CN116837216B - Impurity removal method for recycling positive electrode powder of lithium ion battery - Google Patents
Impurity removal method for recycling positive electrode powder of lithium ion battery Download PDFInfo
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- CN116837216B CN116837216B CN202311124181.4A CN202311124181A CN116837216B CN 116837216 B CN116837216 B CN 116837216B CN 202311124181 A CN202311124181 A CN 202311124181A CN 116837216 B CN116837216 B CN 116837216B
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- ion battery
- lithium ion
- lithium
- positive electrode
- precipitate
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- 239000000843 powder Substances 0.000 title claims abstract description 97
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 87
- 239000012535 impurity Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000004064 recycling Methods 0.000 title claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000002244 precipitate Substances 0.000 claims abstract description 57
- 229910052742 iron Inorganic materials 0.000 claims abstract description 53
- 238000002791 soaking Methods 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 41
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 39
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 39
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000004062 sedimentation Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 56
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 238000003828 vacuum filtration Methods 0.000 claims description 8
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims 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 claims 1
- 238000010902 jet-milling Methods 0.000 claims 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 239000010949 copper Substances 0.000 abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011572 manganese Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 abstract description 5
- 239000010941 cobalt Substances 0.000 abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 17
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 16
- 238000010298 pulverizing process Methods 0.000 description 11
- 238000007873 sieving Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Abstract
A method for removing impurities from lithium ion battery recovered anode powder belongs to the technical field of lithium ion battery recovery. The method comprises the steps of firstly, putting the recovered positive electrode powder of the lithium ion battery into a liquid medium, fully dispersing, then standing for sedimentation, taking suspension, and carrying out solid-liquid separation to obtain a precipitate; and then placing the precipitate into an ammonia water solution, stirring while soaking, and finally filtering and drying to obtain the lithium ion battery recovered anode powder after impurity removal. The method can effectively remove most of metal impurities such as copper, iron, aluminum and the like in the lithium ion battery recovered anode powder, does not damage the original structure of the material, does not cause loss of rare metals such as nickel, cobalt, manganese and the like, has simple process and operation, shorter process flow, low equipment requirement and energy consumption, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery recovery, and particularly relates to a method for removing impurities from lithium ion battery recovered anode powder.
Background
For organic solvents and heavy metals in lithium ion batteries, serious environmental pollution can be caused if the organic solvents and the heavy metals are improperly disposed. The impurities in lithium ion batteries, mainly copper, aluminum, iron and other metals, have also received extensive attention and research by students how to effectively remove these impurities.
At present, a hydrometallurgy method is mainly adopted to recycle the waste lithium ion batteries. The method is characterized in that the black powder is obtained after the waste lithium ion batteries are subjected to pretreatment such as discharging, disassembling, crushing, sorting and the like, then the black powder is dissolved by adopting an acid leaching method, and various leached valuable metals are recovered by adopting methods such as extraction, precipitation and the like after impurity removal. However, the traditional impurity removal process has lower removal rate of copper and aluminum impurities, and new iron impurities can be introduced by adopting iron powder to replace and remove copper, so that the utilization value of iron-aluminum waste residues can be reduced, the loss of rare metals such as nickel, cobalt, manganese and the like can be increased, and the recovery rate of the lithium ion battery is greatly influenced. In addition, the process flow of the method is longer, and a large amount of alkali liquor is needed in the later stage to neutralize excessive acid liquor in the earlier stage, so that a large amount of wastewater is generated, and the method is not beneficial to environmental protection and industrial clean production.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for removing impurities from recovered positive electrode powder of a lithium ion battery. The method of the invention does not damage the original structure of the material, does not cause loss of rare metals such as nickel, cobalt, manganese and the like, has simple and easy impurity removal process and shorter process flow, can effectively remove metal impurities such as copper, iron, aluminum and the like, and can realize industrial production.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the impurity removing method for the lithium ion battery recovered positive electrode powder comprises the following steps:
s1, placing the recovered positive electrode powder of the lithium ion battery into a liquid medium, fully dispersing, standing and settling the obtained slurry, taking a suspension, and carrying out solid-liquid separation to obtain a precipitate;
the liquid medium is at least one of aqueous solution containing lithium ions, N-methyl pyrrolidone (NMP), glycol and glycerol;
s2, placing the precipitate into an ammonia water solution, stirring while soaking, and then filtering and drying to obtain the lithium ion battery recovered anode powder after impurity removal.
