CN116544546A - Method for recycling waste lithium battery material - Google Patents
Method for recycling waste lithium battery material Download PDFInfo
- Publication number
- CN116544546A CN116544546A CN202310820401.0A CN202310820401A CN116544546A CN 116544546 A CN116544546 A CN 116544546A CN 202310820401 A CN202310820401 A CN 202310820401A CN 116544546 A CN116544546 A CN 116544546A
- Authority
- CN
- China
- Prior art keywords
- solution
- mixed
- battery
- waste lithium
- wet material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 136
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 77
- 239000002699 waste material Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000004064 recycling Methods 0.000 title claims abstract description 26
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 100
- 230000005593 dissociations Effects 0.000 claims abstract description 100
- 239000007788 liquid Substances 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000243 solution Substances 0.000 claims abstract description 67
- 239000011259 mixed solution Substances 0.000 claims abstract description 61
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 50
- 238000000926 separation method Methods 0.000 claims abstract description 44
- 239000012634 fragment Substances 0.000 claims abstract description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000012216 screening Methods 0.000 claims abstract description 35
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 31
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 30
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 claims abstract description 28
- 229940045872 sodium percarbonate Drugs 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 26
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011888 foil Substances 0.000 claims abstract description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011889 copper foil Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 230000005291 magnetic effect Effects 0.000 claims abstract description 13
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 230000005307 ferromagnetism Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 239000010406 cathode material Substances 0.000 claims description 17
- 239000010405 anode material Substances 0.000 claims description 15
- 238000005520 cutting process Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- 238000007885 magnetic separation Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 42
- 238000004880 explosion Methods 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 230000005294 ferromagnetic effect Effects 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000238367 Mya arenaria Species 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002912 waste gas 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
-
- 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
Abstract
The invention discloses a method for recycling waste lithium battery materials, which comprises the following steps: placing the discharged waste lithium batteries in water-based dissociation liquid to be disassembled into battery fragments; wherein the water-based dissociation liquid is an aqueous solution of sodium percarbonate, or a mixed solution of sodium carbonate and hydrogen peroxide; recovering the magnetic piece with ferromagnetism; recovering the suspended plastic parts; filtering to obtain filter residue and filtrate; distilling the filtrate, condensing and recovering organic electrolyte, adding saturated sodium carbonate solution into the rest solution, and precipitating to obtain crude lithium carbonate; and (3) drying the filter residues, and screening to at least obtain copper foil, aluminum foil, positive electrode material and negative electrode material. According to the invention, the discharged waste lithium batteries are disassembled under the condition of water system dissociation liquid seal, and then are separated for multiple times, so that the operation cost can be reduced, the explosion is avoided, the disassembly safety is ensured, the water system dissociation liquid can promote the efficient separation of the component materials, the recovery rate is ensured, and the separation recovery efficiency is improved.
Description
Technical Field
The invention relates to the technical field of battery recovery, in particular to a method for recovering waste lithium battery materials.
Background
The battery capacity of the power battery can be gradually reduced in the cyclic charge and discharge process, when the battery capacity is reduced to below 80%, the power battery can be retired, and the retired power battery can be disassembled and recycled, especially the retired lithium battery comprises nickel, cobalt, lithium and other elements which can be recycled, so that the power battery has obvious economic value. Under the background that the prices of upstream materials of lithium batteries are continuously rising and upstream metal resources are increasingly in shortage, the economic benefit of lithium battery recovery is more and more prominent.
GB/T33598.2-2020 "vehicle Power Battery recycle and recycle part 2: the material recovery requirement requires that the comprehensive recovery rate of nickel, cobalt and manganese in the lithium ion power storage battery material is not less than 98%, the recovery rate of lithium is not less than 85%, the recovery rate of nickel in the nickel-hydrogen power storage battery material is not less than 98%, and the recovery rate of other elements such as rare earth is not less than 95%.
At present, the recovery of waste lithium batteries in China mainly comprises two major parts of front-end battery pretreatment and rear-end wet extraction, and specifically comprises technological processes of battery discharging, disassembly, crushing, sorting, element extraction and the like, while the safe disassembly of the front-end batteries and the high-efficiency separation and recovery of each component are hot spots studied at present, the multi-stage crushing and sorting of the lithium batteries in air or inert gas protective atmosphere are methods used in the industry by a dry process, chinese patent with publication number of CN112108377A, CN102347520B, CN109193064A and the like all adopt the methods, the lithium batteries are disassembled and crushed in air or inert atmosphere, and each component of the lithium batteries is separated and recovered by physical means such as wind force, gravity, magnetic force, floatation and the like.
However, the lithium battery is inflammable and explosive, and more volatile organic electrolyte (usually accounting for 5-10%) exists in the lithium battery, and the waste lithium battery is crushed and disassembled under the dry condition, so that the mechanical friction inevitably generates heat or fires, and the dry crushing process needs to be protected by using harsh atmosphere conditions, so that the operation cost is high, and the risk of explosion still exists; in addition, the dry process needs to carry out multistage crushing and repeated sorting on the lithium battery to achieve the required recovery rate, and the efficiency is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for recycling waste lithium battery materials, which comprises the steps of firstly disassembling discharged waste lithium batteries at one time under the condition of water system dissociation liquid sealing, then separating and recycling for multiple times, so that the operation cost can be reduced, the explosion can be avoided, the safety of the disassembly process of the waste lithium batteries is ensured, the water system dissociation liquid can promote the efficient separation of the component materials, and the separation and recycling efficiency can be improved while the recovery rate is ensured.
