CN117096486A - Repairing and regenerating method for waste lithium ion battery anode material - Google Patents
Repairing and regenerating method for waste lithium ion battery anode material Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 54
- 239000002699 waste material Substances 0.000 title claims abstract description 46
- 239000010405 anode material Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 claims abstract description 105
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002245 particle Substances 0.000 claims abstract description 62
- 238000005245 sintering Methods 0.000 claims abstract description 58
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 239000011833 salt mixture Substances 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 48
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- 230000008439 repair process Effects 0.000 claims description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- 238000011069 regeneration method Methods 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 abstract description 15
- 238000002844 melting Methods 0.000 abstract description 9
- 230000008018 melting Effects 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 238000007873 sieving Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 230000009469 supplementation Effects 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000004246 zinc acetate Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- FCGXLCNBWYIEAA-UHFFFAOYSA-N 1,3-benzothiazol-6-ylmethanamine Chemical compound NCC1=CC=C2N=CSC2=C1 FCGXLCNBWYIEAA-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum ion Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 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 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000010926 waste battery Substances 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a repairing and regenerating method of a waste lithium ion battery anode material, and belongs to the technical field of battery material recovery. Firstly, performing ball milling treatment on an aged positive electrode material of a waste lithium ion battery to obtain a single-particle positive electrode material; mixing the single-particle positive electrode material with the lithium-rich salt mixture, and then performing primary sintering to obtain a lithium-supplementing single-particle positive electrode material; and finally, mixing the lithium-supplementing single-particle positive electrode material with a lithium compound, and then performing secondary sintering to obtain the repaired single-crystal positive electrode material. According to the invention, the multicomponent lithium-rich salt mixture and the aged positive electrode material are mixed, the lithium supplementing amount required for repairing the positive electrode material is not required to be accurately controlled, the purpose of melting and supplementing lithium can be realized at a lower temperature, and the operation is not required to be at high temperature and high pressure, so that the method is safer and has low energy consumption.
Description
Technical Field
The invention relates to the technical field of battery material recovery, in particular to a method for repairing and regenerating a waste lithium ion battery anode material.
Background
Lithium ion batteries have been attracting attention because of their significant advantages in energy density, rate capability, and cycle life. In recent years, with rapid development of renewable energy sources and uneven space-time distribution of generated energy, the demand for energy storage is increasingly urgent. The lithium ion battery is used as a high-efficiency energy storage carrier, is widely applied to household and commercial energy storage systems, and effectively improves the stability of a power grid and the energy supply safety. The rapid rise in the electric automobile industry has also driven an increasing demand for high energy density lithium ion batteries, particularly represented by ternary nickel cobalt lithium manganate (NCM) positive electrode materials. However, after the lithium ion battery is subjected to long-period circulation in the use process, the lithium ion battery is inevitably unsuitable for continuous use due to the factors of reversible lithium loss, material structure transformation, ohmic resistance increase and the like, so that capacity and voltage are attenuated, and a large number of waste batteries needing to be properly disposed of are caused.
As a component of highest economic value in lithium ion batteries, recycling of the positive electrode material has been one of the most interesting core technologies. The nickel, cobalt and lithium metal resources in China respectively occupy 2.1 percent, 1.84 percent and 7.69 percent of the world proved exploitation reserves, and the grade of the metal resources in the waste ternary lithium ion battery is far higher than that of the original ore. Therefore, the recycling of the lithium ion battery is a necessary trend of sustainable development of new energy industry. The ternary nickel-cobalt-manganese anode material contains rich Li, ni, co, mn metal elements, but the traditional recovery method mainly adopts pyrometallurgy and hydrometallurgy, and the waste lithium ion battery is simply regarded as a mixture containing a plurality of metal elements, so that the components are difficult to separate and recycle efficiently. The pyrogenic recovery process is simple in operation and short in flow, but part of metal resources are difficult to recover (lithium exists in the flue gas in the form of lithium oxide, transition metal exists in the slag in the form of alloy), and the treatment process is high in energy consumption, so that waste residues, smoke dust, waste gas and the like which pollute the environment are generated; the wet process is represented by domestic Bungpu circulation, grid Lin Mei and other companies (CN 116065033A, CN113802002A, CN111276767A, CN115505753A and the like), the recovery rate of metal resources of the wet recovery process is higher, the impurity content of the final product is low, the purity is higher, high-temperature smelting and the like are not needed, but the wet process flow is complex, a large amount of acid-base reagents are needed, and waste water needing further treatment is generated.