Preferably, in step S1, before the lithium ion battery recycled positive electrode powder is put into the liquid medium, the lithium ion battery recycled positive electrode powder is crushed; more preferably, the pulverization is at least one of mechanical pulverization, gas flow pulverization, and liquid flow pulverization.
Preferably, in step S1, before the lithium ion battery recycled positive electrode powder is placed in the liquid medium, the permanent magnet iron remover and/or the electromagnetic iron remover is used to remove the magnetic foreign matters in the lithium ion battery recycled positive electrode powder.
Preferably, in step S1, the method of sufficiently dispersing is to perform ultrasonic dispersion first and then uniformly stir.
Preferably, in step S1, the slurry is screened before it is subjected to a still settling; more preferably, the number of the sieved meshes is 50-600 mesh.
Preferably, in the step S1, the standing time is 0.5-90 min in the standing sedimentation.
Preferably, in step S1, the solid-liquid separation is at least one of centrifugal filtration, vacuum filtration, and pressure filtration.
Preferably, in step S1, the lithium ion battery is at least one of a lithium cobaltate battery, a lithium manganate battery, a lithium iron phosphate battery, and a lithium nickel cobalt manganate battery.
Preferably, in step S1, the aqueous solution containing lithium ions is at least one of a lithium chloride solution, a lithium bromide solution, a lithium iodide solution, a lithium nitrate solution, a lithium sulfate solution, a lithium perchlorate solution, a lithium acetate solution, and a lithium hydroxide solution.
Preferably, in step S1, the concentration of lithium ions in the aqueous solution containing lithium ions is 0.01 to 1mol/L.
Preferably, in step S1, the liquid medium is N-methylpyrrolidone.
Preferably, in the step S1, the ratio of the recovered positive electrode powder to the liquid medium of the lithium ion battery is (10-500 g): 1L.
Preferably, in step S2, the process of the present invention,
when in soaking, a permanent magnet iron remover and/or an electromagnetic iron remover are adopted to remove magnetic foreign matters in the sediment;
or, after drying, removing magnetic foreign matters in the precipitate by adopting a permanent magnet iron remover and/or an electromagnetic iron remover;
or, during soaking and after drying, removing magnetic foreign matters in the precipitate by adopting a permanent magnet iron remover and/or an electromagnetic iron remover.
Preferably, in step S2, the precipitate is placed in an aqueous ammonia solution, stirred while being soaked, filtered, repeatedly operated for more than 1 time, and then dried to obtain the lithium ion battery recovered anode powder after impurity removal; the process of each repeated operation is as follows: placing the precipitate into new ammonia water solution, stirring while soaking, and filtering the precipitate; more preferably, the operation is repeated 1 to 2 times.
Preferably, in the step S2, the ratio of the recovered positive electrode powder to the total ammonia water solution for soaking is (24-50 g) (600-900) mL.
Preferably, in the step S2, the pH of the aqueous ammonia solution is 9 to 13; more preferably 11.7.
Preferably, in the step S2, the total soaking time is 0.5-72 h.
Preferably, in step S2, the stirring speed is 100-1000 r/min.
Preferably, in step S2, the temperature of the drying is 50-200 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The impurity removal method for the lithium ion battery recovered positive electrode powder can effectively remove most of metal impurities such as copper, iron, aluminum and the like in the lithium ion battery recovered positive electrode powder, and cannot cause the damage of the original structure of the material and the loss of rare metals such as nickel, cobalt, manganese and the like.