The invention provides a method for recycling waste lithium battery materials, which comprises the following steps:
disassembling a liquid seal, namely disassembling the discharged waste lithium battery into battery fragments in an aqueous dissociation liquid, and mixing the battery fragments with the aqueous dissociation liquid to form a first mixed wet material; wherein the water-based dissociation liquid is an aqueous solution of sodium percarbonate, and the concentration of the sodium percarbonate is 0.5-3.0 mol/L; or the water system dissociation solution is a mixed solution of sodium carbonate and hydrogen peroxide, the concentration of the sodium carbonate is 0.5-3.0 mol/L, and the volume concentration of the hydrogen peroxide is 5-30%;
magnetic sorting, namely magnetic sorting the first mixed wet material, recovering a magnetic piece with ferromagnetism, wherein the rest material is a second mixed wet material;
plastic sorting, namely stirring the second mixed wet material, recycling plastic pieces suspended on the upper layer of the second mixed wet material, and enabling the rest materials to be third mixed wet materials;
solid-liquid separation, filtering the third mixed wet material to obtain filter residues and filtrate;
treating filtrate, distilling the filtrate, condensing and recovering organic electrolyte, adding saturated sodium carbonate solution into the rest solution, and precipitating to obtain crude lithium carbonate;
and (3) treating filter residues, and screening the filter residues after drying to at least obtain copper foil, aluminum foil, anode material and cathode material.
Specifically, the water-based dissociation liquid submerges the waste lithium batteries completely, and the mass of the water-based dissociation liquid is 2-10 times of the total mass of the waste lithium batteries.
Specifically, the step of disassembling the discharged waste lithium battery into battery fragments by placing the battery in an aqueous dissociation solution comprises the following steps:
and (3) at normal temperature, placing the discharged waste lithium batteries into water-based dissociation liquid, and cutting and disassembling the waste lithium batteries into battery fragments with the length of 2-5 cm.
Specifically, before the first mixed wet material is magnetically separated, the first mixed wet material is stirred for 20-120 min at a speed of 20-100 rpm by using a stirrer.
Specifically, the stirring the second mixed wet material includes: and stirring the second mixed wet material at a speed of 20-100 rpm for 20-120 min by using a stirrer.
Specifically, the filtrate treatment includes:
distilling the filtrate at 80-200 ℃, condensing and recovering the organic electrolyte at 0-35 ℃, wherein the residual solution is a first mixed solution;
evaporating and concentrating the first mixed solution at 65-100 ℃, adding saturated sodium carbonate solution into the first mixed solution after evaporating and concentrating, and precipitating to obtain crude lithium carbonate;
the crude lithium carbonate is filtered off, the remaining solution is a second mixed solution, and the second mixed solution is stored for standby.
Specifically, adding one or more of sodium percarbonate, sodium carbonate, hydrogen peroxide and water into the second mixed solution to prepare the replenishing solution of the water-based dissociation solution.
Specifically, the step of screening the filter residues after drying comprises the following steps:
first-stage screening, namely screening the dried filter residues by using a first screen to obtain a first mixture and a second mixture;
physical sorting, namely sorting the first mixture by using any two or three of gravity, wind power and vibration to obtain at least the copper foil and the aluminum foil;
and (3) secondary screening, namely screening the second mixture by using a second screen to obtain the positive electrode material and the negative electrode material.
Specifically, the aperture of the first screen is 10-15 mm; the aperture of the second screen is 0.5-2.0 mm.
Specifically, in the magnetic separation, an iron remover is used for carrying out magnetic separation on the first mixed wet material;
in the plastic sorting process, the second mixed wet material is stirred by using stirring slurry with a hairbrush, and a screen is used for recycling plastic pieces suspended on the upper layer of the second mixed wet material.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the discharged waste lithium batteries are disassembled once under the condition of liquid sealing of an aqueous dissociation liquid, and then separation and recovery are carried out for a plurality of times, in the disassembly process, the aqueous dissociation liquid can absorb heat generated by mechanical friction and avoid the occurrence of a sparking phenomenon in the disassembly process, meanwhile, the aqueous dissociation liquid is an aqueous solution of sodium percarbonate or a mixed solution of sodium carbonate and hydrogen peroxide, is alkaline, can effectively dissolve the organic electrolyte, and avoids volatilization of the organic electrolyte, so that the risk of explosion generated in the disassembly process of the waste lithium batteries is effectively avoided, the safety of the disassembly process of the waste lithium batteries is ensured, harsh atmosphere conditions are avoided, and the running cost is effectively reduced;
the water-based dissociation solution is an aqueous solution of sodium percarbonate or a mixed solution of sodium carbonate and hydrogen peroxide, a large amount of tiny oxygen bubbles can be generated to impact and dissociate battery fragments, and the high-efficiency separation of the component materials is promoted, wherein when the bonding interface of the current collector and the anode and cathode materials is impacted by the tiny oxygen bubbles, the anode and cathode materials are broken down due to intermolecular forces combined with the current collector to form a block, the anode materials bonded and formed by the aqueous binder can form anode material small particles with smaller particles due to the dissolution of the subsequent binder, and favorable conditions are created for the subsequent separation and recovery of the component materials; the water-based dissociation liquid is insoluble and does not corrode the metal materials in the waste lithium batteries, thereby providing a precondition for high recovery rate of the metal materials; the water system dissociation liquid contains a large amount of carbonate radicals, thereby providing convenience for the subsequent formation of lithium carbonate precipitation; therefore, the water dissociation liquid can improve the separation recovery efficiency while ensuring the recovery rate.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for recycling waste lithium battery material in an embodiment of the invention;
FIG. 2 is a positive electrode material obtained by dissociation recovery in example 1;
fig. 3 is a negative electrode material obtained by dissociation recovery in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Fig. 1 shows a flowchart of a method for recycling waste lithium battery material according to an embodiment of the present invention, including the steps of:
s1, dismantling a liquid seal;
the discharged waste lithium batteries are placed in water-based dissociation liquid to be disassembled into battery fragments, and the battery fragments and the water-based dissociation liquid are mixed to form first mixed wet materials; wherein the water-based dissociation liquid is an aqueous solution of sodium percarbonate, and the concentration of the sodium percarbonate is 0.5-3.0 mol/L; or the water system dissociation solution is a mixed solution of sodium carbonate and hydrogen peroxide, the concentration of the sodium carbonate is 0.5-3.0 mol/L, and the volume concentration of the hydrogen peroxide is 5-30%.
