500, drying the wet crushed material; s600, carrying out bar pin type scattering treatment on the dried material; s700, separating the scattered materials; s800, crushing the separated pole powder; s900, screening and demagnetizing the crushed pole powder. According to the wet recycling method of the poor lithium iron phosphate battery anode material, wet recycling and regeneration are realized on the poor lithium iron phosphate battery anode material, so that on one hand, the poor product of the lithium iron phosphate battery anode material is fully utilized, and the waste of resources is avoided; on the other hand, the wet method is adopted to recycle the lithium iron phosphate anode material in the defective products, and the wet method is adopted to separate active substances and aluminum foils, so that the polyvinylidene fluoride does not generate pyrolysis reaction; and the drying process does not need protective gas, the disposal cost is low, the surface of the positive electrode material with the activity destroyed by the decomposition of polyvinylidene fluoride can be avoided, and the recovered positive electrode material is ensured to maintain the original electrochemical performance as much as possible.
Generally, a positive electrode material of a lithium iron phosphate battery mainly includes: lithium iron phosphate, conductive carbon black, PVDF as a binder, N-methylpyrrolidone (NMP) as a solvent, and the like. The positive electrode material is usually formed into a sheet shape, and is led out through aluminum foil current collection, namely, bad materials mainly comprise lithium iron phosphate positive electrode materials, a binder and aluminum foil, and the lithium iron phosphate positive electrode materials mainly need to be recovered.
In order to avoid wasting the poor lithium iron phosphate battery anode material or producing the poor lithium iron phosphate battery anode material in the process upgrading and acceptance standard change, the application provides a wet recycling method of the poor lithium iron phosphate battery anode material, and in each embodiment, in the step S200, the poor material is integrally soaked by a solvent; further, in one embodiment, the solvent is adopted to soak the poor materials integrally in a single-layer soaking mode, namely, the materials in soaking are integral, and the single-layer soaking mode is adopted, and the materials can be cut into sheets with the length and the width of more than 40 cm and more than 80 cm if necessary; the area of the sheet does not need to be too small, because the too small area adversely affects the consistency and separation effect of the results obtained in the subsequent wet crushing related step; also stacks with voids are possible, but less effective. In one embodiment, in step S200, the poor materials are immersed in the solvent as a whole at normal temperature and pressure. On one hand, the method is applied to the poor lithium iron phosphate battery anode material, and is different from a repairing method of the waste lithium iron phosphate battery anode material, the poor lithium iron phosphate battery anode material is never contacted with electrolyte and other reagents, and the anode material in the poor lithium iron phosphate battery anode material still has better electrochemical performance, so that a soaking mode at normal temperature and normal pressure can be adopted. On the other hand, the method is applied to recycling the poor lithium iron phosphate battery anode material, namely the poor product of the lithium iron phosphate battery anode material, so that the poor material is integrally soaked by the solvent, and compared with the prior art, the method has the advantage that the problem that the whole poor material is completely soaked is solved, and the method can avoid the irrelevancy of the relevant steps of removing part of the solvent and the relevant steps of wet crushing from the roller, namely the uniformity is also called consistency.