Compared with the two processes, the repairing and regenerating technology is a novel scheme provided on the basis of the chemical components and crystal structure characteristics of the aged positive electrode material, the electrochemical performance degradation of the aged positive electrode material is mainly caused by active material loss, reversible lithium loss and conductive performance loss, by taking ternary nickel cobalt manganese material as an example, part of reversible lithium can generate SEI film, lithium dendrite and the like to become irreversible lithium in the cyclic aging process, the lamellar crystal structure of the surface layer which is convenient for lithium ion deintercalation can be converted into a spinel structure and a rock salt structure with larger resistance, and the separation and denaturation of the binder and the conductive agent can cause the conductive performance to be poor. The repair and regeneration technology supplements lithium for the aged positive electrode material by hydrothermal, molten salt, electrochemistry and other methods, and realizes repair of the layered crystal structure under the induction of the subsequent high-temperature sintering condition. CN112670602a proposes a method for regenerating and repairing ternary positive electrode material based on lithium-ion-containing solution hydrothermal compensation and high-temperature calcination to repair rock salt phase, which does not damage the structure of the positive electrode material, but coats the surface of the positive electrode material to form a CEI film through hydrothermal process, and CO in air during high-temperature calcination 2 And generating lithium carbonate molten salt through reaction, so as to repair the rock salt phase on the surface layer of the anode material. However, the method needs to use a high-concentration LiOH solution (2-4 mol/L) and carry out hydrothermal reaction under high-pressure conditions, so that certain potential safety hazards exist, and the calcination temperature and time need to be determined after the CEI film thickness is measured by means of an expensive transmission electron microscope. CN116216794a proposes a method for recovering and regenerating hexagonal prism single crystal ternary positive electrode material from lithium ion battery, which comprises sintering quantitative lithium salt and waste ternary positive electrode material under oxygen atmosphere, crushing, sieving, dissolving in water, mixing dry positive electrode material with a small amount of lithium salt again, sintering, obtaining crystal face advantageAnd (3) growing the hexagonal prism single crystal ternary positive electrode material. The method does not need high-pressure reaction conditions of hydrothermal process, but the melting point of the lithium salt is higher, such as LiOH (462 ℃), li 2 CO 3 (720℃)、Li 2 SO 4 (859 ℃) so that the primary sintering temperature required by lithium supplementing is 300-1300 ℃, compared with a hydrothermal method, the energy consumption is higher, and the sintering time is longer (10 hours).
In view of the above analysis of the prior art, the microscopic mechanism of the repairing process of the aged cathode material is complex, and how to improve the repairing method to achieve the goal of recycling at a lower temperature and in a shorter flow is still a current technical problem.
Disclosure of Invention
The invention aims to provide a method for repairing and regenerating a waste lithium ion battery anode material, which aims to solve the problem of lithium supplementation at a higher sintering temperature and a longer sintering time in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a repairing and regenerating method of a waste lithium ion battery anode material, which comprises the following steps:
(1) Performing ball milling treatment on the aged positive electrode material of the waste lithium ion battery to obtain a single-particle positive electrode material;
(2) Mixing the single-particle positive electrode material with the lithium-rich salt mixture, and then performing primary sintering to obtain a lithium-supplementing single-particle positive electrode material;
(3) And mixing the lithium-supplementing single-particle positive electrode material with a lithium compound, and then performing secondary sintering to obtain the repaired single-crystal positive electrode material.
Preferably, in the step (1), the ball-milling treatment is carried out at a ball-material ratio of 1-3:1, a rotational speed of 4000-6000 rpm and a time of 3-15 min.
Preferably, in the step (2), the lithium-rich salt mixture is a mixture of two or more of lithium chloride, potassium chloride, aluminum chloride and lithium carbonate; the molar ratio of the single-particle positive electrode material to the lithium-rich salt mixture is 1:3 to 5.
Preferably, the lithium-rich salt mixture is lithium chloride and aluminum chloride, wherein the molar ratio of lithium chloride to aluminum chloride is 3:1 to 2.
Preferably, in the step (2), the temperature of the primary sintering is 150 to 400 ℃ and the time is 2 to 6 hours.
Preferably, in the step (3), the molar ratio of the lithium-supplementing single-particle positive electrode material to the lithium compound is 100:4 to 6.
Preferably, in the step (3), the lithium compound includes one or more of lithium chloride, lithium nitrate, lithium hydroxide and lithium carbonate.
Preferably, in the step (3), the secondary sintering is performed at 600 to 1000 ℃ for 6 to 10 hours.
The invention has the beneficial effects that:
(1) According to the invention, the aged positive electrode material is subjected to ball milling treatment, so that a single-particle positive electrode material can be obtained, on one hand, the specific surface area of the positive electrode material is increased, the subsequent lithium supplementing and crystal form repairing can be ensured to be more uniform, and on the other hand, the repairing and regenerating positive electrode material with good single crystal morphology is also obtained.
(2) The invention mixes the multi-component lithium-rich salt mixture and the aged positive electrode material, and does not need to accurately control the lithium supplementing amount required by repairing the positive electrode material, thereby carrying out self-limiting lithium supplementing on the positive electrode material. The purpose of melting and supplementing lithium can be realized at a lower temperature, and the operation does not need high temperature and high pressure, so that the method is safer and has low energy consumption.
(3) The invention can realize the restoration purpose of the opposite layered transition of the surface layer crystal structure from rock salt phase and spinel after secondary sintering of the lithium supplementing single-particle positive electrode material, and obtain the regenerated positive electrode material with good electrochemical performance.
Drawings
FIG. 1 is an SEM image of a single-particle positive electrode material of example 1;
FIG. 2 is an SEM image of a single-particle positive electrode material of example 2;
FIG. 3 is an SEM image of a single-particle positive electrode material of example 3;
FIG. 4 is an SEM image of a single-particle positive electrode material of example 4;
FIG. 5 is an SEM image of a single-particle positive electrode material of example 5;
FIG. 6 is an SEM image of a single-particle positive electrode material of example 5 for lithium supplementation;
FIG. 7 is an SEM image of a repaired single crystal positive electrode material of example 5;
FIG. 8 is an XRD pattern of the aged and repaired single-crystal cathode materials of example 5;
fig. 9 is a graph of the 0.5C charge-discharge cycle of the button half cell reassembled with the single crystal positive material repaired in example 5.
Detailed Description
The invention provides a repairing and regenerating method of a waste lithium ion battery anode material, which comprises the following steps:
(1) Performing ball milling treatment on the aged positive electrode material of the waste lithium ion battery to obtain a single-particle positive electrode material;
(2) Mixing the single-particle positive electrode material with the lithium-rich salt mixture, and then performing primary sintering to obtain a lithium-supplementing single-particle positive electrode material;
(3) And mixing the lithium-supplementing single-particle positive electrode material with a lithium compound, and then performing secondary sintering to obtain the repaired single-crystal positive electrode material.
In the invention, the treatment method of the aged positive electrode material of the waste lithium ion battery comprises the following steps:
s1, thoroughly discharging a waste lithium ion battery and then disassembling the waste lithium ion battery to obtain a positive plate;
and S2, mixing the positive electrode plate and the organic solvent, and sequentially stripping, sieving, centrifugally separating and drying to obtain the aged positive electrode material of the waste lithium ion battery.
In the present invention, in the step S1, the waste lithium ion battery is preferably soaked in the salt solution for complete discharge, and the soaking time is 0.5-6 hours, preferably 1-5 hours, and more preferably 2-4 hours.
The salt solution preferably used in the present invention is a zinc acetate solution, a ferrous sulfate solution or a zinc sulfate solution, and more preferably a zinc acetate solution, wherein the concentration of the salt solution is 0.5 to 1mol/L, preferably 0.5mol/L, 0.8mol/L, 1mol/L, and still more preferably 0.5mol/L.
In the invention, in the step S1, the waste lithium ion battery is disassembled into accessories such as a battery positive pole piece, a battery negative pole piece, a diaphragm, a shell and the like during disassembly, and the positive pole piece is taken out.
In the present invention, in the step S2, it is preferable that the positive electrode sheet is rinsed with dimethyl carbonate and then naturally dried.
The invention adopts dimethyl carbonate to wash the positive pole piece to remove electrolyte remained on the surface of the pole piece.
In the present invention, in the step S2, the solid-to-liquid ratio of the positive electrode sheet and the organic solvent is 1g: 8-12 mL, preferably 1g:9 to 11mL, more preferably 1g:10mL.
In the present invention, the organic solvent contains gamma valerolactone, dihydro-l-glucosone or isosorbide dimethyl ether, preferably gamma valerolactone or isosorbide dimethyl ether, and more preferably gamma valerolactone.
In the present invention, in the step S2, the positive electrode sheet and the organic solvent are mixed and then heated to 60 to 100 ℃, preferably 70 to 90 ℃, and more preferably 80 ℃.
In the present invention, in the step S2, the peeling is performed under an ultrasonic condition, wherein the power of the ultrasonic is 90 to 150W, preferably 100 to 140W, preferably 110 to 130W, and the ultrasonic time is 2 to 10min, preferably 3 to 9min, further preferably 4 to 8min.