The discharged waste lithium batteries are disassembled into battery fragments at one time under the condition of liquid sealing of the water-based dissociation liquid, the water-based dissociation liquid can absorb heat generated by mechanical friction in the disassembly process, the ignition phenomenon in the disassembly process is avoided, the water-based dissociation liquid is alkaline, the organic dissociation liquid can be effectively dissolved, and volatilization of the organic dissociation liquid is avoided, so that the risk of explosion in the disassembly process of the waste lithium batteries is effectively avoided, the safety of the disassembly process of the waste lithium batteries is ensured, the harsh atmosphere condition is avoided, and the running cost is effectively reduced; the organic electrolyte is dissolved in the water-based dissociation liquid, so that the organic electrolyte is convenient to recover in the subsequent steps, and the organic electrolyte is prevented from volatilizing during disassembly, so that the physical health of on-site operators is ensured; the water system dissociation liquid and the battery fragments form mixed wet materials for subsequent sorting and recycling, so that dust generation can be effectively reduced, the environment of a lithium battery recycling workshop is improved, and the physical health of on-site operators is ensured; the water-based dissociation solution contains a large amount of anions and cations, and can release the residual electric quantity in the waste lithium battery in an electrolysis mode, so that the disassembly safety is improved.
In addition, a large amount of tiny oxygen bubbles can be generated by the water-based dissociation liquid to impact and dissociate battery fragments, and the efficient separation of each component material is promoted, wherein when the bonding interface of the current collector and the anode and cathode materials is impacted by the tiny oxygen bubbles, the anode and cathode materials are broken down to form a block due to intermolecular forces combined with the current collector, and the cathode materials bonded and formed by the water-based binder can form small cathode material particles with smaller particles due to the dissolution of the subsequent binder, so that favorable conditions are created for the subsequent separation and recovery of each component material; the water-based dissociation liquid is insoluble and does not corrode the metal materials in the waste lithium batteries, thereby providing a precondition for high recovery rate of the metal materials; the water system dissociation liquid contains a large amount of carbonate radicals, thereby providing convenience for the subsequent formation of lithium carbonate precipitation; therefore, the water dissociation liquid can improve the separation recovery efficiency while ensuring the recovery rate.
The positive electrode material of the waste lithium battery is adhered to the aluminum foil of the positive electrode current collector, the negative electrode material is adhered to the copper foil of the negative electrode current collector, the negative electrode material is adhered and formed through an aqueous binder, after the negative electrode material falls off from the copper foil, the graphite of the block-shaped negative electrode material is gradually crushed and becomes smaller as the aqueous binder is gradually dissolved in aqueous dissociation liquid, the positive electrode material is adhered and formed through PVDF, and the binder PVDF of the positive electrode material is not dissolved in the aqueous dissociation liquid, so that the block-shaped positive electrode material has no obvious trend of diminishing; the size of the positive and negative electrode materials after being dissociated from the current collector is obviously different, and favorable conditions are created for subsequent screening and separation.
In addition, at the interface of the aluminum foil and the positive electrode material, oxygen generated by the water-based dissociation liquid can instantly oxidize the surface of the aluminum foil into a compact aluminum oxide layer to prevent the aluminum foil from being further dissolved, and the water-based dissociation liquid is alkaline and does not dissolve the positive electrode material and other metals, so that the purity of each component substance obtained by subsequent recovery is high.
Optionally, when the aqueous dissociation solution is an aqueous solution of sodium percarbonate, the concentration of the sodium percarbonate is 0.5-3.0 mol/L, and the aqueous solution of sodium percarbonate in the concentration range can release a large amount of tiny oxygen bubbles, so that impact dissociation is carried out on battery fragments, and if the concentration is too high, sodium percarbonate is wasted; moreover, the aqueous solution of sodium percarbonate can also provide a large amount of carbonate radicals, which is convenient for the subsequent formation of lithium carbonate precipitate.
Optionally, when the water-based dissociation solution is a mixed solution of sodium carbonate and hydrogen peroxide, the concentration of the sodium carbonate is 0.5-3.0 mol/L, the volume concentration of the hydrogen peroxide is 5-30%, and the hydrogen peroxide with the volume concentration can release a large amount of tiny oxygen bubbles, so that the impact dissociation of battery fragments is enough, and if the volume concentration is too high, the hydrogen peroxide is wasted; the sodium carbonate can provide a large amount of carbonate radicals, and is convenient for the subsequent formation of lithium carbonate precipitation.
Specifically, the water-based dissociation liquid fully submerges the waste lithium batteries, the mass of the water-based dissociation liquid is 2-10 times of the total mass of the waste lithium batteries, and a sufficient amount of water-based dissociation liquid can ensure that the waste lithium batteries are fully submerged, so that heat generated by mechanical friction during disassembly is effectively absorbed, a sparking phenomenon is avoided, and the organic electrolyte is fully dissolved, so that volatilization of the organic electrolyte is avoided, and the risk of burning explosion of the organic electrolyte during the disassembly is effectively avoided; in addition, the sufficient water dissociation liquid is favorable for the sufficient dissociation of the battery fragments, is favorable for the layering of the component materials with different densities in the battery fragments, and is convenient for the separation and recovery of the component materials in the follow-up process.
Further, at normal temperature, the discharged waste lithium battery is placed in water dissociation liquid to be cut and disassembled into battery fragments with the length of 2-5 cm, cutting equipment such as a underwater cutting circular saw and the like can be used, if the battery fragments are too large, the battery fragments are not beneficial to fully dissociating under the action of the water dissociation liquid, and if the battery fragments are too small, the disassembly time and cost are increased, and the subsequent sorting and recycling of various materials are not beneficial.
S2, magnetic separation;
magnetically sorting the first mixed wet material, recovering a magnetic part with ferromagnetism, and taking the rest material as a second mixed wet material; specifically, the magnetic parts such as the pole lugs and the iron shells with ferromagnetism are separated by using equipment such as an iron remover, and the rest materials are used as second mixed wet materials to enter the next working procedure.