In one embodiment, a sodium hydroxide solution with a concentration of 0.001mol/L to 0.005mol/L is used as the solvent, the solid-to-liquid ratio of the positive electrode material to the solvent is 1:10 to 1:30, and the sodium hydroxide solution is used as the solvent to remove the residual aluminum and the binder in the positive electrode material at normal temperature and normal pressure. The rest of the embodiments are analogized and will not be described in detail. In addition, considering the cost issue and the recovery rate issue, in one embodiment, in step S200, the solvent is water, that is, the poorly soaked material is integrally soaked with water; the method is applicable to materials such as aqueous carbon-coated aluminum foil which adopt aqueous adhesives; the method comprises the steps of adopting water to integrally soak bad materials, wherein the materials are adhered with the anode material of the lithium iron phosphate battery by adopting an aqueous adhesive. In one embodiment, in step S200, water is used to soak the poor materials in its entirety until a preset period of time expires; in one embodiment, in step S200, the soaking liquid-solid ratio is 2:1 to 10:1, the soaking time is not more than 10 hours, and the soaking temperature is not more than 100 ℃; i.e. the preset time period is less than 10 hours. In one embodiment, in step S200, the soaking liquid-solid ratio is 2:1 to 6:1. In general, the situation is easy to misunderstand that the more water is, the better the water is, but the fact is not the same, bad materials can be completely soaked when the soaking liquid-solid ratio is 2:1, and the allowance can be reserved after the soaking is finished when the soaking liquid-solid ratio is 6:1, so the proportion design is beneficial to reducing the space occupation, saving the water consumption and reducing the waste water consumption. In one embodiment, the preset time period is greater than 0.5 hours. In other embodiments, the solvent may also be ethanol or carbonate organic solvents. But the comprehensive cost and the separation and recovery effect are realized, the solvent is water, purified water or deionized water and the like can be adopted, so that the wet recovery rate of the poor lithium iron phosphate battery anode material is ensured, and the method has the advantages of low cost and low cost. The soaking method is adopted to promote the stripping between the positive electrode material and the foil, so that the method is free from the defect that an alkaline solvent or an organic solvent is required to separate the aluminum foil from the positive electrode sheet in the traditional thought, and the design purpose can be achieved by matching with the following process. In one embodiment, in step S200, the soaking solution has a pH of 6 to 11. Further, the solid-liquid ratio of the soaking solution is 3:1 to 5:1, the soaking time is not more than 1 hour, and the pH of the soaking solution is 7 to 11. Generally, if purified water is used, the pH of the soaking solution is 7, and the soaking may be acidic due to the influence of the positive electrode sheet, such as residual electrolyte, during the soaking process, and the pH may be adjusted to 7 to 11, which is advantageous for improving the soaking efficiency, i.e., shortening the preset time period, and may be implemented in combination with the following examples.
Considering that the soaking environment may be acidic as part of the material is released during the soaking, in one embodiment, in step S200, 0.01mol/L lithium hydroxide solution is added according to a preset time-quantity curve during the soaking. The time-quantity curve is a relation curve of the quantity of the added 0.01mol/L lithium hydroxide solution along with the change of soaking time; further, in one embodiment, during the soaking process, 0.01mol/L lithium hydroxide solution is added according to a preset time-quantity curve, so that the soaking environment is kept at a pH value of 7 to 9, namely, is in a neutral to weak alkaline environment; further, in one of the embodiments, during the soaking, a lithium hydroxide solution or a lithium carbonate solution of 0.01mol/L to 0.03mol/L is added in a preset time-quantity curve so as to maintain the soaking environment at a pH value of 7 to 8. This is because it has been found in practice that it is difficult to maintain a neutral pH of 7 at all times, and it is desirable to provide a range of elasticity that will allow the entire soaking process of the undesirable materials to remain in a neutral or even slightly alkaline environment.
In each embodiment, in step S300, a roller is used to remove a part of the solvent from the soaked material to a preset content; for the embodiment using water as the solvent, the soaked material is soaked in water for a preset period of time, and the soaked material is still sheet-shaped, so that the soaked material can be called as a positive plate. In one embodiment, in step S300, the water content of the dehydrated material is not higher than 60%; in one embodiment, the water content of the dehydrated material is not less than 30%. The rest of the embodiments are analogized and will not be described in detail. The dewatering of the drum is advantageous for controlling the moisture content of the dewatered material to cooperate with a subsequent wet crushing step.
In each embodiment, in step S400, wet crushing the material after removing part of the solvent to a preset size; in one embodiment, the predetermined size is greater than 5 cm in at least one of length and width. For the embodiment using water as the solvent, wet crushing the dehydrated material to a preset size; the dehydrated material includes, but is not limited to, a positive electrode sheet obtained after dehydration treatment by a roller. Further, in one embodiment, in step S400, the moisture content of the material in the wet crushing process is not higher than 60%; and/or the water content of the materials in the wet crushing process is not lower than 30%. On one hand, the roller dehydration is carried out before wet crushing, which is beneficial to avoiding that excessive moisture or other solvents influence the wet crushing efficiency and uniformity; on the other hand, the roller dehydration is matched with wet crushing, which is favorable for matching with the precondition of achieving the subsequent drying and dehydration.
In each embodiment, in step S500, the wet crushed material is dried; taking water as an example, the wet crushed material is dried and dehydrated, and the rest of the solvent is the same, and the description is omitted. The wet crushed material is dried and dehydrated, for example, by feeding the wet crushed material into a drying device, and the step is a drying step, for example, drying and dehydrating by adopting a drying method, so as to further reduce the water content of the wet crushed positive electrode sheet to, for example, less than 1% or even less than 0.1%. Further, in one embodiment, the temperature of the drying dehydration is not higher than 200 ℃ and the drying time is 2 to 10 hours. Further, in one embodiment, the wet crushed material is dried and dehydrated by adopting a low-temperature drying mode, the temperature of the drying and dehydrating is not higher than 100 ℃, and the drying time is 4 to 10 hours. Unlike traditional implementation mode, the important application point of the application is that soaking, dewatering and wet crushing are carried out before drying and dewatering, so that the treatment is beneficial to avoiding that the electrochemical performance of regenerated positive electrode material is deteriorated as far as possible due to F generated by PVDF decomposition and reaction with the positive electrode material caused by earlier heating or baking.
In each embodiment, in step S600, the dried material is subjected to scattering treatment; for example, a bar pin type breaker or other breaker is used for breaking; further, in step S600, the dried material is subjected to a pin breaking process. Taking water as an example, the dried and dehydrated material is subjected to bar pin type scattering treatment. In one embodiment, in step S600, a pin breaker is used to perform pin breaking, where the pin breaker has a working speed of 20m/S to 80m/S and a working time of 2S to 30S. In this embodiment, the rod pin type breaker or the rod pin mill is used to separate the pole powder from the pole piece deeply, which is especially suitable for the situation that the pole powder separating effect is poor, and the rod pin type breaker is used to separate the pole powder from the foil on one hand, and is used as a pretreatment step to achieve a better superfine grinding effect in cooperation with the crushing treatment of the subsequent step S800.
In each embodiment, in step S700, the scattered material is subjected to separation treatment, for example, sent to a vibration separation device to be subjected to separation treatment, so as to realize separation of the polar powder and the foil; and separating the materials to obtain an aluminum current collector, namely aluminum foil, namely foil, and separating the foil to obtain the polar powder, namely powdery lithium iron phosphate. Further, as the solvent is adopted to integrally soak bad materials in the previous step S200, and the processes of roller and wet crushing are combined, the finely crushed aluminum sheets are thoroughly separated in the step S700, so that the phenomenon that the broken aluminum is mixed into the electrode powder to cause that a finished product punctures a battery diaphragm is avoided, bad occurs when the finished product is light, and the use safety is influenced when the finished product is heavy is avoided.
In each embodiment, in step S800, the pole powder after the separation treatment is subjected to the crushing treatment; for example, using a jaw crusher or a fine crusher; the crushing may be performed by using an air jet mill as the crushing treatment. Further, in step S800, the crushing process further includes a grinding process such as further crushing with a jaw crusher or a fine crusher, and then grinding with a grinder such as a three-head grinder to obtain a positive electrode powder.
In each embodiment, in step S900, the crushed pole powder is subjected to sieving and demagnetizing treatment. Thus, the positive electrode material, for example, powdery lithium iron phosphate, which is a powdery positive electrode material from which aluminum foil, binder, and the like are removed, can be recovered by subsequent steps such as sieving, demagnetizing, and the like. The poor lithium iron phosphate battery anode material is regenerated and recovered, and can be called as anode active material or anode active material powder, and can be packaged and further regenerated to improve the performance.
In such a design, the residual aluminum and binder in the positive electrode material can be removed by using a solvent at normal temperature and normal pressure, and further, if necessary, it is also considered to use warm water of 20 to 40 ℃ for washing in step S100 and warm water of 20 to 40 ℃ for soaking in step S200, so as to improve the separation effect of the aluminum foil and the electrode powder. The design mode of wet recovery is given to the whole, the electrochemical performance of the original lithium iron phosphate active material can be reserved to the greatest extent, the binding force between the material bonded on the aluminum foil and the aluminum foil is not strong because the pole piece is not circulated, and the gap between the material and the aluminum foil can be filled with water molecules with smaller mass, so that the separation of the anode material and the aluminum foil is facilitated; on the other hand, when the dehydrated material is dried at low temperature, the moisture in the gaps of the anode material and the aluminum foil is evaporated, the peeling of the foil and the anode material can be further promoted, PVDF aging can be promoted by the low-temperature drying treatment, the anode material is separated from the aluminum foil on the premise of avoiding the decomposition of PVDF,
In contrast, in the conventional pyrolysis powder removal process, the pyrolysis temperature is generally 300 ℃ to 500 ℃, and nitrogen protection is required, so that the process is complex, the energy consumption is high, PVDF can be decomposed, and the decomposed part F can erode the positive electrode material to damage the surface of the active positive electrode material, so that the electrochemical performance of the active material is deteriorated. In the embodiment, the lithium iron phosphate positive electrode material is recovered by adopting a wet method, active substances and aluminum foils are separated by adopting a wet method, and PVDF does not undergo pyrolysis reaction; the drying process does not need protective gas, the disposal cost is low, the PVDF can be prevented from decomposing and damaging the surface of the active material, and the original electrochemical performance of the material is ensured to be maintained as much as possible; in the process of carrying out the breaking-up treatment, for example, the drying material is treated by a bar pin type breaking-up machine, the aluminum foil has ductility and toughness, and the positive electrode material is easily separated from the aluminum foil, namely, the foil due to the fact that the aluminum foil is broken up in the equipment through vibration. The separated polar powder retains the original performance, can be directly put into reproduction without source supplementing and/or solid phase repairing, and is beneficial to saving the energy consumption of the traditional recovery and regeneration process, improving the production efficiency and avoiding the resource waste.
In one embodiment, before step S200, the wet recycling method of the poor lithium iron phosphate battery cathode material further includes the steps of: s100, for bad materials, water and ethanol are adopted for cleaning at least once in turn, namely at least one time of water cleaning and at least one time of ethanol cleaning, one time of ethanol cleaning is arranged between two times of water cleaning, and one time of water cleaning is arranged between two times of ethanol cleaning; wherein a single water wash in combination with a single ethanol wash may be referred to as a single wash cycle. Further, in one embodiment, in step S100, the poor material containing the fine powder of lithium iron phosphate is washed with water and ethanol at least three times in turn, i.e. three washing cycles as described above. In one embodiment, the wet recovery method of the poor lithium iron phosphate battery cathode material is as shown in fig. 2, and includes the steps of: s100, for bad materials, water and ethanol are adopted to alternately clean at least once; s200, integrally soaking bad materials by adopting a solvent; s300, removing part of the solvent from the soaked material to a preset content by adopting a roller; s400, carrying out wet crushing on the material from which part of the solvent is removed to a preset size; s500, drying the wet crushed material; s600, carrying out bar pin type scattering treatment on the dried material; s700, separating the scattered materials; s800, crushing the separated pole powder; s900, screening and demagnetizing the crushed pole powder. The rest of the embodiments are analogized and will not be described in detail.
In one embodiment, a regenerated poor lithium iron phosphate battery positive electrode material is produced using the wet recovery method of the poor lithium iron phosphate battery positive electrode material of any of the embodiments. Namely, the regenerated poor lithium iron phosphate battery positive electrode material prepared by the wet recovery method of the poor lithium iron phosphate battery positive electrode material according to any embodiment. According to the regenerated poor lithium iron phosphate battery anode material, wet recycling regeneration is realized on the poor lithium iron phosphate battery anode material, so that on one hand, the poor product of the lithium iron phosphate battery anode material is fully utilized, and the waste of resources is avoided; on the other hand, the wet method is adopted to recycle the lithium iron phosphate anode material in the defective products, and the wet method is adopted to separate active substances and aluminum foils, so that the polyvinylidene fluoride does not generate pyrolysis reaction; and the drying process does not need protective gas, the disposal cost is low, the surface of the positive electrode material with the activity destroyed by the decomposition of polyvinylidene fluoride can be avoided, and the recovered positive electrode material is ensured to maintain the original electrochemical performance as much as possible.
In one embodiment, a lithium iron phosphate battery includes the regenerated poor lithium iron phosphate battery positive electrode material of any of the embodiments. It will be appreciated that the lithium iron phosphate battery also includes other configurations, in one embodiment, the lithium iron phosphate battery includes a positive electrode including the regenerated poor lithium iron phosphate battery positive electrode material of any of the embodiments, and a negative electrode. The rest of the embodiments are analogized and will not be described in detail.
The wet recovery method of the poor lithium iron phosphate battery cathode material is further described below with reference to a graph.
Example 1:
In this embodiment, the core-rolled pole piece is taken as an example of the poor material, and it can be understood that the wet recovery method of the poor lithium iron phosphate battery positive electrode material is also applicable to pole pieces with other shapes.
Under the water soaking condition of soaking for 2 hours at the temperature of 60 ℃, the materials after water soaking are subjected to roller dehydration, wet crushing, drying dehydration, bar pin type scattering and separation treatment, the obtained anode material is shown in a graph 3, the obtained aluminum foil is shown in a graph 4, and the wet recovery method of the poor lithium iron phosphate battery anode material can realize the complete separation of the anode material and the aluminum foil in the coiled lithium iron phosphate pole piece. And further crushing, screening, demagnetizing and grinding the anode material to obtain the anode powder. The content of the detected element in the obtained positive electrode powder is shown in the following table 1:
TABLE 1
As can be seen from table 1, the chemical element analysis results show that the main elements are Fe, P, and C, and the balance (Other) is mainly oxygen, and further includes Other elements, and the Other elements in table 1 are not suitable to write O directly or consider all O, although the Other elements are mainly O, because the oxygen element is easy to dissipate and combine with Other elements; the positive electrode powder also contains 0.0566% of Al, and the aluminum content is extremely low. It can be considered that the complete separation of the aluminum foil is substantially achieved.
The positive electrode powder was used for trial production and assembly to form a button cell, and then the charge-discharge cycle performance was tested, and the results are shown in fig. 5 and table 2 below:
TABLE 2
The specific capacity of the button cell in cyclic charge and discharge is shown in fig. 6, the median voltage is shown in fig. 7, and the initial charge specific capacity of 0.1C is up to 165.82mAh/g and the specific discharge capacity is 157.19mAh/g as can be seen from the combination of fig. 5 to 7 and the table 2; the initial charging specific capacity of 0.2C is up to 158.17mAh/g, and the specific discharge capacity is 155.90mAh/g; the initial charging specific capacity of 0.5C is up to 156.40mAh/g, and the specific discharge capacity is 152.58mAh/g; the initial charging specific capacity of 1C is up to 152.62mAh/g, the specific discharge capacity is 147.44mAh/g, and after 78 times of circulation, the specific charge and discharge capacity is always kept at about 143 mAh/g; and the median voltage is always between 3.26V and 3.5V, and the battery performance is kept better, namely the regenerated poor lithium iron phosphate battery anode material has better electrical performance.
Comparative example 1:
after the positive electrode powder is obtained by adopting the traditional pyrolysis method in the same batch of core pole pieces as in the embodiment 1 and adopting the traditional pyrolysis method, the positive electrode powder is assembled into a button cell by trial production, and then the charge-discharge cycle performance test is carried out, and the results are shown in fig. 8 and the following table 3:
TABLE 3 Table 3
The specific capacity of the button cell in cyclic charge and discharge is shown in fig. 9, the median voltage is shown in fig. 10, and as can be seen from fig. 8 to fig. 10 and the table 3 above, the voltage difference shown in fig. 8 is large, which means that the internal polarization of the cell is relatively serious, and the cell performance is affected; the initial charging specific capacity of 0.1C is up to 173.16mAh/g, and the specific discharge capacity is 153.29mAh/g; the initial charging specific capacity of 0.2C is up to 154.40mAh/g, and the specific discharge capacity is 149.36mAh/g; the initial charging specific capacity of 0.5C is up to 149.65mAh/g, and the specific discharge capacity is 142.03mAh/g; the initial charging specific capacity of 1C is up to 140.68mAh/g, and the specific discharge capacity is 129.20mAh/g; after 90 cycles, the specific charge-discharge capacity is always kept at about 123mAh/g, and is relatively low compared with the embodiment 1; and the median voltage is in a continuously reduced state, and the battery performance is poor.
Example 2:
in this embodiment, the sheet-shaped electrode sheet is taken as an example of the poor material, and the material after soaking is subjected to drum dehydration, wet crushing, drying dehydration, bar pin type scattering and separation treatment under the soaking condition of soaking for 2 hours at the temperature of 60 ℃ to obtain the positive electrode material. The content of the element detected for the positive electrode powder is shown in the following table 4:
TABLE 4 Table 4
As can be seen from table 4 above, the chemical element analysis results show that the main elements are also Fe, P, C, and the balance (Other) is mainly oxygen; 0.03% Al is present. It is also believed that substantially complete separation of the positive electrode powder from the aluminum foil is achieved.
The above positive electrode powder was used for trial assembly to form a button cell, and then charge-discharge cycle performance was tested, and the results are shown in fig. 11 and table 5 below:
TABLE 5
The specific capacity of the button cell in cyclic charge and discharge is shown in fig. 12, the median voltage is shown in fig. 13, and the initial charge specific capacity of 0.1C is up to 168.55mAh/g and the specific discharge capacity is 155.38mAh/g as can be seen from the combination of fig. 11 to 13 and table 5; the initial charging specific capacity of 0.2C is up to 156.54mAh/g, and the specific discharge capacity is 153.20mAh/g; the initial charging specific capacity of 0.5C is up to 153.61mAh/g, and the specific discharge capacity is 147.67mAh/g; the initial charge specific capacity of 1C is up to 147.76mAh/g, the specific discharge capacity is 139.14mAh/g, and after 90 times of circulation, the specific charge and discharge capacity is always kept at about 141 mAh/g; the median voltage is always kept between 3.26V and 3.5V, so that the battery has better electrical performance.
Comparative example 2:
After the positive electrode powder is obtained by adopting the traditional pyrolysis method in the same type and same batch of core pole pieces in example 2 and adopting the background technology, the positive electrode powder is assembled into a button cell by trial production, and then the charge-discharge cycle performance test is carried out, and the result is shown in the following table 6:
TABLE 6
The test result of the charge-discharge cycle performance of the button cell, the specific capacity of the cycle charge and discharge and the change of the median voltage are similar to those of fig. 8 to 10, and it can be seen from the above table 6 that the comparative example 2 also has the problem of larger voltage difference, which means that the internal polarization of the cell is relatively serious, and the cell performance is affected; the initial charging specific capacity of 0.1C is up to 154.90mAh/g, and the specific discharge capacity is 150.07mAh/g; the initial charging specific capacity of 0.2C is up to 151.18mAh/g, and the specific discharge capacity is 147.35mAh/g; the initial charging specific capacity of 0.5C is up to 147.43mAh/g, and the specific discharge capacity is 140.55mAh/g; the initial charge specific capacity of 1C is up to 141.56mAh/g, the specific discharge capacity is 133.10mAh/g, and after 90 times of circulation, the specific charge and discharge capacity is always kept about 121mAh/g and is relatively lower than that of the embodiment 2; and the median voltage is in a continuously reduced state, and the battery performance is poor.
Further, another embodiment of the present application includes a method for wet recycling of a defective positive electrode material, a positive electrode material, and a lithium iron phosphate battery, which are implemented by combining the technical features of the above embodiments, wherein the wet recycling method of the defective positive electrode material is a wet recycling method of the defective lithium iron phosphate battery positive electrode material, and the positive electrode material is a regenerated defective lithium iron phosphate battery positive electrode material.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of the application should be determined from the following claims.
Claims (10)
1. The wet recovery method of the poor lithium iron phosphate battery anode material is characterized by comprising the following steps of:
S200, integrally soaking bad materials by adopting a solvent; wherein the solvent is water, the solid-liquid ratio of the soaking solution is 2:1 to 10:1, the soaking time is not more than 10 hours and more than 0.5 hour, and the soaking temperature is not more than 100 ℃;
S300, removing part of the solvent from the soaked material to a preset content by adopting a roller; wherein the water content of the dehydrated material is not higher than 60% and not lower than 30%;
S400, carrying out wet crushing on the material from which part of the solvent is removed to a preset size;
S500, drying the wet crushed material;
s600, scattering the dried material;
S700, separating the scattered materials to separate the polar powder from the foil;
s800, crushing the separated pole powder;
S900, screening and demagnetizing the crushed pole powder.
2. The method for wet recycling of poor lithium iron phosphate battery positive electrode material according to claim 1, further comprising, before step S200: s100, for bad materials, water and ethanol are adopted for cleaning at least once in turn.
3. The method for wet recycling of poor lithium iron phosphate battery positive electrode material according to claim 1, wherein in step S200, poor materials are immersed in the solvent as a whole at normal temperature and pressure.
4. The method for wet recycling of poor lithium iron phosphate battery positive electrode material according to claim 1, wherein in step S200, the poor materials are soaked in a single-layer soaking manner.
5. The wet recycling method of bad lithium iron phosphate battery positive electrode material according to claim 1, wherein in step S200, 0.01mol/L to 0.03mol/L of lithium hydroxide solution or lithium carbonate solution is added according to a preset time-quantity curve during the soaking process.
6. The method for wet recycling of poor lithium iron phosphate battery positive electrode material according to claim 1, wherein in step S500, the temperature of drying and dehydration is not higher than 200 ℃, and the drying time is 2 hours to 10 hours.
7. The method for wet recycling of poor lithium iron phosphate battery positive electrode material according to claim 6, wherein the temperature of drying and dehydration is not higher than 100 ℃, and the drying time is 4 hours to 10 hours.
8. The method for wet recycling of poor lithium iron phosphate battery positive electrode materials according to any one of claims 1 to 7, wherein in step S600, a bar pin type breaker is used for bar pin type breaking treatment, the working speed of the bar pin type breaker is 20m/S to 80m/S, and the working time is 2S to 30S.
9. A regenerated poor lithium iron phosphate battery positive electrode material, characterized in that the poor lithium iron phosphate battery positive electrode material is prepared by a wet recovery method according to any one of claims 1 to 8.
10. A lithium iron phosphate battery comprising the regenerated poor lithium iron phosphate battery positive electrode material of claim 9.
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| CN117577991A (en) | 2024-02-20 |
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