CN115911635A - Low-copper aluminum fluoride-free black powder and preparation method thereof - Google Patents
Low-copper aluminum fluoride-free black powder and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 71
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 52
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000197 pyrolysis Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011888 foil Substances 0.000 claims abstract description 17
- 239000011889 copper foil Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims description 17
- 238000012216 screening Methods 0.000 claims description 15
- 239000002699 waste material Substances 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- -1 iron ions Chemical class 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims 1
- 238000006115 defluorination reaction Methods 0.000 abstract description 4
- 238000003795 desorption Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 230000001698 pyrogenic effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000007873 sieving Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007133 aluminothermic reaction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
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
- C22B1/00—Preliminary treatment of ores or scrap
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting 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
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses low-copper aluminum fluoride-free black powder and a preparation method thereof. The invention adopts the combined process of low-temperature pyrolysis, color separation, salt-washing desorption and pyrogenic defluorination to recover and obtain high-value copper foil, aluminum foil and black powder.
Description
Technical Field
The invention belongs to the technical field of lithium battery recovery, and particularly relates to low-copper aluminum fluoride-free black powder and a preparation method thereof.
Background
The lithium ion battery has the advantages of high voltage, small volume, high energy density, small self-discharge, high safety and the like, and is widely applied to various fields of consumer electronics, power batteries, industrial energy storage and the like. In recent years, with the rapid increase of the production quantity and the use quantity of lithium ion batteries, the quantity of waste lithium ion batteries is more and more huge. At present, the recycling of lithium ion batteries has received more and more attention.
The waste battery black powder is black powder containing metals such as nickel, cobalt, manganese, copper, aluminum, lithium and the like and carbon powder, which is obtained by the working procedures of disassembling, crushing, sieving, pyrolyzing, sorting and the like on a waste lithium ion battery.
Typically, black powders employ a wet leaching process to recover the metal values therein. The method specifically comprises the following steps: leaching nickel, cobalt, manganese and lithium in a sulfuric acid system with a reducing agent; removing impurities from the leachate, extracting, back extracting and the like to respectively obtain nickel sulfate, manganese sulfate and cobalt sulfate solutions; and finally, evaporating and concentrating the final extract liquor, and precipitating lithium carbonate by adopting a supersaturated sodium carbonate solution.
However, in the preparation process of black powder, the pyrolysis pretreatment process is widely used in the existing industrial production, but there are some major problems, such as: (1) the conventional pyrolysis temperature is above 500 ℃, and due to the complex material types, the electrolyte and the diaphragm are combusted at the temperature, so that local reaction in the pyrolysis furnace is severe easily, the temperature is out of control, and the aluminum metal in the battery can generate aluminothermic reaction at the temperature of above 600 ℃, so that the instantaneous temperature is greatly increased, and the pyrolysis furnace is burnt through, thereby bringing greater safety risk; (2) at the temperature, metal copper and aluminum in the battery are greatly oxidized, so that the impurity content in battery powder is high, and in the subsequent acid liquor leaching, oxides are dissolved to generate a large amount of copper-aluminum slag, so that the acid and alkali consumption is large, the added value of products is low, and a large pressure is brought to the subsequent purification. Although the oxidation condition of copper and aluminum can be improved by introducing inert gas for anaerobic pyrolysis, the existing equipment is difficult to completely seal, and the copper and aluminum are still partially oxidized; (3) in the pyrolysis process, the binder PVDF, lithium hexafluorophosphate and the like in the electrolyte are decomposed and remained, so that the fluoride content in the black powder is higher, the black powder is treated by a wet method, wastewater discharge is not up to the standard due to entering of the black powder, calcium fluoride slag generated after calcium solidification belongs to hazardous waste, special treatment needs to be performed by qualified treatment factories, lithium fluoride belongs to precipitation, part of fluorine enters lithium extraction liquid, the subsequent lithium extraction rate is reduced, the purity of lithium carbonate is reduced, and the fluorine impurity content is increased.
Therefore, in order to avoid the trouble brought to downstream manufacturers who treat the black powder by the wet method, it is necessary to improve the front-end process to prepare the black powder with low copper aluminum fluorine content.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides the low-copper aluminum fluoride-free black powder and the preparation method thereof, which can recover the copper aluminum foil through low-temperature pyrolysis and carry out defluorination treatment to prepare the low-copper aluminum fluoride-free black powder.