In some specific embodiments, before the first mixed wet material is magnetically separated, the first mixed wet material is stirred for 20-120 min at a speed of 20-100 rpm by using a stirrer, and the stirring operation is beneficial to promoting separation and layering of component materials with different densities in the battery fragments, so that separation and recovery of magnetic pieces are facilitated; and moreover, the stirring operation is beneficial to promoting the water system dissociation liquid to quickly release a large amount of tiny oxygen bubbles, so that the dissociation speed of the battery fragments in the water system dissociation liquid is effectively accelerated, the dissociation effect of each component material of the battery fragments is enhanced, the magnetic piece is fully separated from other component materials, and the adhesion of the magnetic piece is reduced to take away the anode and cathode materials.
S3, plastic sorting;
stirring the second mixed wet material, recycling plastic pieces suspended on the upper layer of the second mixed wet material, and taking the rest materials as third mixed wet materials; specifically, the second mixed wet material is stirred for 20-120 min at the speed of 20-100 rpm by using a stirrer, so that plastic parts such as a diaphragm, a plastic shell and the like are promoted to be separated from other component materials, and the plastic parts float on the upper layer of the second mixed wet material due to the fact that the density of the plastic parts is smaller than that of water, and can be selectively separated and recycled by using a screen mesh and the like; and moreover, the stirring operation is beneficial to promoting the water-based dissociation liquid to quickly release a large amount of tiny oxygen bubbles, so that the dissociation speed of the battery fragments in the water-based dissociation liquid is effectively accelerated, the dissociation effect of each component material of the battery fragments is enhanced, the plastic piece is fully separated from other component materials, and the adhesion of the plastic piece to the anode and cathode materials is reduced.
In some specific embodiments, in plastic separation, the stirring slurry with the brush is used for stirring the second mixed wet material, so that the stirring effect can be enhanced, separation of each component material is promoted, in particular separation of the diaphragm and other component materials is promoted, and adhesion of the diaphragm to the anode material and the cathode material is reduced.
S4, solid-liquid separation is carried out,
and filtering the third mixed wet material to obtain filter residues and filtrate, and specifically, according to the filtering amount, performing solid-liquid separation on the third mixed wet material by using a filter membrane, a filter cloth, a drum screen, an arc hydraulic screen, a drum hydraulic screen or the like to obtain the filter residues and the filtrate.
S41, treating the filtrate,
and distilling the filtrate, condensing to recover organic electrolyte, adding saturated sodium carbonate solution into the rest solution, and precipitating to obtain crude lithium carbonate.
Specifically, distilling the filtrate at 80-200 ℃, condensing and recovering the organic electrolyte at 0-30 ℃, wherein the residual solution is a first mixed solution; evaporating and concentrating the first mixed solution at 65-100 ℃, adding saturated sodium carbonate solution into the first mixed solution after evaporating and concentrating, and precipitating to obtain crude lithium carbonate; the crude lithium carbonate is filtered off, the remaining solution is a second mixed solution, and the second mixed solution is stored for standby.
Concentrating the volume of the first mixed solution to one half to three fifths of the original volume; because the solute of the water system dissociation solution is sodium percarbonate or sodium carbonate, the water system dissociation solution has abundant carbonate, namely the first mixed solution has abundant carbonate, and the concentration of lithium ions and carbonate in the first mixed solution can be improved by concentrating the first mixed solution, so that the combination of the lithium ions and the carbonate is promoted to precipitate, and the precipitation is convenient for extracting lithium; the saturated sodium carbonate solution, namely a large amount of carbonate is added, so that lithium ion precipitation in the concentrated first mixed solution can be fully promoted, loss caused by a small amount of lithium element dissolved in the water system dissociation solution in the dissociation process is avoided, other elements are prevented from being introduced, the purity of the lithium carbonate precipitation is ensured to a certain extent, and the recycling of the second mixed solution is not influenced.
Further, adding one or more of sodium percarbonate, sodium carbonate, hydrogen peroxide and water into the second mixed solution to prepare a replenishing solution of the water-based dissociation liquid, and adding one or more of sodium carbonate, hydrogen peroxide and water into the second mixed solution to prepare the replenishing solution, so that the concentration of groups such as carbonate radicals, peroxy radicals and the like in the prepared second mixed solution is recovered to the standard level of the water-based dissociation liquid, and the replenishing solution can be used as the replenishing solution of the water-based dissociation liquid, thereby reducing sewage treatment and emission, being green and environment-friendly and having the effects of reducing cost and enhancing efficiency.
S42, treating the filter residues,
and drying the filter residues, and screening to obtain at least copper foil, aluminum foil, positive electrode material and negative electrode material.
Specifically, before screening, the filter residues are put into a drying device such as a drying roller and the like, and are dried for 60-90 min under the condition of 110-130 ℃, so that the water content of the filter residues is reduced to 5% or below, the adhesion of the filter residues can be avoided, and the screening efficiency is improved.
Further, the screening includes:
first-stage screening, wherein a screen with the aperture of 10-15 mm is used for screening the dried filter residues to obtain a first mixture and a second mixture; the first mixture is oversize, with a particle size greater than 15mm, typically copper foil, aluminum foil, etc.; the second mixture is a undersize, the particle size of which is less than 10mm, and is usually powder of positive and negative electrode materials, and the like; because the battery fragments are fully dissociated in the water-based dissociating liquid and the filter residues are dried, the second mixture (namely the powder of the anode and cathode materials) attached to the surface of the first mixture (namely the materials such as copper foil, aluminum foil and the like) is extremely small, the generation of dust in the separation process is greatly reduced, and the recovery rate of the second mixture (namely the powder of the anode and cathode materials) is improved.
Physical separation, namely, the density, the size and the thickness of materials such as copper foil, aluminum foil and the like are different, and the materials can be easily separated in a physical separation mode; and the first mixture is separated by using any two or three of gravity, wind force and vibration, so that at least the copper foil and the aluminum foil are obtained, the separation effect is excellent, and the separation effect is thorough.