(2) The impurity removal method for recycling the positive electrode powder of the lithium ion battery has the advantages of simple process and operation, short process flow, low equipment requirement and energy consumption and suitability for large-scale industrial production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention and that other drawings can be obtained without inventive effort for a person skilled in the art.
Fig. 1 is a process flow diagram of the method for removing impurities from the recovered positive electrode powder of the lithium ion battery.
Detailed Description
For a thorough understanding of the present invention, the preferred embodiments of the present invention will be described to further illustrate the features and advantages of the present invention, and any changes or modifications that do not depart from the gist of the present invention will be understood by those skilled in the art to which the present invention pertains, the scope of which is defined by the appended claims.
As shown in fig. 1, the impurity removal method for recycling positive electrode powder of the lithium ion battery at least comprises the following steps:
s1, placing the recovered positive electrode powder of the lithium ion battery into a liquid medium, fully dispersing, standing and settling the obtained slurry, taking a suspension, and carrying out solid-liquid separation to obtain a precipitate (the liquid medium obtained by the solid-liquid separation can be reused);
s2, placing the precipitate into an ammonia water solution, stirring while soaking, filtering (the ammonia water solution obtained by filtering can be reused) and drying to obtain the lithium ion battery recovered anode powder after impurity removal.
In a preferred embodiment, in step S1, the lithium ion battery recycled positive electrode powder may be further pulverized before being placed in the liquid medium. The pulverizing method is not particularly limited, and may be at least one of mechanical pulverizing, jet-pulverizing, and fluid-flow pulverizing.
In the preferred embodiment, in step S1, before the lithium ion battery recycled positive electrode powder is placed in the liquid medium, a permanent magnet iron remover and/or an electromagnetic iron remover may be used to remove magnetic foreign matters in the lithium ion battery recycled positive electrode powder. The magnetic material mainly contains iron, and may also contain other magnetic materials such as Cr, ni, etc.
In the step S1, the method of fully dispersing may be to perform ultrasonic dispersion first and then uniformly stirring, and the ultrasonic temperature is preferably 30-90 ℃ and the ultrasonic time is preferably 5-60 min.
Preferably, in step S1, the slurry may be screened before the slurry is subjected to the standing sedimentation; wherein, the mesh number of the sieving is preferably 50-600 meshes.
In the step S1, the standing time is 0.5-90 min in the standing sedimentation.
In the step S1, the solid-liquid separation is preferably at least one of centrifugal filtration, vacuum filtration and pressure filtration, wherein the centrifugal speed is preferably 5000-10000 r/min, and the time is preferably 3-30 min.
In the step S1, the lithium ion battery may be at least one of a lithium cobaltate battery, a lithium manganate battery, a lithium iron phosphate battery, and a lithium nickel cobalt manganate battery, and is not particularly limited.
In the invention, because the density of the lithium ion battery recovered positive electrode powder is greatly different from that of the metal impurities, the lithium ion-containing aqueous solution, glycol, glycerol and NMP which do not react with the lithium ion battery recovered positive electrode powder are selected as liquid media (solvents), so that the lithium ion battery recovered positive electrode powder can be subjected to impurity removal under the condition of not damaging the lithium ion battery recovered positive electrode powder. Wherein, considering that the lithium ion battery reclaimed positive electrode powder has the problem of lithium dissolution in water, the aqueous solution containing lithium ions is selected as a liquid medium, and specifically, the aqueous solution containing lithium ions is preferably at least one of lithium chloride solution, lithium bromide solution, lithium iodide solution, lithium nitrate solution, lithium sulfate solution, lithium perchlorate solution, lithium acetate solution and lithium hydroxide solution; and preferably, the lithium ion concentration in the aqueous solution is 0.01 to 1mol/L. In addition, NMP has weak alkalinity, residual PVDF in the lithium ion battery reclaimed positive electrode powder can generate elimination reaction in NMP, and C=C double bond formed by induction generates chemical crosslinking and generates sol, so that the viscosity of a liquid medium is increased, the sedimentation speed of the lithium ion battery reclaimed positive electrode powder in the liquid medium is reduced, and the lithium ion battery reclaimed positive electrode powder is better separated from metal impurities, so that better impurity removal effect is achieved. Therefore, NMP is preferred for the liquid medium of the present invention.
In the preferred embodiment, in step S1, the ratio of the lithium ion battery recovered positive electrode powder to the liquid medium is (10 to 500 g): 1L.
In a preferred scheme, in the step S2, a permanent magnet iron remover and/or an electromagnetic iron remover is adopted to remove magnetic foreign matters in the sediment during soaking; or, after drying, removing magnetic foreign matters in the precipitate by adopting a permanent magnet iron remover and/or an electromagnetic iron remover; or, during soaking and after drying, removing magnetic foreign matters in the precipitate by adopting a permanent magnet iron remover and/or an electromagnetic iron remover. The magnetic material mainly contains iron, and may also contain other magnetic materials such as Cr, ni, etc.
In the step S2, the pH of the ammonia water solution is 9-13; more preferably, the pH of the aqueous ammonia solution is 11.7. In the present invention, the aqueous ammonia solution has the following functions: 1) Ionized OH from aqueous ammonia solution - The ion can effectively inhibit the dissolution of lithium in the recovered positive electrode powder of the lithium ion battery on the basis of not damaging the material structure so as to reduce the influence on the electrochemical performance of the lithium ion battery; 2) NH in aqueous ammonia solution 3 With Cu 2+ The equilibrium constant after the ion is subjected to complexation reaction is larger than Ni dissolved out of the ternary positive electrode material 2 + 、Co 2+ 、Mn 2+ The equilibrium constant after ion complexation reaction, namely ammonia water solution and Cu 2+ Ions have stronger complexing ability, so copper can be effectively removed; 3) In the presence of oxygen, copper and ligand with weak coordination ability in ammonia water solution can act to generate tetramine copper ions, and the reaction equation is as follows: 2Cu+8NH 3 +O 2 +2H 2 O=2[Cu(NH 3 ) 4 ] 2+ +4OH - Furthermore, the introduction of the ammonia water solution can realize accurate impurity removal on the basis of the previous step; 4) And the ammonia water can be recycled, so that the aims of energy conservation, consumption reduction and environmental protection can be achieved.
In the step S2, the precipitate is placed into an ammonia water solution, and after being soaked and stirred, the precipitate can be filtered, and the process is repeated for more than 1 time (each repeated process means that the precipitate is placed into a new ammonia water solution, and is soaked and stirred, and filtered), and then the precipitate is dried, so that the lithium ion battery recovered anode powder after impurity removal is obtained; more preferably, the operation is repeated 1 to 2 times.
In the step S2, the use amount of the ammonia water solution is not particularly limited, and the soaking condition can be generally met, and as a preferable scheme, the ratio of the recovered positive electrode powder of the lithium ion battery to the total ammonia water solution for soaking is (24-50 g) (600-900) mL. When repeated operation is adopted for a plurality of times, the ratio of the recovered positive electrode powder of the lithium ion battery to the ammonia water solution for each soaking is (24-50 g): 300mL.
In the preferred embodiment, in the step S2, the soaking time may be 0.5 to 72 hours, and when repeated operations are adopted, the soaking time refers to the total time of soaking the precipitate in the aqueous ammonia solution, and the time of each operation is not particularly limited.
In a preferred embodiment, in step S2, the precipitate and the aqueous ammonia solution are allowed to react more sufficiently by stirring while soaking, and the stirring speed is preferably 100 to 1000r/min.
In the step S2, the drying temperature is preferably 50-200 ℃.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated.
In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be described in further detail with reference to examples.
In the following examples, various processes and methods, which are not described in detail, are conventional methods well known in the art. Materials, reagents, devices, instruments, equipment and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
The impurity removal method for recycling positive electrode powder of the lithium ion battery comprises the following steps:
s1, mechanically crushing the recovered positive electrode powder of the nickel cobalt lithium manganate battery in a mechanical mill, removing magnetic foreign matters by adopting an electromagnetic iron remover and a permanent magnetic iron remover, then mixing 4g of the positive electrode powder after mechanical crushing with 40 mLN-methyl pyrrolidone, carrying out ultrasonic treatment at 70 ℃ for 5min, uniformly stirring, sieving with a 300-mesh sieve, standing for 5min, transferring an upper suspension into a centrifuge tube, and carrying out centrifugal filtration at a centrifugal speed of 9000r/min for 5min to obtain a precipitate;
s2, placing the precipitate into 50mL of ammonia water solution with pH value of 11.7, stirring while soaking, wherein the stirring speed is 500r/min, filtering the precipitate, repeating for 1 time, wherein each soaking time is 8 hours, removing magnetic foreign matters by adopting a permanent magnet iron remover during soaking, and drying to obtain 2.38g of purified nickel cobalt lithium manganate battery recovered anode powder.
The composition changes before and after impurity removal of the sample of this example are shown in Table 1.
TABLE 1 variation of the ingredients before and after sample treatment
Example 2
The impurity removal method for recycling positive electrode powder of the lithium ion battery comprises the following steps:
s1, placing recovered positive electrode powder of a nickel cobalt lithium manganate battery into an air flow mill for air flow crushing, then mixing 5g of air flow crushed positive electrode powder with 80mL of glycerol, carrying out ultrasonic treatment at 90 ℃ for 10min, then uniformly stirring, sieving with a 300-mesh sieve, standing for 1min, and carrying out vacuum filtration on an upper suspension to obtain a precipitate;
s2, placing the precipitate into 60mL of ammonia water solution with pH value of 10.5, stirring while soaking, wherein the stirring speed is 400r/min, filtering the precipitate, repeating twice, wherein the soaking time is 6h each time, drying, and removing magnetic foreign matters by adopting an electromagnetic iron remover to obtain 3.75g of purified nickel cobalt lithium manganate battery recovered anode powder.
The composition changes before and after impurity removal of the sample of this example are shown in Table 2.
TABLE 2 variation of the ingredients before and after sample treatment
Example 3
The impurity removal method for recycling positive electrode powder of the lithium ion battery comprises the following steps:
s1, placing recovered positive electrode powder of a nickel cobalt lithium manganate battery into a liquid flow pulverizer to perform liquid flow pulverization, adopting a permanent magnet iron remover to remove magnetic foreign matters, then mixing 10g of the liquid flow pulverized positive electrode powder with 50mL of ethylene glycol, performing ultrasonic treatment at 80 ℃ for 20min, uniformly stirring, sieving with a 400-mesh sieve, standing for 3min, transferring an upper suspension into a centrifuge tube, performing centrifugal filtration, and obtaining a precipitate at a centrifugal speed of 10000r/min for 3 min;
s2, placing the precipitate into 100mL of ammonia water solution with pH value of 10.9, stirring while soaking, wherein the stirring speed is 600r/min, filtering the precipitate, repeating twice, wherein the soaking time is 8h each time, removing magnetic foreign matters by adopting a permanent magnet iron remover during soaking, drying, and removing the magnetic foreign matters by adopting an electromagnetic iron remover again, thereby obtaining 7.63g of purified nickel cobalt lithium manganate battery recovered anode powder.
The composition changes before and after the impurity removal of the sample of this example are shown in Table 3.
TABLE 3 variation of the composition before and after sample treatment
Example 4
The impurity removal method for recycling positive electrode powder of the lithium ion battery comprises the following steps:
s1, mechanically crushing the recovered positive electrode powder of the nickel cobalt lithium manganate battery in a mechanical mill, removing magnetic foreign matters by adopting a permanent magnet iron remover, mixing 5g of the mechanically crushed positive electrode powder with 30mL of glycerol, performing ultrasonic treatment at 85 ℃ for 15min, uniformly stirring, sieving with a 325-mesh sieve, standing for 10min, and performing vacuum filtration on an upper suspension to obtain a precipitate;
s2, placing the precipitate into 40mL of ammonia water solution with pH value of 9.8, stirring while soaking, wherein the stirring speed is 200r/min, filtering the precipitate, repeating for 1 time, wherein the soaking time is 6 hours each time, drying, and removing magnetic foreign matters by adopting an electromagnetic iron remover to obtain 3.64g of purified nickel cobalt lithium manganate battery recovered anode powder.
The composition changes before and after the impurity removal of the sample of this example are shown in Table 4.
TABLE 4 variation of the composition before and after sample treatment
Example 5
The impurity removal method for recycling positive electrode powder of the lithium ion battery comprises the following steps:
s1, placing recovered positive electrode powder of a nickel cobalt lithium manganate battery into a liquid flow pulverizer for liquid flow pulverization, mixing 50g of the liquid flow pulverized positive electrode powder with 2000 mLN-methyl pyrrolidone, carrying out ultrasonic treatment at 65 ℃ for 60min, uniformly stirring, sieving with a 400-mesh sieve, standing for 15min, and carrying out filter pressing on an upper suspension to obtain a precipitate;
s2, placing the precipitate into 300mL of ammonia water solution with pH value of 10.6, stirring while soaking, wherein the stirring speed is 800r/min, filtering the precipitate, repeating twice, wherein the soaking time is 5h each time, removing magnetic foreign matters by adopting a permanent magnet iron remover during soaking, drying, and removing the magnetic foreign matters by adopting an electromagnetic iron remover again to obtain 15.35g of purified nickel cobalt lithium manganate battery recovered anode powder.
The composition changes before and after the impurity removal of the sample of this example are shown in Table 5.
TABLE 5 variation of the composition before and after sample treatment
Example 6
The impurity removal method for recycling positive electrode powder of the lithium ion battery comprises the following steps:
s1, placing recovered positive electrode powder of a nickel cobalt lithium manganate battery into an air flow mill for air flow crushing, adopting a permanent magnet iron remover to remove magnetic foreign matters, then mixing 15g of air flow crushed positive electrode powder with 200mL of glycerol, performing ultrasonic treatment at 80 ℃ for 35min, then uniformly stirring, sieving with a 600-mesh sieve, standing for 5min, and performing vacuum filtration on an upper suspension to obtain a precipitate;
s2, placing the precipitate into 100mL of ammonia water solution with pH value of 11.3, stirring while soaking, wherein the stirring speed is 650r/min, filtering the precipitate, repeating for 1 time, wherein the soaking time is 10h each time, removing magnetic foreign matters by adopting an electromagnetic iron remover during soaking, and drying to obtain 10.64g of purified nickel cobalt lithium manganate battery recovered anode powder.
The composition changes before and after the impurity removal of the sample of this example are shown in Table 6.
TABLE 6 variation of the ingredients before and after sample treatment
Example 7
The impurity removal method for recycling positive electrode powder of the lithium ion battery comprises the following steps:
s1, mechanically crushing the recovered positive electrode powder of the nickel cobalt lithium manganate battery in a mechanical mill, mixing 10g of the mechanically crushed positive electrode powder with 150 mLN-methylpyrrolidone, carrying out ultrasonic treatment at 50 ℃ for 25min, uniformly stirring, sieving with a 500-mesh sieve, standing for 20min, and carrying out vacuum filtration on an upper suspension to obtain a precipitate;
s2, placing the precipitate into 80mL of ammonia water solution with pH value of 10.5, stirring while soaking, wherein the stirring speed is 500r/min, filtering the precipitate, repeating twice, wherein the soaking time is 8h each time, removing magnetic foreign matters by adopting an electromagnetic iron remover during soaking, drying, and removing the magnetic foreign matters by adopting a permanent magnet iron remover again to obtain 7.83g of purified nickel cobalt lithium manganate battery recovered anode powder.
The composition changes before and after the impurity removal of the sample of this example are shown in Table 7.
TABLE 7 variation of the composition before and after sample treatment
Example 8
The impurity removal method for recycling positive electrode powder of the lithium ion battery comprises the following steps:
s1, placing reclaimed positive electrode powder of a lithium manganate battery into a liquid flow pulverizer for liquid flow pulverization, then mixing 20g of the liquid flow pulverized positive electrode powder with 200ml of 0.5mol/L lithium nitrate solution, carrying out ultrasonic treatment at 40 ℃ for 45min, then uniformly stirring, sieving with a 400-mesh sieve, standing for 60min, and carrying out vacuum filtration on an upper suspension to obtain a precipitate;
s2, placing the precipitate into 150mL of ammonia water solution with pH value of 11.6, stirring while soaking, wherein the stirring speed is 700r/min, filtering the precipitate, repeating twice, wherein the soaking time is 10h each time, removing magnetic foreign matters by adopting an electromagnetic iron remover during soaking, drying, and removing the magnetic foreign matters by adopting a permanent magnet iron remover again to obtain 13.93g of purified lithium manganate battery recovered anode powder.
The composition changes before and after the impurity removal of the sample of this example are shown in Table 8.
TABLE 8 variation of the composition before and after sample treatment
Example 9
The impurity removal method for recycling positive electrode powder of the lithium ion battery comprises the following steps:
s1, placing recovered positive electrode powder of a lithium cobaltate battery into an air flow mill for air flow crushing, adopting a permanent magnet iron remover to remove magnetic foreign matters, then mixing 5g of air flow crushed positive electrode powder with 30mL of glycerol, performing ultrasonic treatment at 30 ℃ for 30min, then uniformly stirring, sieving with a 300-mesh sieve, standing for 10min, transferring an upper suspension into a centrifuge tube, and performing centrifugal filtration for 15min at a centrifugal speed of 7000r/min to obtain a precipitate;
s2, placing the precipitate into 30mL of ammonia water solution with pH value of 11.9, stirring while soaking, wherein the stirring speed is 900r/min, filtering the precipitate, repeating for 1 time, wherein the soaking time is 10 hours each time, removing magnetic foreign matters by adopting an electromagnetic iron remover during soaking, and drying to obtain 3.68g of purified lithium cobaltate battery recovered anode powder.
The composition changes before and after the impurity removal of the sample of this example are shown in Table 9.
TABLE 9 variation of the composition before and after sample treatment
Example 10
The impurity removal method for recycling positive electrode powder of the lithium ion battery comprises the following steps:
s1, mechanically crushing reclaimed positive electrode powder of a lithium iron phosphate battery in a mechanical mill, mixing 10g of the mechanically crushed positive electrode powder with 50 mLN-methylpyrrolidone, carrying out ultrasonic treatment at 70 ℃ for 40min, uniformly stirring, sieving with a 325-mesh sieve, standing for 3min, transferring an upper suspension into a centrifuge tube, and carrying out centrifugal filtration at a centrifugal speed of 5000r/min for 30min to obtain a precipitate;
s2, placing the precipitate into 80mL of ammonia water solution with pH value of 12.2, stirring while soaking, wherein the stirring speed is 400r/min, filtering the precipitate, repeating twice, wherein each soaking time is 12h, removing magnetic foreign matters by adopting a permanent magnet iron remover during soaking, drying, and removing the magnetic foreign matters by adopting an electromagnetic iron remover again to obtain 7.86g of purified lithium iron phosphate battery recovered anode powder.
The composition changes before and after the impurity removal of the sample of this example are shown in Table 10.
TABLE 10 variation of the composition before and after sample treatment
As can be seen from tables 1-10, the impurity removal method for the lithium ion battery recovered positive electrode powder can effectively remove most of metal impurities such as copper, iron, aluminum and the like in the lithium ion battery recovered positive electrode powder, and cannot damage the original structure of the material and cause loss of rare metals such as nickel, cobalt, manganese and the like.
It should be apparent that the above embodiments are merely examples for clarity of illustration and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (5)
1. The impurity removing method for recycling the positive electrode powder of the lithium ion battery is characterized by at least comprising the following steps:
s1, placing the recovered positive electrode powder of the lithium ion battery into a liquid medium, fully dispersing, standing and settling the obtained slurry, taking a suspension, and carrying out solid-liquid separation to obtain a precipitate;
the liquid medium is at least one of aqueous solution containing lithium ions, N-methyl pyrrolidone, ethylene glycol and glycerol;
s2, placing the precipitate into an ammonia water solution, stirring while soaking, and then filtering and drying to obtain the lithium ion battery recovered anode powder after impurity removal;
wherein the ratio of the recovered positive electrode powder of the lithium ion battery to the total ammonia water solution for soaking is (24-50 g) (600-900 mL);
in the step S2 of the process of the present invention,
placing the precipitate into ammonia water solution, stirring while soaking, filtering the precipitate, repeating the operation for more than 1 time, and drying to obtain the lithium ion battery recovered anode powder after impurity removal;
the process of each repeated operation is as follows: placing the precipitate into new ammonia water solution, stirring while soaking, and filtering the precipitate;
the pH of the ammonia water solution is 9-13;
the total soaking time is 0.5-72 h;
the stirring speed is 100-1000 r/min;
in the step S1 of the process,
the lithium ion battery is at least one of a lithium cobalt oxide battery, a lithium manganese oxide battery, a lithium iron phosphate battery and a lithium nickel cobalt manganese oxide battery;
the aqueous solution containing lithium ions is at least one of a lithium chloride solution, a lithium bromide solution, a lithium iodide solution, a lithium nitrate solution, a lithium sulfate solution, a lithium perchlorate solution, a lithium acetate solution and a lithium hydroxide solution, and the concentration of the lithium ions in the aqueous solution containing lithium ions is 0.01-1 mol/L;
the ratio of the recovered positive electrode powder of the lithium ion battery to the liquid medium is (10-500 g) 1L;
the mode of fully dispersing is that ultrasonic dispersion is carried out firstly and then stirring is carried out uniformly;
in the standing sedimentation, the standing time is 0.5-90 min;
the solid-liquid separation is at least one of centrifugal filtration, vacuum filtration and filter pressing.
2. The method according to claim 1, wherein in step S1, before the lithium ion battery recycled positive electrode powder is placed in the liquid medium, the lithium ion battery recycled positive electrode powder is crushed, wherein the crushing is at least one of mechanical crushing, jet milling and liquid flow crushing.
3. The method according to claim 1, wherein in step S1, before the lithium ion battery recycled positive electrode powder is placed in the liquid medium, the permanent magnet iron remover and/or the electromagnetic iron remover is used to remove the magnetic foreign matters in the lithium ion battery recycled positive electrode powder.
4. The method for removing impurities from a lithium ion battery recovered positive electrode powder according to claim 1, wherein in step S1, the slurry is sieved before the slurry is subjected to standing sedimentation, and the mesh number of the sieved sieve is 50-600 mesh.
5. The method for removing impurities from a lithium ion battery recycled positive electrode powder according to claim 1, wherein, in step S2,
when in soaking, a permanent magnet iron remover and/or an electromagnetic iron remover are adopted to remove magnetic foreign matters in the sediment;
or, after drying, removing magnetic foreign matters in the precipitate by adopting a permanent magnet iron remover and/or an electromagnetic iron remover;
or, during soaking and after drying, removing magnetic foreign matters in the precipitate by adopting a permanent magnet iron remover and/or an electromagnetic iron remover.
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