According to one aspect of the invention, the low-copper aluminum fluoride-free black powder is provided, wherein the water content of the low-copper aluminum fluoride-free black powder is less than or equal to 1.0wt%, the total content of nickel, cobalt and manganese metal elements is greater than or equal to 30.0wt%, the content of lithium element is greater than or equal to 3.3wt%, the content of copper element is less than or equal to 0.8wt%, the content of aluminum is less than or equal to 1.0wt%, and the content of fluorine is less than or equal to 0.1wt%.
In some embodiments of the invention, the low-copper aluminum fluoride-free black powder has a particle size of 0.25mm or less.
The invention also provides a preparation method of the low-copper aluminum fluoride-free black powder, which comprises the following steps:
s1: discharging, disassembling, crushing and screening the waste lithium ion battery for the first time to obtain first black powder and first oversize products;
s2: pyrolyzing the first oversize product at 300-400 ℃ in an inert atmosphere, sieving the pyrolyzed material for the second time to obtain second black powder and a second oversize product, and performing color separation on the second oversize product to obtain a copper foil and an aluminum-containing pole piece;
s3: placing the aluminum-containing pole piece in a trivalent ferric salt solution for reaction, performing third screening on the obtained reaction material to obtain an aluminum foil and slurry, performing solid-liquid separation on the slurry, and drying the obtained solid to obtain third black powder;
s4: and blowing air into the first black powder, the second black powder and the third black powder at 500-1000 ℃ for roasting, wherein the volume content of water vapor in the air is 10% -40%, and thus the low-copper aluminum fluoride-free black powder is obtained.
In some embodiments of the present invention, in step S1, the size of the crushed material obtained after the crushing is less than or equal to 5cm.
In some embodiments of the present invention, in step S1, the waste lithium ion battery is at least one of a ternary lithium ion battery, a lithium cobaltate battery, a lithium manganate battery or a lithium nickelate battery.
In some embodiments of the invention, the mesh size of the first sieving, the second sieving and the third sieving is independently 0.2-0.3mm.
In some embodiments of the invention, in step S2, the pyrolysis is performed in a pyrolysis furnace, and the first oversize material is filled in the pyrolysis furnace at a rate of 5% to 15%.
In some embodiments of the invention, in step S2, the pyrolysis time is 3 to 5 hours.
In some embodiments of the present invention, in step S3, the solid-to-liquid ratio of the aluminum-containing pole piece to the ferric salt solution is 0.5 to 2.0g/mL, and the concentration of iron ions in the ferric salt solution is 0.1 to 0.5mol/L.
In some embodiments of the invention, the temperature of the reaction in step S3 is 40-90 ℃. Further, the reaction time is 0.5-1.0h.
In some embodiments of the invention, in step S3, the ferric salt solution is at least one of a ferric sulfate solution, a ferric nitrate solution, or a ferric chloride solution.
In some embodiments of the present invention, in step S3, the drying temperature is 100-120 ℃, and the drying time is 1-2h.
In some embodiments of the invention, the flow rate of the air in step S4 is 8-15Nm 3 /min。
In some embodiments of the present invention, in step S4, the time for the calcination is 0.5 to 1.0h.
According to a preferred embodiment of the invention, at least the following advantages are achieved:
1. according to the invention, aiming at the problems that potential safety hazards are easy to occur at a high pyrolysis temperature, copper and aluminum are oxidized in a large area and fluorine is remained in black powder, a combined process of low-temperature pyrolysis, color separation, salt washing desorption and pyrogenic defluorination is adopted, and high-value copper foil, aluminum foil and black powder are recovered and obtained.
2. Firstly, crushing the battery through coarse crushing, screening out part of black powder falling off in the crushing process, performing low-temperature pyrolysis to control the temperature of the whole process to be below 400 ℃, performing pyrolysis under an anaerobic condition, avoiding the combustion of electrolyte and a diaphragm in the crushed material, avoiding the phenomenon of temperature runaway caused by thermit reaction, protecting a pyrolysis furnace, reducing the oxidation degree of copper and aluminum, simultaneously carbonizing a binder, and screening out part of black powder falling off in the pyrolysis process again; because of low-temperature reaction, the desorption of the positive electrode powder is incomplete, and the negative electrode binder is decomposed at a slightly higher temperature and is easy to fall off, the copper foil is selected by adopting a color selection method, and the aluminum-containing pole piece enters a salt washing process; in the salt washing process, aluminum is corroded by utilizing the principle that ferric ions react with metal aluminum, so that black powder falls off, and the reaction equation is as follows:
Al+3Fe 3+ →Al 3+ +3Fe 2+
3. carrying out high-temperature defluorination on the obtained black powder, wherein on one hand, the adhesive attached at high temperature is completely carbonized and decomposed, and fluorine is dissociated in a gas form; on the other hand, during the decomposition process of the binder, fluorine is also combined with metal elements to generate fluoride, and the fluorine can be removed by displacement through high-temperature steam, and the reaction equation is as follows:
2LiF+H 2 O→Li 2 O+2HF
MeF 2 +H 2 O→MeO+2HF(Me＝Ni,Co,Mn)
drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic process flow diagram of example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts are within the protection scope of the present invention based on the embodiments of the present invention.
Example 1
A method for reducing the content of copper, aluminum and fluorine in battery black powder comprises the following specific steps:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, screening the crushed material for the first time through a screen with the aperture of 0.25mm to obtain undersize as first black powder and first oversize;
step 3, adding the first oversize product into a pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to be 5%, continuously introducing nitrogen, heating to 300 ℃, and continuing for 5 hours;
step 4, sieving the pyrolyzed material for the second time through a sieve with the aperture of 0.25mm to obtain undersize products which are second black powder and second oversize products;
step 5, carrying out color sorting separation on the second oversize product through a color sorter to obtain copper foil and an aluminum-containing pole piece;
step 6, adding an aluminum-containing pole piece into a ferric sulfate solution with the iron ion concentration of 0.1mol/L according to the solid-to-liquid ratio of 0.5g/mL, and reacting for 0.5h at 90 ℃;
step 7, sieving the reacted mixed material for the third time through a sieve with the aperture of 0.25mm to obtain aluminum foil and slurry;
step 8, performing filter pressing on the obtained slurry, and drying for 2 hours at 100 ℃ to obtain third black powder;
step 9, placing the obtained first, second and third black powders in a fluidized bed roasting furnace, blowing air at 500 ℃ for 1.0h, wherein the volume content of water vapor in the air is 40%, and the air flow is 15Nm 3 /min；
And step 10, collecting dust at the outlet of the fluidized bed roasting furnace to obtain black powder with low copper aluminum fluorine content.
Monitoring the conditions in the pyrolysis furnace: no obvious sparks exist in the furnace.
Example 2
A method for reducing the content of copper, aluminum and fluorine in battery black powder comprises the following specific processes:
step 1, discharging and disassembling a waste lithium cobaltate battery, and crushing the waste lithium cobaltate battery into a crushed material with the granularity of less than 5 cm;
step 2, screening the crushed material for the first time through a screen with the aperture of 0.25mm to obtain undersize as first black powder and first oversize;
step 3, adding the first oversize product into a pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to be 10%, continuously introducing nitrogen, heating to 350 ℃, and continuing for 4 hours;
step 4, sieving the pyrolyzed material for the second time by using a sieve with the aperture of 0.25mm to obtain undersize products which are second black powder and second oversize products;
step 5, performing color sorting separation on the second oversize product through a color sorting machine to obtain copper foil and an aluminum-containing pole piece;
step 6, adding an aluminum-containing pole piece into a ferric nitrate solution with the concentration of iron ions of 0.3mol/L according to the solid-to-liquid ratio of 1.0g/mL, and reacting for 1.0h at 60 ℃;
step 7, sieving the reacted mixture for the third time through a sieve with the aperture of 0.25mm to obtain aluminum foil and slurry;
step 8, carrying out filter pressing on the obtained slurry, and drying for 1.5 hours at 110 ℃ to obtain third black powder;
step 9, placing the obtained first, second and third black powders in a fluidized bed roasting furnace, blowing air at 800 ℃ for 1.0h, wherein the volume content of water vapor in the air is 20%, and the air flow is 12Nm 3 /min；
And step 10, collecting dust at the outlet of the fluidized bed roasting furnace to obtain black powder with low copper aluminum fluorine content.
Monitoring the conditions in the pyrolysis furnace: no obvious sparks are generated in the furnace.
Example 3
A method for reducing the content of copper, aluminum and fluorine in battery black powder comprises the following specific steps:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the battery into a crushed material with the granularity of less than 5 cm;
step 2, sieving the crushed materials for the first time through a sieve with the aperture of 0.25mm to obtain undersize products which are first black powder and first oversize products;
step 3, adding the first oversize product into a pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to be 15%, continuously introducing nitrogen, heating to 400 ℃, and continuing for 3 hours;
step 4, sieving the pyrolyzed material for the second time through a sieve with the aperture of 0.25mm to obtain undersize products which are second black powder and second oversize products;
step 5, performing color sorting separation on the second oversize product through a color sorting machine to obtain copper foil and an aluminum-containing pole piece;
step 6, adding an aluminum-containing pole piece into a ferric chloride solution with the iron ion concentration of 0.5mol/L according to the solid-to-liquid ratio of 2.0g/mL, and reacting for 1.0h at 40 ℃;
step 7, sieving the reacted mixed material for the third time through a sieve with the aperture of 0.25mm to obtain aluminum foil and slurry;
step 8, carrying out filter pressing on the obtained slurry, and drying for 1h at 120 ℃ to obtain third black powder;
step 9, placing the obtained first, second and third black powders in a fluidized bed roasting furnace, blowing air at 1000 ℃ for 0.5h, wherein the volume content of water vapor in the air is 10 percent, and the air flow is 8Nm 3 /min；
And step 10, collecting dust at the outlet of the fluidized bed roasting furnace to obtain black powder with low copper aluminum fluorine content.
Monitoring the conditions in the pyrolysis furnace: no obvious sparks are generated in the furnace.
Comparative example 1
The preparation method of the black powder is different from the embodiment 1 in that the crushed material is directly subjected to low-temperature pyrolysis and screening, and the specific process is as follows:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, adding the crushed materials into a pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to be 5%, continuously introducing nitrogen, heating to 300 ℃, and keeping for 5 hours;
step 3, screening the pyrolyzed material by using a screen with the aperture of 0.25mm to obtain undersize black powder and oversize copper-aluminum foil;
and 4, separating the copper foil and the aluminum foil through color selection to obtain the copper foil and the aluminum foil.
Monitoring the conditions in the pyrolysis furnace: no obvious sparks exist in the furnace.
Comparative example 2
The preparation method of the black powder is different from the embodiment 2 in that the crushed material is directly subjected to low-temperature pyrolysis and screening, and the specific process is as follows:
step 1, discharging and disassembling a waste lithium cobalt oxide battery, and crushing the battery into a crushed material with the particle size of below 5 cm;
step 2, adding the crushed materials into a pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to be 10%, continuously introducing nitrogen, heating to 350 ℃, and continuing for 4 hours;
step 3, screening the pyrolyzed material by using a screen with the aperture of 0.25mm to obtain undersize black powder and oversize copper-aluminum foil;
and 4, separating the copper foil and the aluminum foil through color selection to obtain the copper foil and the aluminum foil.
Monitoring the conditions in the pyrolysis furnace: no obvious sparks exist in the furnace.
Comparative example 3
The preparation method of the black powder is different from the embodiment 3 in that the crushed material is directly subjected to low-temperature pyrolysis and screening, and the specific process is as follows:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the battery into a crushed material with the granularity of less than 5 cm;
step 2, adding the crushed materials into a pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to be 15%, continuously introducing nitrogen, heating to 400 ℃, and continuing for 3 hours;
step 3, screening the pyrolyzed material through a screen with the aperture of 0.25mm to obtain undersize black powder and oversize copper-aluminum foil;
and 4, separating the copper foil and the aluminum foil through color selection to obtain the copper foil and the aluminum foil.
Monitoring the conditions in the pyrolysis furnace: no obvious sparks are generated in the furnace.
The black powders obtained in examples 1 to 3 and comparative examples 1 to 3 were examined, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, in comparative examples 1 to 3, the content of fluorine in the black powder was high, indicating that there was much fluoride residue; comparative examples 1-3 have insufficient pyrolysis temperature, difficult complete pyrolysis reaction, and low total nickel, cobalt and manganese content, which indicates that the desorption rate of the cathode powder is low.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The low-copper aluminum fluoride-free black powder is characterized by comprising the following components, by weight, less than or equal to 1.0% of water, more than or equal to 30.0% of total content of nickel, cobalt and manganese metal elements, more than or equal to 3.3% of lithium elements, less than or equal to 0.8% of copper elements, less than or equal to 1.0% of aluminum elements and less than or equal to 0.1% of fluorine elements.
2. The method for preparing low copper aluminum fluoride-free black powder as claimed in claim 1, comprising the steps of:
s1: discharging, disassembling, crushing and primary screening the waste lithium ion battery to obtain first black powder and first oversize products;
s2: pyrolyzing the first oversize product at 300-400 ℃ in an inert atmosphere, screening the pyrolyzed material for the second time to obtain second black powder and a second oversize product, and carrying out color separation on the second oversize product to obtain copper foil and an aluminum-containing pole piece;
s3: placing the aluminum-containing pole piece in a ferric iron salt solution for reaction, carrying out third screening on the obtained reaction material to obtain an aluminum foil and slurry, carrying out solid-liquid separation on the slurry, and drying the obtained solid to obtain third black powder;
s4: and blowing air into the first black powder, the second black powder and the third black powder at 500-1000 ℃ for roasting, wherein the volume content of water vapor in the air is 10-40%, and thus the low-copper aluminum fluoride-free black powder is obtained.
3. The method according to claim 2, wherein in step S1, the size of the crushed material obtained after crushing is 5cm or less.
4. The preparation method according to claim 2, wherein in step S1, the waste lithium ion battery is at least one of a ternary lithium ion battery, a lithium cobalt oxide battery, a lithium manganate battery or a lithium nickel oxide battery.
5. The method according to claim 2, wherein the first, second and third sifts have mesh sizes of 0.2-0.3mm.
6. The method according to claim 2, wherein in step S2, the pyrolysis time is 3 to 5 hours.
7. The preparation method according to claim 2, wherein in step S3, the solid-to-liquid ratio of the aluminum-containing pole piece to the ferric salt solution is 0.5-2.0g/mL, and the concentration of iron ions in the ferric salt solution is 0.1-0.5mol/L.
8. The method according to claim 2, wherein the temperature of the reaction in step S3 is 40 to 90 ℃.
9. The method according to claim 2, wherein in step S3, the ferric salt solution is at least one of a ferric sulfate solution, a ferric nitrate solution, or a ferric chloride solution.
10. The production method according to claim 2, wherein the flow rate of the air in step S4 is 8 to 15Nm 3 /min。
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| CN202211740271.1A CN115911635A (en) | 2022-12-22 | 2022-12-22 | Low-copper aluminum fluoride-free black powder and preparation method thereof |
| PCT/CN2023/080229 WO2024130855A1 (en) | 2022-12-22 | 2023-03-08 | Low-copper-aluminum fluorine-free black powder and preparation method therefor |
| FR2313160A FR3144166A1 (en) | 2022-12-22 | 2023-11-28 | FLUORINE-FREE BLACK MASS WITH LOW COPPER AND ALUMINUM CONTENT AND PREPARATION METHOD THEREFOR |
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| CN202211740271.1A CN115911635A (en) | 2022-12-22 | 2022-12-22 | Low-copper aluminum fluoride-free black powder and preparation method thereof |
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| JP6798918B2 (en) * | 2017-03-30 | 2020-12-09 | Ｊｘ金属株式会社 | Lithium-ion battery scrap disposal method |
| CN108666645B (en) * | 2018-06-26 | 2023-05-26 | 中国科学院生态环境研究中心 | Green stripping method for waste lithium ion power battery electrode material |
| CN111495925B (en) * | 2020-04-20 | 2021-09-24 | 北京矿冶科技集团有限公司 | Method for pyrolyzing and defluorinating chlorine of waste lithium battery |
| CN114147043B (en) * | 2021-09-30 | 2024-05-10 | 湖南江冶新能源科技股份有限公司 | Sorting method for recycling anode and cathode powder of waste lithium batteries |
| CN115172923A (en) * | 2022-06-23 | 2022-10-11 | 广东邦普循环科技有限公司 | Method for recovering battery powder through low-temperature pyrolysis desorption |
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