Secondary screening, wherein a screen with the aperture of 0.5-2.0 mm is used for screening the second mixture to obtain the positive electrode material and the negative electrode material; the second mixture is a mixture of positive and negative electrode materials, in the process of disassembling and sorting the waste lithium batteries, as the negative electrode materials of the waste lithium batteries are bonded and formed through the aqueous binder, after the negative electrode materials fall off from the copper foil, the graphite of the block-shaped negative electrode materials can be gradually crushed and become smaller as the aqueous binder is gradually dissolved in the aqueous dissociation liquid, and the positive electrode materials are bonded and formed through PVDF, and as the binder PVDF is not dissolved in the aqueous dissociation liquid, the block-shaped positive electrode materials have no obvious trend of diminishing; the positive electrode material and the negative electrode material have obvious difference in size after being dissociated from the current collector, can be easily separated through secondary screening after being dried, the particle size of the positive electrode material is larger than 2.0mm, the particle size of the negative electrode material is smaller than 0.5mm, and the separation effect is excellent.
According to the invention, discharged waste lithium batteries are disassembled into battery fragments at one time under the condition of water-based dissociation liquid sealing, the water-based dissociation liquid can absorb heat generated by mechanical friction in the disassembly process, the ignition phenomenon in the disassembly process is avoided, the water-based dissociation liquid is alkaline, the organic electrolyte can be effectively dissolved, and the volatilization of the organic electrolyte is avoided, so that the risk of explosion in the disassembly process of the waste lithium batteries is fundamentally effectively avoided, the safety of the disassembly process of the waste lithium batteries is ensured, the harsh atmosphere condition is avoided, and the running cost is effectively reduced; the organic electrolyte is dissolved in the water-based dissociation liquid, so that the organic electrolyte is convenient to recover in the subsequent steps, and the organic electrolyte is prevented from volatilizing during disassembly, so that the physical health of on-site operators is ensured; the water system dissociation liquid and the battery fragments form mixed wet materials for subsequent sorting and recycling, so that dust generation can be effectively reduced, the environment of a lithium battery recycling workshop is improved, and the physical health of on-site operators is ensured; the water-based dissociation solution contains a large amount of anions and cations, and can release the residual electric quantity in the waste lithium battery in an electrolysis mode, so that the disassembly safety is improved.
In addition, a large amount of tiny oxygen bubbles can be generated by the water-based dissociation liquid to impact and dissociate battery fragments, and the efficient separation of each component material is promoted, wherein when the bonding interface of the current collector and the anode and cathode materials is impacted by the tiny oxygen bubbles, the anode and cathode materials are broken down to form a block due to intermolecular forces combined with the current collector, and the cathode materials bonded and formed by the water-based binder can form small cathode material particles with smaller particles due to the dissolution of the subsequent binder, so that favorable conditions are created for the subsequent separation and recovery of each component material; the water-based dissociation solution is insoluble and does not corrode metal materials in the waste lithium batteries, and dust emission or leakage taking electrode materials as main components does not occur, so that a precondition is provided for high recovery rate, the operation environment is friendly, and industrial application is facilitated; the water system dissociation liquid contains a large amount of carbonate radicals, thereby providing convenience for the subsequent formation of lithium carbonate precipitation; therefore, the water dissociation liquid can improve the separation recovery efficiency while ensuring the recovery rate.
In addition, at the interface of the aluminum foil and the positive electrode material, oxygen generated by the water-based dissociation liquid can instantly oxidize the surface of the aluminum foil into a compact aluminum oxide layer to prevent the aluminum foil from being further dissolved, and the water-based dissociation liquid is alkaline and does not dissolve the positive electrode material and other metals, so that the purity of each component substance obtained by subsequent recovery is high.
The anion of the water system dissociation solution is carbonate, and the filtrate can be directly precipitated and recovered to obtain crude lithium carbonate by concentrating and supplementing carbonate, and other impurity pollution groups can not be introduced; the solution remained after filtering out the crude lithium carbonate can be reused for preparing water system dissociation liquid, thereby reducing sewage treatment and emission, and being environment-friendly.
According to the invention, all component materials of the waste lithium battery, such as a shell, a tab, a diaphragm, an organic electrolyte, lithium ions, a copper foil, an aluminum foil, a positive electrode material, a negative electrode material and the like are comprehensively and efficiently separated and recycled, and all component materials are thoroughly separated, so that the recovery rate and purity of the positive electrode material and the negative electrode material are effectively improved; the whole process has no production wastewater and waste gas discharge, small dust generation amount, clean and friendly workshop environment and high efficiency.
Example 1
The embodiment provides a method for recycling waste lithium battery materials, which specifically comprises the following steps:
(1) Immersing a discharged 18650 type cylindrical lithium battery (125 kg) in 1.5mol/L sodium percarbonate solution (750 kg), cutting and disassembling by using an underwater cutting circular saw to obtain battery fragments with the length of 3-4 cm, and mixing the battery fragments with the sodium percarbonate solution to form a first mixed wet material;
(2) Magnetically sorting the first mixed wet material by using an iron remover, and recovering ferromagnetic lugs and iron shells (the weight of the lugs and the iron shells after drying is 20.85 kg), wherein the rest materials are second mixed wet materials;
(3) Stirring the second mixed wet material for 60min at a speed of 60 revolutions per min by using a stirrer, then fishing out and recovering a diaphragm suspended on the upper layer of the second mixed wet material by using a screen (the weight of the diaphragm after drying is 5.51 kg), and taking the rest material as a third mixed wet material;
(4) Filtering the third mixed wet material by using a rotary screen with the aperture of 0.1mm to obtain filter residues and filtrate;
(5) Distilling the filtrate at 105 ℃, condensing and recovering organic electrolyte (6.21 kg) at 28 ℃, wherein the residual solution is a first mixed solution;
(6) Evaporating and concentrating the first mixed solution at 80 ℃, concentrating the volume of the first mixed solution to three fifths of the original volume, adding a saturated sodium carbonate solution into the concentrated first mixed solution, precipitating to obtain crude lithium carbonate, recovering the crude lithium carbonate (the weight of the dried crude lithium carbonate is 3.99 kg), taking the rest solution as a second mixed solution, adding a sodium percarbonate solution into the second mixed solution, preparing and supplementing reduced carbonate radicals and peroxy radicals, and then reusing the mixture as an aqueous dissociation solution;
(7) Drying the filter residue at 110 ℃ for 60min, and carrying out primary screening by using a screen with the aperture of 10mm to obtain a first mixture and a second mixture;
(8) Gravity separation, wind separation and vibration separation are carried out on the first mixture, and copper foil (14.9 kg) and aluminum foil (8.83 kg) are obtained through separation;
(9) The second mixture was subjected to secondary screening with a screen having a pore diameter of 0.8mm, and a positive electrode material (40.13 kg) and a negative electrode material (26.66 kg) were obtained by the screening.