In the present invention, in the step S2, the solid-liquid mixture obtained by the separation is passed through a 5-mesh sieve to remove aluminum foil, and then subjected to centrifugal separation, wherein the rotational speed of the centrifugal separation is 5000 to 8000rpm, preferably 5500 to 7500rpm, preferably 6000 to 7000rpm, and the time of the centrifugal separation is 2 to 10 minutes, preferably 3 to 9 minutes, and more preferably 4 to 8 minutes.
In the invention, the lower layer anode material sediment obtained by centrifugal separation is sequentially cleaned, dried and screened to obtain the aged anode material of the waste lithium ion battery.
In the invention, the state of health (SOH) of the aged positive electrode material of the waste lithium ion battery is 50-80%.
In the present invention, in the step (1), the ball milling treatment is performed using zirconia having a particle diameter of 0.5 to 1.5mm, preferably 1.0mm.
In the invention, in the step (1), the ball-milling treatment has a ball-material ratio of 1-3:1, preferably 2:1; the rotation speed is 4000-6000 rpm, preferably 4500-5500 rpm, more preferably 5000rpm; the time is 3-15 min, preferably 3min, 6min, 9min, 12min, 15min, and more preferably 9min, 12min, 15min.
In the present invention, in the step (2), the lithium-rich salt mixture is a mixture of two or more of lithium chloride, potassium chloride, aluminum chloride and lithium carbonate; the molar ratio of the single-particle positive electrode material to the lithium-rich salt mixture is 1:3 to 5, preferably 1: 3. 1:4 or 1:5.
In the present invention, the lithium-rich salt mixture is preferably lithium chloride and aluminum chloride, wherein the molar ratio of lithium chloride to aluminum chloride is 3:1 to 2, preferably 3:2.
the invention adopts the lithium-rich salt mixture, when the lithium-rich salt mixture is prepared from AlCl 3 When mixed with LiCl, the LiCl solid has a melting point of 605 ℃ and AlCl 3 The melting point of the solid is 194 ℃, the two substances are mixed according to a certain mole ratio to form a eutectic mixture, the melting point is lower than that of a single pure phase substance, and AlCl is added under the pressure of 1bar 3 The melting point of the lithium-rich salt mixture is as low as 110 ℃ when the molar ratio of the lithium-rich salt mixture to LiCl is 2:3, and AlCl 3 Is a covalent compound, which is covalently dimerized in its molten state (Al 2 Cl 6 ) In the form, the aluminum ion is easy to absorb moisture in the air, and the aluminum ion is acidic after being partially hydrolyzed. Aging the waste lithium ion battery to obtain an anode material and AlCl 3 The LiCl system can be mixed to realize the purpose of melting and supplementing lithium at 150-400 ℃, and the operation does not need high temperature and high pressure, and is safer and has low energy consumption. The repair and regeneration method does not need to accurately control the lithium supplementing amount required for repairing the positive electrode material, and carries out self-limiting lithium supplementing on the positive electrode material.
In the present invention, in the step (2), the temperature of the primary sintering is 150 to 400 ℃, preferably 200 to 300 ℃, and more preferably 200 ℃; the time is 2 to 6 hours, preferably 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, more preferably 2 hours, 3 hours, 4 hours.
In the present invention, in the step (3), the molar ratio of the lithium-supplementing single-particle positive electrode material to the lithium compound is 100:4 to 6, preferably 100:5.
in the present invention, in the step (3), the lithium compound contains one or more of lithium chloride, lithium nitrate, lithium hydroxide and lithium carbonate, preferably one or more of lithium chloride, lithium hydroxide and lithium carbonate, and more preferably lithium hydroxide and/or lithium carbonate.
In the present invention, in the step (3), the temperature of the secondary sintering is 600 to 1000 ℃, preferably 700 to 900 ℃, and more preferably 800 ℃; the time is 6 to 10 hours, preferably 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, more preferably 6 hours, 7 hours, 8 hours.
In the invention, the primary sintering and the secondary sintering are both performed by adopting a microwave heating mode, wherein the heating rate is 5-10 ℃/min, preferably 6-9 ℃/min, and more preferably 7-8 ℃/min during the microwave heating. When the microwave heating is carried out, a microwave tube type furnace is preferably used, wherein the microwave frequency is 2.45GHz, and the output power of the microwaves is 0.01-1.40 kW and is continuously adjustable.
The invention adopts a microwave heating mode, and can obviously shorten the repairing and regenerating time of the aged positive electrode material of the waste lithium ion battery.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Waste Li 1 Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM 523) lithium ion battery is soaked in 0.5mol/L zinc acetate solution for 6 hours, thoroughly discharged to 0V, the positive electrode plate is manually disassembled and separated, 200mL dimethyl carbonate (DMC) is adopted to clean electrolyte remained on the surface of the positive electrode plate, and the subsequent operation is waited after natural airing.
Cutting the positive electrode plate into 100mm squares, mixing the square with gamma-valerolactone according to the solid-liquid ratio of 1g to 10mL, heating to 80 ℃, stripping for 10min under the ultrasonic condition of 120W, sieving the solid-liquid mixture with a 5-mesh sieve to remove aluminum foil, centrifuging at the rotating speed of 8000rpm for 10min, taking the precipitate of the lower positive electrode material, drying in a vacuum oven at 100 ℃ for 12h, and sieving with a 120-target standard sieve to obtain the aged positive electrode material of the waste lithium ion battery.
Mixing aged anode materials of waste lithium ion batteries and zirconia grinding beads with the diameter of 1mm according to the mass ratio of 2:1, and then placing the mixture into a high-speed micro-vibration ball mill for ball milling treatment for 3min at the rotating speed of 5000rpm to obtain single-particle anode materials; the single particle positive electrode material is then combined with a lithium-rich salt mixture (wherein the lithium-rich salt mixture consists of LiCl and AlCl 3 Mixing according to the molar ratio of 3:2), uniformly mixing in an agate mortar according to the molar ratio of 1:3, then placing into a microwave tube furnace for primary sintering under the oxygen atmosphere, wherein the heating rate is 5 ℃/min, the temperature is 150 ℃, the primary sintering time is 2 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and finally drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain the single-particle anode material for lithium supplementation.
Single particle positive electrode material to be lithium-supplemented and Li 2 CO 3 The molar ratio is 100:5, uniformly mixing, then placing into a microwave tube furnace, and performing secondary sintering in an oxygen atmosphere, wherein the heating rate is 5 ℃/min, the temperature is 800 ℃, the secondary sintering time is 6 hours, and naturally cooling to room temperature after sintering to obtain the repaired monocrystalline anode material.
Example 2
Waste Li 1 Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM 523) lithium ion battery is soaked in 0.5mol/L zinc acetate solution for 6 hours, thoroughly discharged to 0V, the positive electrode plate is manually disassembled and separated, 200mL dimethyl carbonate (DMC) is adopted to clean electrolyte remained on the surface of the positive electrode plate, and the subsequent operation is waited after natural airing.
Cutting the positive electrode plate into 100mm squares, mixing the square with gamma-valerolactone according to the solid-liquid ratio of 1g to 10mL, heating to 80 ℃, stripping for 10min under the ultrasonic condition of 120W, sieving the solid-liquid mixture with a 5-mesh sieve to remove aluminum foil, centrifuging at the rotating speed of 8000rpm for 10min, taking the precipitate of the lower positive electrode material, drying in a vacuum oven at 100 ℃ for 12h, and sieving with a 120-target standard sieve to obtain the aged positive electrode material of the waste lithium ion battery.
Mixing aged anode materials of waste lithium ion batteries and zirconia grinding beads with the diameter of 1mm according to the mass ratio of 2:1, and then placing the mixture into a high-speed micro-vibration ball mill for ball milling treatment for 6 minutes at the rotating speed of 5000rpm to obtain single-particle anode materials; the single particle positive electrode material is then combined with a lithium-rich salt mixture (wherein the lithium-rich salt mixture consists of LiCl and AlCl 3 Mixing according to the molar ratio of 3:2), uniformly mixing in an agate mortar according to the molar ratio of 1:3, then placing into a microwave tube furnace for primary sintering under the oxygen atmosphere, wherein the heating rate is 10 ℃/min, the temperature is 200 ℃, the primary sintering time is 2 hours, naturally cooling to room temperature, washing with deionized water for 3 times, and finally drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain the single-particle anode material for lithium supplementation.
Single particle positive electrode material to be lithium-supplemented and Li 2 CO 3 The molar ratio is 100:5, uniformly mixing, then placing into a microwave tube furnace, and performing secondary sintering in an oxygen atmosphere, wherein the heating rate is 10 ℃/min, the temperature is 800 ℃, the secondary sintering time is 6 hours, and naturally cooling to room temperature after sintering to obtain the repaired monocrystalline anode material.
Example 3
Example 3 differs from example 2 in that the ball milling time was 9min, all other conditions being identical.
