CN113083848A - Sorting and recycling method for positive and negative electrode materials of waste lithium iron phosphate batteries - Google Patents
Sorting and recycling method for positive and negative electrode materials of waste lithium iron phosphate batteries Download PDFInfo
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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 74
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002699 waste material Substances 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 92
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 238000012216 screening Methods 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000006148 magnetic separator Substances 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 239000010406 cathode material Substances 0.000 claims abstract description 8
- 239000008187 granular material Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007770 graphite material Substances 0.000 claims description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000011888 foil Substances 0.000 description 8
- 238000007885 magnetic separation Methods 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010926 waste battery Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
- B09B3/10—Destroying solid waste or transforming solid waste into something useful or harmless involving an adsorption step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07C—POSTAL SORTING; SORTING INDIVIDUAL ARTICLES, OR BULK MATERIAL FIT TO BE SORTED PIECE-MEAL, e.g. BY PICKING
- B07C5/00—Sorting according to a characteristic or feature of the articles or material being sorted, e.g. by control effected by devices which detect or measure such characteristic or feature; Sorting by manually actuated devices, e.g. switches
- B07C5/34—Sorting according to other particular properties
- B07C5/344—Sorting according to other particular properties according to electric or electromagnetic properties
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a sorting and recycling method for positive and negative electrode materials of waste lithium iron phosphate batteries, which is characterized in that a magnetic positive plate material and a non-magnetic negative plate are formed by subjecting a crushed and screened positive and negative plate mixture to an oxidation calcination method, the magnetic positive plate material and the non-magnetic negative plate material are separated after the magnetized positive and negative plate mixture is sorted by a magnetic separator, then the magnetic positive plate material and the non-magnetic negative plate material are separated, then the positive plate material and the negative plate material are selectively crushed and subjected to powder removal treatment respectively, and granular positive and negative electrode lithium iron phosphate powder and powdery negative electrode graphite powder are obtained after vibration screening. The method has simple process, effectively avoids the defect of environmental pollution caused by a large amount of wastewater generated in wet treatment, is favorable for protecting ecological environment, greatly reduces the recovery cost, has high economic benefit and good separation quality, reduces the impurity removal difficulty of subsequent material regeneration and utilization, and realizes high-valued recovery of the anode and cathode materials of the waste lithium iron phosphate battery.
Description
Technical Field
The invention belongs to the technical field of waste lithium battery recovery, and particularly relates to a method for sorting and recovering positive and negative electrode materials of waste lithium iron phosphate batteries.
Background
In recent years, with the rapid development of new energy automobiles, 5G energy storage base stations and the commercialization of products in the 3C field, the usage amount of lithium ion batteries is increasing continuously. The service life of the lithium ion battery is generally 5-8 years, and a large number of obsolete lithium ion batteries are produced. If the waste lithium ion battery can not be properly treated, not only is the waste of resources caused, but also certain pollution is caused to the environment.
In recent years, lithium iron phosphate batteries are introduced into the lithium nickel cobalt manganese oxide ternary battery market at a competitive price and with superior safety performance, so that the application amount of lithium iron phosphate in the fields of electric power and energy is continuously increased. In the market data, the loading amount of lithium iron phosphate on a vehicle in 2020 is close to 20Gwh, and the shipment amount of lithium iron phosphate batteries in the energy storage market is about 10 Gwh. In the recovery method of the waste lithium iron phosphate batteries after failure, the existing mainstream mechanical and physical crushing and sorting process in China generally carries out multistage crushing treatment on the waste lithium iron phosphate batteries, separates out shells and diaphragms by methods such as air separation, gravity separation, magnetic separation and the like, and then processes and processes the positive and negative plate mixture to obtain mixed powder of positive lithium iron phosphate material powder and negative graphite powder. However, the mixed powder of the positive electrode and the negative electrode has large mass and large volume, and meets the requirements of solid-liquid ratio and the like of a subsequent wet treatment process, so that the reactor has large volume, and simultaneously needs to consume a large amount of leaching acid and blending alkali, thereby causing large treatment capacity of subsequent industrial wastewater, high production cost and being not beneficial to large-scale industrialized operation.
Therefore, there is a need to address the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for sorting and recovering positive and negative electrode materials of waste lithium iron phosphate batteries, which has the advantages of simple process, short process flow, low cost, high quality of recovered products and no wastewater discharge.