Example 1 the positive electrode material obtained by dissociation and recovery was in the form of a block (see fig. 2), and the negative electrode material obtained by recovery was in the form of small-particle powder (see fig. 3).
The comprehensive recovery rate of the waste lithium battery material in the embodiment is 99.08% after calculation and analysis.
Example 2
The embodiment provides a method for recycling waste lithium battery materials, which specifically comprises the following steps:
(1) Immersing the discharged 21700 type cylindrical lithium battery (62 kg) in 2.0mol/L sodium percarbonate solution (424 kg), cutting and disassembling by using an underwater cutting circular saw to obtain battery fragments with the length of 3-4 cm, and mixing the battery fragments with the sodium percarbonate solution to form a first mixed wet material;
(2) Stirring the first mixed wet material for 90min at a speed of 50 revolutions per min by using a stirrer, magnetically sorting the first mixed wet material by using an iron remover, and recovering ferromagnetic lugs and iron shells (the weight of the lugs and the iron shells after drying is 9.92 kg), wherein the rest materials are second mixed wet materials;
(3) Stirring the second mixed wet material for 30min at a speed of 20 revolutions per min by using a stirrer, then fishing out and recovering a diaphragm suspended on the upper layer of the second mixed wet material by using a screen (the weight of the diaphragm after being dried is 2.98 kg), and taking the rest material as a third mixed wet material;
(4) Filtering the third mixed wet material by using filter cloth with the aperture of 0.1mm to obtain filter residues and filtrate;
(5) Distilling the filtrate at 80 ℃, condensing and recovering organic electrolyte (3.17 kg) at 0 ℃, wherein the residual solution is a first mixed solution;
(6) Evaporating and concentrating the first mixed solution at 65 ℃, concentrating the volume of the first mixed solution to one half of the original volume, adding saturated sodium carbonate solution into the concentrated first mixed solution, precipitating to obtain crude lithium carbonate, recovering the crude lithium carbonate (the weight of the dried crude lithium carbonate is 2.31 kg), taking the rest solution as a second mixed solution, adding sodium percarbonate solution into the second mixed solution to prepare and supplement reduced carbonate radical and peroxy radical, and then, taking the mixture as an aqueous dissociation solution again;
(7) Drying the filter residue at 110 ℃ for 70min, and carrying out primary screening by using a screen with the aperture of 12mm to obtain a first mixture and a second mixture;
(8) Gravity separation, wind separation and vibration separation are carried out on the first mixture, and copper foil (7.44 kg) and aluminum foil (4.4 kg) are obtained through separation;
(9) The second mixture was subjected to secondary screening with a screen having a pore diameter of 1mm, and a positive electrode material (19.84 kg) and a negative electrode material (13 kg) were obtained by the screening.
The comprehensive recovery rate of the waste lithium battery material in the embodiment is 98.69% after calculation and analysis.
Example 3
The embodiment provides a method for recycling waste lithium battery materials, which specifically comprises the following steps:
(1) Immersing the discharged soft package battery (86.5 kg) in a mixed solution (692 kg) of 2.0mol/L sodium carbonate and 12% hydrogen peroxide, cutting and disassembling by using an underwater cutting circular saw to obtain battery fragments with the length of 4-5 cm, and mixing the battery fragments with the sodium percarbonate solution to form a first mixed wet material;
(2) Magnetically sorting the first mixed wet material by using an iron remover, and recovering ferromagnetic lugs (the weight of the dried lugs is 1.02 kg), wherein the rest materials are second mixed wet materials;
(3) Stirring the second mixed wet material for 35min at a speed of 100 revolutions per min by using stirring slurry with a brush, then fishing and recovering a diaphragm suspended on the upper layer of the second mixed wet material by using a screen (the weight of the diaphragm after drying is 3.89 kg), and taking the rest material as a third mixed wet material;
(4) Filtering the third mixed wet material by using an arc-shaped hydraulic sieve with the aperture of 0.1mm to obtain filter residues and filtrate;
(5) Distilling the filtrate at 120 ℃, condensing and recovering organic electrolyte (9.01 kg) at 18 ℃, wherein the residual solution is a first mixed solution;
(6) Evaporating and concentrating the first mixed solution at 90 ℃, concentrating the volume of the first mixed solution to one half of the original volume, adding saturated sodium carbonate solution into the concentrated first mixed solution, precipitating to obtain crude lithium carbonate, recovering the crude lithium carbonate (the weight of the dried crude lithium carbonate is 4.36 kg), taking the rest solution as a second mixed solution, adding sodium percarbonate solution into the second mixed solution to prepare and supplement reduced carbonate radical and peroxy radical, and then reusing the second mixed solution as an aqueous dissociation solution;
(7) Drying the filter residue at 120 ℃ for 80min, and carrying out primary screening by using a screen with the aperture of 15mm to obtain a first mixture and a second mixture;
(8) Gravity sorting, wind sorting and vibration sorting are carried out on the first mixture, and copper foil (5.5 kg), aluminum foil (5.67 kg) and soft shell (2.85 kg) are obtained through sorting;
(9) The second mixture was subjected to secondary screening with a screen having a pore diameter of 1mm, and a positive electrode material (32.54 kg) and a negative electrode material (24.19 kg) were obtained by the screening.
The comprehensive recovery rate of the waste lithium battery material in the embodiment is 98.84% after calculation and analysis.