Example 4
Waste Li 1 Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM 523) lithium ion battery is soaked in 0.5mol/L zinc acetate solution for 6 hours, thoroughly discharged to 0V, the positive electrode plate is manually disassembled and separated, 200mL dimethyl carbonate (DMC) is adopted to clean electrolyte remained on the surface of the positive electrode plate, and the subsequent operation is waited after natural airing.
Cutting the positive electrode plate into 100mm squares, mixing the square with gamma-valerolactone according to the solid-liquid ratio of 1g to 10mL, heating to 80 ℃, stripping for 10min under the ultrasonic condition of 120W, sieving the solid-liquid mixture with a 5-mesh sieve to remove aluminum foil, centrifuging at the rotating speed of 8000rpm for 10min, taking the precipitate of the lower positive electrode material, drying in a vacuum oven at 100 ℃ for 12h, and sieving with a 120-target standard sieve to obtain the aged positive electrode material of the waste lithium ion battery.
Mixing aged anode materials of waste lithium ion batteries and zirconia grinding beads with the diameter of 1mm according to the mass ratio of 2:1, and then placing the mixture into a high-speed micro-vibration ball mill for ball milling treatment for 12 minutes at the rotating speed of 5000rpm to obtain single-particle anode materials; the single particle positive electrode material is then combined with a lithium-rich salt mixture (wherein the lithium-rich salt mixture consists of LiCl and AlCl 3 Mixing according to the molar ratio of 3:2), uniformly mixing in an agate mortar according to the molar ratio of 1:5, then placing into a microwave tube furnace for primary sintering under the oxygen atmosphere, wherein the heating rate is 10 ℃/min, the temperature is 200 ℃, the primary sintering time is 2 hours, naturally cooling to room temperature, washing with deionized water for 6 times, and finally drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain the single-particle anode material for lithium supplementation.
Single particle positive electrode material to be lithium-supplemented and Li 2 CO 3 The molar ratio is 100:5, uniformly mixing, then placing into a microwave tube furnace, and performing secondary sintering in an oxygen atmosphere, wherein the heating rate is 10 ℃/min, the temperature is 900 ℃, the secondary sintering time is 6 hours, and naturally cooling to room temperature after sintering to obtain the repaired monocrystalline anode material.
Example 5
Waste Li 1 Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM 523) lithium ion battery is soaked in 0.5mol/L zinc acetate solution for 6 hours, thoroughly discharged to 0V, the positive electrode plate is manually disassembled and separated, 200mL dimethyl carbonate (DMC) is adopted to clean electrolyte remained on the surface of the positive electrode plate, and the subsequent operation is waited after natural airing.
Cutting the positive electrode plate into 100mm squares, mixing the square with gamma-valerolactone according to the solid-liquid ratio of 1g to 10mL, heating to 80 ℃, stripping for 10min under the ultrasonic condition of 120W, sieving the solid-liquid mixture with a 5-mesh sieve to remove aluminum foil, centrifuging at the rotating speed of 8000rpm for 10min, taking the precipitate of the lower positive electrode material, drying in a vacuum oven at 100 ℃ for 12h, and sieving with a 120-target standard sieve to obtain the aged positive electrode material of the waste lithium ion battery.
Mixing aged anode materials of waste lithium ion batteries and zirconia grinding beads with the diameter of 1mm according to the mass ratio of 2:1, and then placing the mixture into a high-speed micro-vibration ball mill for ball milling treatment for 15min at the rotating speed of 5000rpm to obtain single-particle anode materials; the single particle positive electrode material is then combined with a lithium-rich salt mixture (wherein the lithium-rich salt mixture consists of LiCl and AlCl 3 Mixing according to the molar ratio of 3:2), uniformly mixing in an agate mortar according to the molar ratio of 1:5, then placing into a microwave tube furnace for primary sintering under the oxygen atmosphere, wherein the heating rate is 10 ℃/min, the temperature is 200 ℃, the primary sintering time is 2 hours, naturally cooling to room temperature, washing with deionized water for 6 times, and finally drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain the single-particle anode material for lithium supplementation.
Single particle positive electrode material to be lithium-supplemented and Li 2 CO 3 The molar ratio is 100:5, uniformly mixing, then placing into a microwave tube furnace, and performing secondary sintering in an oxygen atmosphere, wherein the heating rate is 10 ℃/min, the temperature is 900 ℃, the secondary sintering time is 8 hours, and naturally cooling to room temperature after sintering to obtain the repaired monocrystalline anode material.
Example 6
Waste Li 1 Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM 523) soaking the lithium ion battery in a ferrous sulfate solution of 1mol/L for 4 hours, thoroughly discharging to 0V, manually disassembling and sorting out the positive plate, cleaning electrolyte remained on the surface of the positive plate by using 200mL of dimethyl carbonate (DMC), naturally airing, and waiting for subsequent operation.
Cutting the positive electrode plate into 100mm squares, mixing 1 g/12 mL of the positive electrode plate with isosorbide dimethyl ether according to a solid-liquid ratio, heating to 100 ℃, peeling off the mixture for 5min under the ultrasonic condition of 90W, sieving the solid-liquid mixture with a 5-mesh sieve to remove aluminum foil, centrifuging and separating the mixture for 5min at the rotating speed of 5000rpm, taking out the precipitate of the lower layer positive electrode material, drying the precipitate in a vacuum oven at 100 ℃ for 12 hours, and sieving the precipitate with a 120-target standard sieve to obtain the aged positive electrode material of the waste lithium ion battery.
Mixing an aged positive electrode material of a waste lithium ion battery and zirconia grinding beads with the diameter of 0.5mm according to the mass ratio of 1:1, and then placing the mixture into a high-speed micro-vibration ball mill for ball milling treatment at the rotating speed of 4000rpm for 15min to obtain a single-particle positive electrode material; the single particle positive electrode material is then combined with a lithium-rich salt mixture (wherein the lithium-rich salt mixture consists of LiCl and AlCl 3 Mixing according to the molar ratio of 3:2), uniformly mixing in an agate mortar according to the molar ratio of 1:5, then placing into a microwave tube furnace for primary sintering under the oxygen atmosphere, wherein the heating rate is 10 ℃/min, the temperature is 400 ℃, the primary sintering time is 2 hours, naturally cooling to room temperature, washing with deionized water for 6 times, and finally drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain the single-particle anode material for lithium supplementation.
The single-particle positive electrode material for supplementing lithium and lithium nitrate are mixed according to the molar ratio of 100:6, uniformly mixing, then placing into a microwave tube furnace, and performing secondary sintering in an oxygen atmosphere, wherein the heating rate is 10 ℃/min, the temperature is 600 ℃, the secondary sintering time is 10 hours, and naturally cooling to room temperature after sintering to obtain the repaired monocrystalline anode material.
Example 7
Waste Li 1 Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM 523) lithium ion battery is soaked in 0.8mol/L zinc sulfate solution for 6 hours, thoroughly discharged to 0V, the positive electrode plate is manually disassembled and separated, 200mL dimethyl carbonate (DMC) is adopted to clean electrolyte remained on the surface of the positive electrode plate, and the subsequent operation is waited after natural airing.
Cutting the positive electrode plate into 100mm squares, mixing 1 g/8 mL of the positive electrode plate with dihydro-L-glucosone according to a solid-liquid ratio, heating to 60 ℃, stripping for 8min under the ultrasonic condition of 150W, removing aluminum foil from the solid-liquid mixture through a 5-mesh screen, centrifugally separating for 8min at the rotating speed of 7000rpm, taking out the precipitate of the lower positive electrode material, drying for 12 hours at the temperature of 100 ℃ in a vacuum oven, and sieving with a 120-target standard sieve to obtain the aged positive electrode material of the waste lithium ion battery.
Aging a waste lithium ion battery to obtain a positive electrode material and zirconia grinding beads with diameters of 1.5mm according to the mass of 3:1After mixing the mass ratios, placing the mixture into a high-speed micro-vibration ball mill, and performing ball milling treatment for 10min at the rotation speed of 6000rpm to obtain a single-particle anode material; the single particle positive electrode material is then combined with a lithium-rich salt mixture (wherein the lithium-rich salt mixture consists of LiCl and AlCl 3 Mixing according to the molar ratio of 3:1), uniformly mixing in an agate mortar according to the molar ratio of 1:4, then placing into a microwave tube furnace for primary sintering under the oxygen atmosphere, wherein the heating rate is 8 ℃/min, the temperature is 300 ℃, the primary sintering time is 3 hours, naturally cooling to room temperature, washing with deionized water for 6 times, and finally drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain the single-particle anode material for lithium supplementation.
The single-particle positive electrode material for lithium supplement and lithium hydroxide are mixed according to the molar ratio of 100:4, uniformly mixing, then placing into a microwave tube furnace, and performing secondary sintering in an oxygen atmosphere, wherein the heating rate is 8 ℃/min, the temperature is 1000 ℃, the secondary sintering time is 7 hours, and naturally cooling to room temperature after sintering to obtain the repaired monocrystalline anode material.