The invention provides a method for sorting and recovering anode and cathode materials of waste lithium iron phosphate batteries, which comprises the following steps:
s1, crushing the positive and negative pole piece mixture obtained by processing the waste lithium iron phosphate battery, and screening to obtain a positive and negative pole piece mixed crushed material with the size range of 3-30 mm;
s2, oxidizing and calcining the mixed crushed material of the positive plate and the negative plate obtained in the step S1 to oxidize part of the lithium iron phosphate material on the surface of the positive plate into magnetic ferroferric oxide;
s3, sorting the magnetized anode and cathode mixed crushed materials by a magnetic separator to separate magnetic anode plate materials from non-magnetic cathode plate materials;
s4, selectively crushing the sorted positive plate materials and negative plate materials respectively, so that the positive lithium iron phosphate materials and the negative graphite materials fall off from the positive current collector and the negative current collector respectively to form powdery materials, the positive current collector and the negative current collector form a coiled granular material, and a positive mixture composed of lithium iron phosphate powder and the coiled positive current collector granular material and a negative mixture composed of graphite powder and the coiled negative current collector granular material are obtained;
s5, respectively carrying out vibration screening treatment on the positive electrode mixture and the negative electrode mixture, and recycling to obtain positive electrode current collector particles, negative electrode current collector particles, positive electrode lithium iron phosphate powder and negative electrode graphite powder.
The invention has the following technical effects:
(1) the invention adopts the oxidation and calcination process to carry out magnetization treatment on the anode and cathode sheets of the waste lithium iron phosphate battery, belongs to the dry treatment process, effectively avoids the defect of environmental pollution caused by a large amount of wastewater generated in the wet treatment, is beneficial to protecting the ecological environment, greatly reduces the recovery cost and has high economic benefit.
(2) The method has the advantages of simple process, mild treatment conditions and low requirements on equipment, can respectively recover the lithium iron phosphate positive electrode powder, the graphite negative electrode powder, the positive current collector aluminum particles and the negative current collector copper particles through magnetization, magnetic separation and selective crushing in sequence, has high separation efficiency, and realizes high-valued recovery of the positive and negative electrode materials of the waste lithium iron phosphate batteries.
(3) The sorting and recycling process does not introduce any newly added impurities, so that the grades of the recycled lithium iron phosphate anode powder, graphite cathode powder, anode current collector aluminum particles and cathode current collector copper particles are high, the impurity removal difficulty and the regeneration treatment cost of the subsequent material recycling are greatly reduced, and the industrial large-scale application is facilitated.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is an XRF test analysis chart of the waste battery positive electrode lithium iron phosphate powder recovered in embodiment 1 of the present invention.
FIG. 3 is an XRD test analysis chart of the graphite powder of the waste battery cathode recovered in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, the method for sorting and recovering the positive and negative electrode materials of the waste lithium iron phosphate batteries provided by the embodiment of the invention comprises the following steps:
s1, crushing the positive and negative pole piece mixture obtained by processing the waste lithium iron phosphate battery, and screening to obtain the positive and negative pole piece mixed crushed material with the size range of 3-30 mm.
The obtained positive and negative pole piece mixed materials are subjected to crushing treatment by adopting a shear type crusher after the waste lithium iron phosphate batteries are recycled, and then the mixed crushed materials with the size range of 3-30mm under the sieve are collected through a vibrating screen.
And S2, oxidizing and calcining the mixed crushed material of the positive plate and the negative plate obtained in the step S1 to oxidize part of the lithium iron phosphate material on the surface of the material of the positive plate into magnetic ferroferric oxide.
The step is to carry out magnetization treatment on the surface of the positive plate through oxidation and calcination, and prepare for subsequent magnetic separation. Under the aerobic condition, the surface of the lithium iron phosphate material on the positive plate can be partially oxidized by calcination to form magnetic ferroferric oxide, and the chemical reaction equation is as follows:
specifically, the calcination temperature is 150-. The oxygen amount introduced is controlled within the temperature range for aerobic calcination, so that the surface of the lithium iron phosphate anode material can be partially oxidized, the surface of the anode plate has certain magnetism, and the lithium iron phosphate anode material cannot be completely oxidized. If the oxygen volume is too much in the air that lets in, aerobic calcination temperature is too high, and the time overlength can make lithium iron phosphate cathode material oxidize completely, will the follow-up wet process of greatly increased retrieve the degree of difficulty that acid dip dissolves cathode material to increase the recovery cost, if the oxygen volume that lets in is too little, the temperature is low excessively, and the time is too short, and the magnetic strength on positive plate surface is not enough, is unfavorable for subsequent magnetic separation.
Aiming at the characteristics of the positive active material on the positive plate, the step leads the positive plate to form a magnetic material through oxidation and calcination, and leads the positive plate and the negative plate to be separated through subsequent magnetic separation. The method magnetizes all the positive plates to form the magnetic positive plates and the non-magnetic negative plates, the positive plates are very easy to identify, reliable guarantee is provided for magnetic separation between the subsequent positive plates and the subsequent negative plates, the defects that the recycled positive active materials contain copper impurities and the recycled negative active materials contain aluminum impurities can be avoided, the impurity removal difficulty and the recycling cost of the subsequent materials in recycling are greatly reduced, and the recycling quality of the positive active materials and the negative active materials is improved.
S3, sorting the magnetized anode and cathode mixed crushed materials by a magnetic separator to separate the magnetic anode plate material from the non-magnetic cathode plate material.
The magnetic separator with a certain magnetic field intensity is adopted to separate the magnetized anode and cathode mixed crushed materials, and the magnetic induction intensity of the surface of a separation magnetic roller in the magnetic separator is 500-3000 Gs.
The size of the mixed crushed material of the positive plate and the negative plate is controlled within the range of 3-30mm, the mixed crushed material is flaky, and under the magnetic induction intensity, the magnetic positive plate with ferroferric oxide on the surface after oxidation is easily captured by a magnetic roller on a magnetic separator, so that the magnetic positive plate and the non-magnetic negative plate are simply and quickly separated.
S4, selectively crushing the sorted positive plate material and negative plate material, so that the positive lithium iron phosphate material and the negative graphite material respectively fall off from the positive current collector and the negative current collector to form powdery materials, the positive current collector and the negative current collector form a coiled granular material, and a positive mixture composed of lithium iron phosphate powder and the coiled positive current collector granular material and a negative mixture composed of graphite powder and the coiled negative current collector granular material are obtained.
The step can adopt a hammer crusher to respectively crush the sorted positive plate and the sorted negative plate. Because the positive current collector of the positive plate of the waste lithium iron phosphate battery is an aluminum foil, the negative current collector of the negative plate is a copper foil, after aerobic calcination at 300 ℃, the binder for binding the positive lithium iron phosphate material and the negative graphite material is damaged, the binding performance is reduced and the positive plate and the negative plate are brittle, after the sorted positive plate and the negative plate respectively enter respective hammer crushers, under the impact force of a hammer head rotating at high speed, the positive plate and the negative plate are rushed towards the inner cavity of the crusher at high speed, meanwhile, the positive plate or the negative plate are mutually impacted in the inner cavity of the crusher, after multiple crushing, the positive lithium iron phosphate material is dropped from the aluminum foil, the negative graphite material powder is dropped from the copper foil, and the copper and the aluminum have certain ductility, so that materials with the granularity consistent with the positive lithium iron phosphate material and the negative graphite material can not be formed, and coiled aluminum particles or copper particles can be formed, after crushing treatment, a positive electrode mixture consisting of the positive electrode lithium iron phosphate powder and the coiled positive electrode current collector granular material and a negative electrode mixture consisting of the graphite powder and the coiled negative electrode current collector granular material can be respectively obtained.
S5, respectively carrying out vibration screening treatment on the positive electrode mixture and the negative electrode mixture, and recycling to obtain positive electrode current collector particles, negative electrode current collector particles, positive electrode lithium iron phosphate powder and negative electrode graphite powder.
Because the positive active material lithium iron phosphate in the positive mixture is powder, the positive current collector is a coiled granular material, the negative active material graphite in the negative mixture is also powder, and the coiled granular material of the negative current collector is screened by a vibrating screen, the materials are easily separated, and finally, the positive current collector particles, the negative current collector particles, the positive lithium iron phosphate powder and the negative graphite powder are obtained.
The sorting method comprises the steps of screening by using a shearing crusher to obtain a positive plate and a negative plate mixed crushed material meeting the size requirement, magnetizing the positive plate and the negative plate mixed crushed material by using an oxidation and calcination method to form a magnetic positive plate material and a non-magnetic negative plate, sorting the magnetized positive plate and negative plate mixed crushed material by using a magnetic separator to thoroughly separate the positive plate material and the negative plate material, then performing powder removal treatment on the positive plate and the negative plate respectively by using a positive current collector and a positive lithium iron phosphate material adhered to the positive plate and a negative current collector and a negative graphite material adhered to the negative plate and forming oxidation damage of different degrees on binders on the positive plate and the negative plate in the oxidation and calcination treatment process, and vibrating and screening to obtain granular positive plate and negative current collectors and powdery positive lithium iron phosphate powder, The whole sorting process of the cathode graphite powder adopts a physical method without a reactor, the problems of waste water generated by consuming a large amount of acid and alkali in a wet sorting method and low single-stage sorting efficiency are solved, and the sorted cathode lithium iron phosphate powder and cathode graphite powder have high purity.
The present invention will be described in further detail with reference to examples.
Example 1:
s1, processing a positive plate and negative plate mixture obtained by recycling waste lithium iron phosphate batteries by using a shear type crusher, and screening to obtain a preferred mixed crushed material of the positive plate and the negative plate with the longest dimension range under the screen of about 25mm, wherein the oversize plate which does not meet the dimension requirement returns to the crusher to be continuously crushed;
s2, under the conditions that the temperature is 150 ℃ and the calcining time is 3 hours, oxidizing, calcining and magnetizing the mixed crushed materials of the positive plate and the negative plate qualified in the step S1 in an air atmosphere, so that the part of the lithium iron phosphate material on the surface of the positive plate is oxidized into magnetic ferroferric oxide, the oxidation rate of iron is about 15%, and the magnetic positive plate material and the non-magnetic negative plate material are obtained;
s3, sorting the magnetized positive and negative pole mixed crushed materials in the step S2 by using a magnetic separator with the magnetic field intensity of 3000Gs on the surface of the sorting magnetic roller to separate magnetic positive pole piece materials from non-magnetic negative pole piece materials;
s4, selectively crushing the positive plate and the negative plate which are selected in the step S3 by using an impact crusher, wherein a positive lithium iron phosphate material and a negative graphite material fall off from respective current collectors to form powdery materials, a positive current collector aluminum foil and a negative current collector copper foil form a coiled granular material, and a positive mixture of lithium iron phosphate powder and the coiled aluminum foil granular material and a negative mixture of graphite powder and the coiled copper foil granular material are obtained;
and S5, respectively carrying out vibration screening treatment on the positive electrode mixture and the negative electrode mixture obtained in the step S4, and respectively recovering to obtain granular aluminum particles, copper particles, positive lithium iron phosphate powder and negative graphite powder.
As shown in fig. 2, it can be seen from an XRF test analysis chart of the recovered waste battery positive lithium iron phosphate powder, that the main elements are iron and phosphorus, and the copper impurity content is lower than the detection limit, which indicates that the positive plate separated and recovered by the method of the present invention does not contain a negative plate, and the separation rate is high. Through detection, the recovery rate of the positive lithium iron phosphate positive powder in the embodiment is 98.5%.
As shown in figure 3, the XRD test analysis chart of the recovered graphite powder of the waste battery negative electrode shows that the graphite peak is obvious and has no impurity peak, so that the negative electrode plate recovered by the method does not contain a positive electrode plate, the content of metal impurities is low, and the separation rate is high. Through detection, the recovery rate of the negative electrode graphite powder in the embodiment is 98.7%.
Example 2:
s1, processing a positive plate and negative plate mixture obtained by recycling waste lithium iron phosphate batteries by using a shear type crusher, and screening to obtain a preferred mixed crushed material of the positive plate and the negative plate with the longest dimension range under the screen of about 15mm, wherein the oversize plate which does not meet the dimension requirement returns to the crusher to be continuously crushed;
s2, under the conditions that the temperature is 200 ℃ and the calcining time is 2 hours, oxidizing, calcining and magnetizing the mixed crushed materials of the positive plate and the negative plate qualified in the step S1 in an air atmosphere, so that the part of the lithium iron phosphate material on the surface of the positive plate is oxidized into magnetic ferroferric oxide, the oxidation rate of iron is about 20%, and the magnetic positive plate material and the non-magnetic negative plate material are obtained;
s3, sorting the magnetized positive and negative pole mixed crushed materials in the step S2 by using a magnetic separator with the magnetic field intensity of 1500Gs on the surface of the sorting magnetic roller to separate magnetic positive pole piece materials from non-magnetic negative pole piece materials;
s4, selectively crushing the positive plate and the negative plate which are selected in the step S3 by using an impact crusher, wherein a positive lithium iron phosphate material and a negative graphite material fall off from respective current collectors to form powdery materials, a positive current collector aluminum foil and a negative current collector copper foil form a coiled granular material, and a positive mixture of lithium iron phosphate powder and the coiled aluminum foil granular material and a negative mixture of graphite powder and the coiled copper foil granular material are obtained;
and S5, respectively carrying out vibration screening treatment on the positive electrode mixture and the negative electrode mixture in the step S4, and respectively recovering to obtain granular aluminum particles, copper particles, positive lithium iron phosphate powder and negative graphite powder.
Example 3:
s1, processing a positive plate and negative plate mixture obtained by recycling waste lithium iron phosphate batteries by using a shear type crusher, and screening to obtain a preferred mixed crushed material of the positive plate and the negative plate with the longest undersize range of 30mm, wherein the oversize plate which does not meet the size requirement returns to the crusher to be continuously crushed;
s2, under the conditions that the temperature is 300 ℃ and the calcining time is 1.0h, oxidizing, calcining and magnetizing the mixed crushed material of the positive plate and the negative plate qualified in the step S1 in an air atmosphere to enable part of the lithium iron phosphate material on the surface of the positive plate to be oxidized into magnetic ferroferric oxide, wherein the oxidation rate of iron is about 25 percent, so that the magnetic positive plate material and the non-magnetic negative plate material are obtained;
s3, sorting the magnetized positive and negative pole mixed crushed materials in the step S2 by using a magnetic separator with the magnetic field intensity of 2000Gs on the surface of the sorting magnetic roller to separate magnetic positive pole piece materials from non-magnetic negative pole piece materials;
s4, selectively crushing the positive plate and the negative plate which are selected in the step S3 by using an impact crusher, wherein a positive lithium iron phosphate material and a negative graphite material fall off from respective current collectors to form powdery materials, a positive current collector aluminum foil and a negative current collector copper foil form a coiled granular material, and a positive mixture of lithium iron phosphate powder and the coiled aluminum foil granular material and a negative mixture of graphite powder and the coiled copper foil granular material are obtained;
and S5, respectively carrying out vibration screening treatment on the positive electrode mixture and the negative electrode mixture in the step S4, and respectively recovering to obtain granular aluminum particles, copper particles, positive lithium iron phosphate powder and negative graphite powder.
The above-described embodiments of the present invention are merely exemplary and not intended to limit the present invention, and those skilled in the art may make various modifications, substitutions and improvements without departing from the spirit of the present invention.
Claims (5)
1. A method for sorting and recovering anode and cathode materials of waste lithium iron phosphate batteries is characterized by comprising the following steps:
s1, crushing the positive and negative pole piece mixture obtained by processing the waste lithium iron phosphate battery, and screening to obtain a positive and negative pole piece mixed crushed material with the size range of 3-30 mm;
s2, oxidizing and calcining the mixed crushed material of the positive plate and the negative plate obtained in the step S1 to oxidize part of the lithium iron phosphate material on the surface of the positive plate into magnetic ferroferric oxide;
s3, sorting the magnetized anode and cathode mixed crushed materials by a magnetic separator to separate magnetic anode plate materials from non-magnetic cathode plate materials;
s4, selectively crushing the sorted positive plate materials and negative plate materials respectively, so that the positive lithium iron phosphate materials and the negative graphite materials fall off from the positive current collector and the negative current collector respectively to form powdery materials, the positive current collector and the negative current collector form a coiled granular material, and a positive mixture composed of lithium iron phosphate powder and the coiled positive current collector granular material and a negative mixture composed of graphite powder and the coiled negative current collector granular material are obtained;
s5, respectively carrying out vibration screening treatment on the positive electrode mixture and the negative electrode mixture, and recycling to obtain positive electrode current collector particles, negative electrode current collector particles, positive electrode lithium iron phosphate powder and negative electrode graphite powder.
2. The method for sorting and recovering the anode and cathode materials of the waste lithium iron phosphate batteries as claimed in claim 1, wherein in the step S2, the temperature of the oxidation calcination is 150-300 ℃, and the calcination time is 0.1-3 h.
3. The method for sorting and recovering the anode material and the cathode material of the waste lithium iron phosphate batteries according to claim 1 or 2, wherein in the step S2, the amount of oxygen in the air introduced during the oxidizing calcination satisfies the requirement of controlling the iron oxidation rate in the lithium iron phosphate anode material on the surface of the anode plate to 10% -30%.
4. The method for sorting and recovering the anode and cathode materials of the waste lithium iron phosphate batteries as claimed in claim 1, wherein in the step S3, the magnetic induction intensity on the surface of the sorting magnetic roller in the magnetic separator is 500-3000 Gs.
5. The method for sorting and recovering the positive and negative electrode materials of the waste lithium iron phosphate batteries according to claim 1, wherein in the step S4, a hammer crusher is used to selectively crush the positive electrode plate material and the negative electrode plate material respectively.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113948789A (en) * | 2021-11-20 | 2022-01-18 | 陆越自动化科技(上海)有限公司 | Liquid-injected lithium battery positive plate crushing and recycling system and method |
| CN115007614A (en) * | 2022-07-22 | 2022-09-06 | 北辰先进循环科技(青岛)有限公司 | Sorting method for broken materials of positive and negative pole pieces of waste lithium ion battery |
| CN115148988A (en) * | 2022-06-24 | 2022-10-04 | 河北工业大学 | Preparation method and application of composite nano catalyst based on anode and cathode materials of waste lithium ion battery |
| CN115156243A (en) * | 2022-07-18 | 2022-10-11 | 中国地质科学院郑州矿产综合利用研究所 | Recovery process of anode and cathode materials of waste battery |
| CN115709978A (en) * | 2022-11-30 | 2023-02-24 | 安徽鑫梓润发展科技有限公司 | Method for recovering positive plate material in lithium iron phosphate battery |
| CN115784192A (en) * | 2023-02-02 | 2023-03-14 | 中国科学院过程工程研究所 | A kind of recycling method of lithium iron phosphate battery cathode powder |
| CN117655066A (en) * | 2023-12-18 | 2024-03-08 | 隽诺环保装备科技(肇庆)有限公司 | Broken line of sorting of waste battery |
| CN117772612A (en) * | 2024-01-18 | 2024-03-29 | 江苏隆兴德锂业循环科技有限公司 | Gravity separation method for battery crushing |
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| CN119702635A (en) * | 2024-12-20 | 2025-03-28 | 中南大学 | Magnetic separation method for mixed pole pieces of waste lithium ion batteries |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113948789A (en) * | 2021-11-20 | 2022-01-18 | 陆越自动化科技(上海)有限公司 | Liquid-injected lithium battery positive plate crushing and recycling system and method |
| CN115148988A (en) * | 2022-06-24 | 2022-10-04 | 河北工业大学 | Preparation method and application of composite nano catalyst based on anode and cathode materials of waste lithium ion battery |
| CN115148988B (en) * | 2022-06-24 | 2024-05-17 | 河北工业大学 | Preparation method and application of composite nanocatalyst based on positive and negative electrode materials of waste lithium-ion batteries |
| CN115156243A (en) * | 2022-07-18 | 2022-10-11 | 中国地质科学院郑州矿产综合利用研究所 | Recovery process of anode and cathode materials of waste battery |
| CN115007614A (en) * | 2022-07-22 | 2022-09-06 | 北辰先进循环科技(青岛)有限公司 | Sorting method for broken materials of positive and negative pole pieces of waste lithium ion battery |
| CN115709978A (en) * | 2022-11-30 | 2023-02-24 | 安徽鑫梓润发展科技有限公司 | Method for recovering positive plate material in lithium iron phosphate battery |
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| WO2024160769A1 (en) | 2023-01-30 | 2024-08-08 | Materials Processing Institute | Process for the recovery of a useful material from a battery |
| CN115784192A (en) * | 2023-02-02 | 2023-03-14 | 中国科学院过程工程研究所 | A kind of recycling method of lithium iron phosphate battery cathode powder |
| CN117655066A (en) * | 2023-12-18 | 2024-03-08 | 隽诺环保装备科技(肇庆)有限公司 | Broken line of sorting of waste battery |
| CN117772612A (en) * | 2024-01-18 | 2024-03-29 | 江苏隆兴德锂业循环科技有限公司 | Gravity separation method for battery crushing |
| CN119702635A (en) * | 2024-12-20 | 2025-03-28 | 中南大学 | Magnetic separation method for mixed pole pieces of waste lithium ion batteries |
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