Example 4
The embodiment provides a method for recycling waste lithium battery materials, which specifically comprises the following steps:
(1) Immersing the discharged square aluminum shell battery (101 kg) in a mixed solution (1000 kg) of 1.2mol/L sodium carbonate and 15% hydrogen peroxide, cutting and disassembling by using an underwater cutting circular saw to obtain battery fragments with the length of 3.5-4.5 cm, and mixing the battery fragments with the sodium percarbonate solution to form a first mixed wet material;
(2) Magnetically sorting the first mixed wet material by using an iron remover, and recovering ferromagnetic lugs (the weight of the dried lugs is 1.63 kg), wherein the rest materials are second mixed wet materials;
(3) Stirring the second mixed wet material for 35min at a speed of 100 revolutions per min by using a stirrer, then fishing out and recovering a diaphragm suspended on the upper layer of the second mixed wet material by using a screen (the weight of the diaphragm after being dried is 3.07 kg), and taking the rest material as a third mixed wet material;
(4) Filtering the third mixed wet material by using a rotary drum type hydraulic sieve with the aperture of 0.1mm to obtain filter residues and filtrate;
(5) Distilling the filtrate at 200 ℃, and condensing and recovering organic electrolyte (9.71 kg) at 10 ℃, wherein the residual solution is a first mixed solution;
(6) Evaporating and concentrating the first mixed solution at 100 ℃, concentrating the volume of the first mixed solution to one half of the original volume, adding saturated sodium carbonate solution into the concentrated first mixed solution, precipitating to obtain crude lithium carbonate, recovering the crude lithium carbonate (the weight of the dried crude lithium carbonate is 2.8 kg), taking the rest solution as a second mixed solution, adding sodium percarbonate solution into the second mixed solution to prepare and supplement reduced carbonate radical and peroxy radical, and then reusing the second mixed solution as an aqueous dissociation solution;
(7) Drying the filter residue at 130 ℃ for 90min, and carrying out primary screening by using a screen with the aperture of 10mm to obtain a first mixture and a second mixture;
(8) Gravity separation, wind separation and vibration separation are carried out on the first mixture, and copper foil (11.22 kg), aluminum foil (8.16 kg) and aluminum shell (11.29 kg) are obtained through separation;
(9) The second mixture was subjected to secondary screening with a screen having a pore diameter of 1.5mm, and a positive electrode material (30.66 kg) and a negative electrode material (23.35 kg) were obtained by the screening.
The comprehensive recovery rate of the waste lithium battery material in the embodiment is 98.63% after calculation and analysis.
The results of comprehensive examples 1-4 show that the comprehensive recovery rate of the waste lithium battery material of the method for recovering the waste lithium battery material provided by the invention is more than 98%, the recovery rate is high, and the method has a very wide application prospect.
The above description is made in detail of a method for recycling waste lithium battery materials provided by the embodiment of the present invention, and specific examples should be adopted herein to illustrate the principles and embodiments of the present invention, where the above description of the examples is only for helping to understand the method and core ideas of the present invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (10)
1. The method for recycling the waste lithium battery material is characterized by comprising the following steps of:
disassembling a liquid seal, namely disassembling the discharged waste lithium battery into battery fragments in an aqueous dissociation liquid, and mixing the battery fragments with the aqueous dissociation liquid to form a first mixed wet material; wherein the water-based dissociation liquid is an aqueous solution of sodium percarbonate, and the concentration of the sodium percarbonate is 0.5-3.0 mol/L; or the water system dissociation solution is a mixed solution of sodium carbonate and hydrogen peroxide, the concentration of the sodium carbonate is 0.5-3.0 mol/L, and the volume concentration of the hydrogen peroxide is 5-30%;
magnetic sorting, namely magnetic sorting the first mixed wet material, recovering a magnetic piece with ferromagnetism, wherein the rest material is a second mixed wet material;
plastic sorting, namely stirring the second mixed wet material, recycling plastic pieces suspended on the upper layer of the second mixed wet material, and enabling the rest materials to be third mixed wet materials;
solid-liquid separation, filtering the third mixed wet material to obtain filter residues and filtrate;
treating filtrate, distilling the filtrate, condensing and recovering organic electrolyte, adding saturated sodium carbonate solution into the rest solution, and precipitating to obtain crude lithium carbonate;
and (3) treating filter residues, and screening the filter residues after drying to at least obtain copper foil, aluminum foil, anode material and cathode material.
2. The method of claim 1, wherein the aqueous dissociation liquid submerges the entire waste lithium battery, the mass of the aqueous dissociation liquid being 2 to 10 times the total mass of the waste lithium battery.
3. The method of claim 1, wherein the step of disassembling the discharged waste lithium battery into battery fragments by placing the battery in an aqueous dissociation liquid comprises:
and (3) at normal temperature, placing the discharged waste lithium batteries into water-based dissociation liquid, and cutting and disassembling the waste lithium batteries into battery fragments with the length of 2-5 cm.
4. The method of claim 1, wherein the first mixed wet material is stirred at a speed of 20 to 100 revolutions per minute for 20 to 120 minutes using a stirrer prior to magnetically sorting the first mixed wet material.
5. The method of claim 1, wherein the agitating the second mixed wet material comprises: and stirring the second mixed wet material at a speed of 20-100 rpm for 20-120 min by using a stirrer.
6. The method of claim 1, wherein the filtrate treatment comprises:
distilling the filtrate at 80-200 ℃, condensing and recovering the organic electrolyte at 0-35 ℃, wherein the residual solution is a first mixed solution;
evaporating and concentrating the first mixed solution at 65-100 ℃, adding saturated sodium carbonate solution into the first mixed solution after evaporating and concentrating, and precipitating to obtain crude lithium carbonate;
the crude lithium carbonate is filtered off, the remaining solution is a second mixed solution, and the second mixed solution is stored for standby.
7. The method of claim 6, wherein a make-up solution of the aqueous dissociation liquid is prepared by adding one or more of sodium percarbonate, sodium carbonate, hydrogen peroxide, and water to the second mixed solution.
8. The method of claim 1, wherein said drying said filter residue followed by screening comprises:
first-stage screening, namely screening the dried filter residues by using a first screen to obtain a first mixture and a second mixture;
physical sorting, namely sorting the first mixture by using any two or three of gravity, wind power and vibration to obtain at least the copper foil and the aluminum foil;
and (3) secondary screening, namely screening the second mixture by using a second screen to obtain the positive electrode material and the negative electrode material.