And (3) performance verification:
the single crystal cathode material repaired in example 5 was mixed with a binder PVDF and a conductive agent acetylene black according to 0.8g:0.1g: mixing 0.1g of the mixture with 2.5mLNMP solvent for pulping, uniformly coating on aluminum foil, drying overnight at 80 ℃ in a vacuum oven, cutting a positive plate with the diameter of 14mm by a sheet punching machine, and using 1mol/L LiPF 6 +EC: DEC (1:1wt%) commercial electrolyte and lithium sheet negative electrode were assembled into CR2032 coin cell and tested for charge and discharge performance, and the results are shown in FIG. 9.
As can be seen from FIGS. 1 to 5, the high-speed micro-vibration ball mill can obtain the single-particle positive electrode material with good dispersibility only after the treatment time of more than 9 minutes under the rotation speed of 5000 rpm.
As can be seen from FIGS. 6 and 7, example 5 is conducted under AlCl conditions 3 The positive electrode material after LiCl primary sintering lithium supplementing presents single particle microcosmic appearance with clear edges and corners, cracks and damages exist on the crystal surface, but the repaired single crystal positive electrode material obtained after secondary sintering presents good edge smooth single crystal appearance, and the particle size is in the range of 1-3 mu mGood dispersibility and no surface cracks.
As can be seen from fig. 8, the crystalline structure of the repaired single-crystal cathode material of example 5 has been significantly recovered compared to the crystalline structure of the aged cathode material that has not been subjected to the repair treatment. It can also be seen from fig. 9 that the single crystal cathode material repaired in example 5 is reconstituted into a button half cell, the initial specific discharge capacity can reach 157mAh/g, and the specific discharge capacity is still higher than 140mAh/g after 70 cycles of 0.5C charge-discharge cycle, which indicates that the electrochemical performance of the repaired cathode material is improved.
From the above embodiments, the present invention provides a method for repairing and regenerating a waste lithium ion battery positive electrode material, which comprises the steps of performing ball milling treatment on a waste lithium ion battery aged positive electrode material to obtain a single-particle positive electrode material; mixing the single-particle positive electrode material with the lithium-rich salt mixture, and then performing primary sintering to obtain a lithium-supplementing single-particle positive electrode material; and finally, mixing the lithium-supplementing single-particle positive electrode material with a lithium compound, and then performing secondary sintering to obtain the repaired single-crystal positive electrode material. According to the invention, the multicomponent lithium-rich salt mixture and the aged positive electrode material are mixed, the lithium supplementing amount required for repairing the positive electrode material is not required to be accurately controlled, the purpose of melting and supplementing lithium can be realized at a lower temperature, and the operation is not required to be at high temperature and high pressure, so that the method is safer and has low energy consumption.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The repairing and regenerating method for the waste lithium ion battery anode material is characterized by comprising the following steps of:
(1) Performing ball milling treatment on the aged positive electrode material of the waste lithium ion battery to obtain a single-particle positive electrode material;
(2) Mixing the single-particle positive electrode material with the lithium-rich salt mixture, and then performing primary sintering to obtain a lithium-supplementing single-particle positive electrode material;
(3) And mixing the lithium-supplementing single-particle positive electrode material with a lithium compound, and then performing secondary sintering to obtain the repaired single-crystal positive electrode material.
2. The repair and regeneration method according to claim 1, wherein in the step (1), the ball-milling treatment has a ball-to-material ratio of 1 to 3:1, the rotating speed is 4000-6000 rpm, and the time is 3-15 min.
3. The repair regeneration method according to claim 1 or 2, wherein in the step (2), the lithium-rich salt mixture is a mixture of two or more of lithium chloride, potassium chloride, aluminum chloride and lithium carbonate; the molar ratio of the single-particle positive electrode material to the lithium-rich salt mixture is 1:3 to 5.
4. A repair regeneration method according to claim 3, wherein the lithium-rich salt mixture is lithium chloride and aluminum chloride, wherein the molar ratio of lithium chloride to aluminum chloride is 3:1 to 2.
5. The repair and regeneration method according to claim 1, 2 or 4, wherein in the step (2), the temperature of the primary sintering is 150 to 400 ℃ and the time is 2 to 6 hours.
6. The repair regeneration method according to claim 5, wherein in the step (3), a molar ratio of the lithium-supplemented single-particle positive electrode material to the lithium compound is 100:4 to 6.
7. The repair and regeneration method according to claim 2 or 6, wherein in the step (3), the lithium compound contains one or more of lithium chloride, lithium nitrate, lithium hydroxide and lithium carbonate.
8. The repair and regeneration method according to claim 7, wherein in the step (3), the secondary sintering is performed at 600 to 1000 ℃ for 6 to 10 hours.
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