9. The method of claim 8, wherein the first screen has a pore size of 10 to 15mm; the aperture of the second screen is 0.5-2.0 mm.
10. The method of claim 1, wherein in the magnetic separation, the first mixed wet material is magnetically separated using an iron separator;
in the plastic sorting process, the second mixed wet material is stirred by using stirring slurry with a hairbrush, and a screen is used for recycling plastic pieces suspended on the upper layer of the second mixed wet material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310820401.0A CN116544546B (en) | 2023-07-06 | 2023-07-06 | Method for recycling waste lithium battery material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310820401.0A CN116544546B (en) | 2023-07-06 | 2023-07-06 | Method for recycling waste lithium battery material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116544546A true CN116544546A (en) | 2023-08-04 |
| CN116544546B CN116544546B (en) | 2023-12-05 |
Family
ID=87454575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310820401.0A Active CN116544546B (en) | 2023-07-06 | 2023-07-06 | Method for recycling waste lithium battery material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116544546B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005246229A (en) * | 2004-03-04 | 2005-09-15 | Kubota Corp | Method and apparatus for concentrating and separating sludge |
| CN101336496A (en) * | 2006-02-02 | 2008-12-31 | 川崎设备系统株式会社 | Recycling method and apparatus for precious material recycling from lithium secondary battery |
| WO2019232574A1 (en) * | 2018-06-07 | 2019-12-12 | Aac-Panels Pty Ltd | Recycling of lithium-based electrochemical cells |
| CN111180821A (en) * | 2020-01-05 | 2020-05-19 | 广东省资源综合利用研究所 | Harmless recycling and sorting method for waste lithium ion batteries |
| CN112441572A (en) * | 2019-08-27 | 2021-03-05 | 比亚迪股份有限公司 | Method for recovering waste lithium iron phosphate anode material |
| CN113571791A (en) * | 2021-07-08 | 2021-10-29 | 天津赛德美新能源科技有限公司 | Method for separating active material layer from current collector in electrode plate |
| CN115332659A (en) * | 2022-07-28 | 2022-11-11 | 广东邦普循环科技有限公司 | Method for recovering electrolyte by underwater crushing waste lithium ion battery |
-
2023
- 2023-07-06 CN CN202310820401.0A patent/CN116544546B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005246229A (en) * | 2004-03-04 | 2005-09-15 | Kubota Corp | Method and apparatus for concentrating and separating sludge |
| CN101336496A (en) * | 2006-02-02 | 2008-12-31 | 川崎设备系统株式会社 | Recycling method and apparatus for precious material recycling from lithium secondary battery |
| WO2019232574A1 (en) * | 2018-06-07 | 2019-12-12 | Aac-Panels Pty Ltd | Recycling of lithium-based electrochemical cells |
| CN112441572A (en) * | 2019-08-27 | 2021-03-05 | 比亚迪股份有限公司 | Method for recovering waste lithium iron phosphate anode material |
| CN111180821A (en) * | 2020-01-05 | 2020-05-19 | 广东省资源综合利用研究所 | Harmless recycling and sorting method for waste lithium ion batteries |
| CN113571791A (en) * | 2021-07-08 | 2021-10-29 | 天津赛德美新能源科技有限公司 | Method for separating active material layer from current collector in electrode plate |
| CN115332659A (en) * | 2022-07-28 | 2022-11-11 | 广东邦普循环科技有限公司 | Method for recovering electrolyte by underwater crushing waste lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 贾晓峰 等: "动力电池梯次利用场景与回收技术经济性研究", 汽车工程师, no. 06 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116544546B (en) | 2023-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110783658B (en) | Ex-service power ternary lithium battery recovery demonstration process method | |
| CN101599563B (en) | Method for efficiently recovering active materials of positive poles in waste lithium batteries | |
| CN100595970C (en) | Method for selectively removing copper from waste lithium ion battery | |
| FI3517641T4 (en) | Method for the utilization of lithium batteries | |
| CN108384955A (en) | A method of from selectively carrying lithium in waste material containing lithium battery | |
| CN107317064A (en) | A kind of recovery method of waste lithium cell | |
| CN107623152B (en) | Applying waste lithium ionic power battery resource recycle method | |
| CN112510281B (en) | Method for recovering all components of waste lithium ion battery | |
| CN112742843B (en) | Method for recycling waste lithium manganate battery through flotation and solid phase sintering | |
| CN107204495A (en) | A kind of method of the environmentally friendly recycling of discarded anode material of lithium battery | |
| CN112410565A (en) | Method for recovering valuable metal elements from waste ternary lithium ion battery positive electrode material | |
| CN112877548B (en) | Method for recovering valuable metals from waste lithium ion battery anode powder | |
| CN110828888A (en) | All-dry purification method of lithium ion battery anode material and lithium ion battery anode material obtained by purification | |
| CN107689465B (en) | Process for recovering valuable metals in waste ternary power battery cell | |
| CN104183887A (en) | Green method for dismantling, separation and recovery of waste LiCoO2 battery | |
| CN108134153A (en) | A kind of processing method of waste and old lithium ion battery | |
| WO2024041398A1 (en) | Multi-component recycling method for spent lithium-ion battery | |
| CN109103534A (en) | A kind of recovery method of waste and old lithium ion battery | |
| CN110034350A (en) | The method of hypoxemia cracking synthetical recovery waste lithium cell | |
| CN113381088B (en) | Method for separating positive active material and aluminum current collector in waste lithium ion battery in a transcritical fluid strengthening way | |
| CN112768796B (en) | Method for treating waste lithium battery | |
| CN112317520B (en) | Method and device for controllably exploding and crushing waste power batteries | |
| CN112201872B (en) | Safe discharge method and wet physical sorting method for retired batteries | |
| CN113200541A (en) | Method for recycling graphite negative electrode of waste battery | |
| CN116544546B (en) | Method for recycling waste lithium battery material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |