CN116588995B - Echelon utilization method of waste ternary cathode material - Google Patents
Echelon utilization method of waste ternary cathode material Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000010406 cathode material Substances 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 189
- 238000005245 sintering Methods 0.000 claims abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 54
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 35
- 230000001502 supplementing effect Effects 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 16
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 36
- 239000000654 additive Substances 0.000 claims description 27
- 230000000996 additive effect Effects 0.000 claims description 23
- 239000012459 cleaning agent Substances 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000013589 supplement Substances 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 6
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 abstract description 23
- 239000013078 crystal Substances 0.000 description 59
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 238000004064 recycling Methods 0.000 description 12
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 8
- 229910001947 lithium oxide Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000306 component Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910012653 LiNi0.5Co0.2Mn0.3 Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- SXGDIBYXFSKCRM-UHFFFAOYSA-L dilithium hydrogen carbonate hydroxide Chemical compound [OH-].[Li+].C([O-])(O)=O.[Li+] SXGDIBYXFSKCRM-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- XWFDVMYCFYYTTG-UHFFFAOYSA-N lithium;nitrate;hydrate Chemical compound [Li+].O.[O-][N+]([O-])=O XWFDVMYCFYYTTG-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The application discloses a gradient utilization method of waste ternary positive electrode materials, which comprises the steps of treating waste ternary positive electrode plates to obtain ternary polycrystalline material powder; mixing ternary polycrystalline material powder with a lithium supplementing agent to obtain a material to be repaired, wherein the lithium supplementing agent comprises at least one of lithium hydroxide, lithium nitrate and lithium carbonate; sintering and crushing the material to be repaired to obtain the ternary monocrystalline material, and realizing gradient utilization of the waste ternary cathode material and forming a monocrystalline structure.
Description
Technical Field
The application relates to the technical field of new energy materials, in particular to a method for echelon utilization of waste ternary cathode materials.
Background
The positive electrode material is one of the core components of a lithium ion battery. Currently, in the field of positive electrode materials of lithium ion batteries, ternary positive electrode materials, lithium iron phosphate, lithium cobaltate, lithium manganate and the like are mainstream. The ternary positive electrode material is used in the field of positive electrode materials of lithium ion batteries and occupies a large area.
The metal lithium contained in the ternary positive electrode material may cause damage to ecological systems such as water, soil and the like. In addition, the metal lithium belongs to valuable metals, and the resources of the metal lithium in China are scarce. Therefore, the recycling of the ternary cathode material is of great importance.
Disclosure of Invention
In view of the technical problems, the application provides a waste ternary cathode material echelon utilization method for recycling waste ternary cathode materials to form a monocrystalline structure.
In a first aspect, the application provides a method for echelon utilization of waste ternary positive electrode materials, which comprises the steps of treating waste ternary positive electrode plates to obtain ternary polycrystalline material powder; mixing the ternary polycrystalline material powder with a lithium supplementing agent to obtain a material to be repaired, wherein the lithium supplementing agent comprises at least one of lithium hydroxide, lithium nitrate and lithium carbonate; and sintering and crushing the material to be repaired to obtain the ternary monocrystalline material.
According to the method for gradient utilization of the waste ternary cathode material, provided by the embodiment of the application, the ternary monocrystalline material is finally obtained through recovery of the ternary polycrystalline cathode material, lithium supplementing, sintering and crushing treatment, and gradient utilization (transformation of polycrystal into monocrystal) of the ternary material is realized. The ternary polycrystalline anode material is recycled, so that the production cost of the battery is reduced; the recycling method provided by the embodiment of the application not only can realize recycling through sintering and crushing, but also has simple process and more advantages in cost.
In one embodiment, the step of sintering and crushing the material to be repaired specifically includes: sintering the material to be repaired for a first preset time period at a first preset temperature; crushing the sintered material to be repaired to obtain the ternary monocrystalline material; wherein the first preset temperature is 870-1000 ℃; and/or the first preset time length is 6-12 h. The ternary material with single crystal morphology is formed through one-step sintering, the process is simple, and the cost is reduced.
In an embodiment, the step of sintering the material to be repaired for a first preset period of time specifically includes: sintering the material to be repaired for the first preset time period in an oxygen atmosphere. And sintering the material to be repaired for a first preset time under the oxygen atmosphere to degrade the lithium salt into lithium oxide for reaction.
In one embodiment, the step of sintering and crushing the material to be repaired specifically includes: sintering the material to be repaired for a second preset time period at a second preset temperature; sintering the material to be repaired again for a third preset time period at a third preset temperature; crushing the sintered material to be repaired to obtain the ternary monocrystalline material; wherein the second preset temperature is 300-500 ℃; and/or, the second preset time length is 3-5 h; and/or, the third preset temperature is 800-1000 ℃; and/or, the third preset time length is 5h-7h. Through twice sintering, the reaction is sufficient, and the ternary material with single crystal morphology is formed, so that the process is simple and the cost is reduced.
In an embodiment, the step of sintering the material to be repaired for a second preset period of time specifically includes: sintering the material to be repaired for the second preset time period in an oxygen atmosphere; and/or, the step of sintering the material to be repaired again for a third preset time length specifically includes: and sintering the material to be repaired again for the third preset time period in the oxygen atmosphere. And sintering the material to be repaired under the oxygen atmosphere to degrade the lithium salt into lithium oxide for reaction.
In an embodiment, the crushing the sintered material to be repaired specifically includes: and crushing the sintered material to be repaired by adopting airflow crushing. The ternary material with single crystal morphology formed by sintering can have a plurality of crystal grains with single crystal morphology adhered together, and the adhered crystal grains are separated by crushing to obtain dispersed primary crystal grains, so as to obtain the ternary single crystal material.
In one embodiment, the step of mixing the ternary polycrystalline material powder with a lithium supplement comprises, prior to: measuring the molar ratio of lithium element in the ternary polycrystalline material powder to nickel cobalt manganese element in the ternary polycrystalline material powder; and calculating the addition amount of the lithium supplementing agent based on the target molar ratio of the lithium element to the nickel cobalt manganese element so as to supplement lithium loss in the ternary polycrystalline material on the waste ternary positive electrode plate, so that the recycled ternary single crystal material can be used for preparing batteries.
In one embodiment, the ternary polycrystalline material comprises lithium nickel cobalt manganese oxide, and the ratio of the number of moles of the lithium element to the sum of the number of moles of the nickel, cobalt and manganese elements is 1.05:1-1.2:1 based on the sum of the number of moles of the nickel, cobalt and manganese elements in the lithium nickel cobalt manganese oxide to supplement lithium loss in the ternary polycrystalline material on the waste ternary positive electrode sheet.
In one embodiment, the mixing the ternary polycrystalline material powder with a lithium supplement further comprises: the ternary polycrystalline material powder is mixed with the lithium supplementing agent and the additive; wherein the additive comprises at least one element of zirconium, strontium and cadmium. The additive is added into the ternary polycrystalline material powder to promote the growth of crystal grains, the binding force among the crystal grains is weakened, and the morphology of single crystals is formed.
In one embodiment, the additive is added in an amount of 800ppm to 1200ppm to grow grains, and the binding force between the grains becomes weak, which is beneficial to the formation of the morphology of single crystals.
In one embodiment, the step of treating the waste ternary positive electrode sheet to obtain ternary polycrystalline material powder specifically includes: cleaning the waste ternary positive electrode plate to obtain a preform; and stripping and drying the preform to obtain the ternary polycrystalline material powder. And cleaning the waste ternary positive electrode plate, removing substances which are not required to be recycled on the waste ternary positive electrode plate, and reducing the influence on the performance of the battery by adopting the ternary material formed by recycling to prepare the battery.
In an embodiment, the step of cleaning the waste ternary positive electrode sheet to obtain a preform specifically includes: cleaning the waste ternary positive pole piece by using a first cleaning agent to remove electrolyte on the surface of the waste ternary positive pole piece, so as to obtain a precursor; immersing the precursor in a second cleaning agent to remove the binder, so as to obtain the preform; wherein the first cleaning agent comprises one or more of dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate; and/or the binder comprises polyvinylidene fluoride, and the second cleaning agent comprises N-methyl pyrrolidone so as to clean the electrolyte and the binder on the waste ternary positive electrode plate.
The foregoing description is only an overview of the present application, and is intended to be implemented in accordance with the teachings of the present application in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present application more readily apparent.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Also, like reference numerals are used to designate like parts throughout the accompanying drawings. In the drawings:
FIG. 1 is a schematic illustration of a vehicle according to some embodiments of the present application;
fig. 2 is a schematic view illustrating an exploded structure of a battery according to some embodiments of the present application;
fig. 3 is a schematic diagram illustrating an exploded structure of a battery cell according to some embodiments of the present application;
FIG. 4 is a schematic flow chart of a method for echelon utilization of waste ternary cathode material provided by the first embodiment of the application;
fig. 5 is a schematic flow chart of step S01 shown in fig. 4;
FIG. 6 is a scanning electron microscope image of the waste ternary cathode material provided by the embodiment of the application;
FIG. 7 is a scanning electron microscope image of ternary monocrystalline materials formed by echelon utilization of waste ternary cathode materials provided by the embodiment of the application.
Detailed Description
Embodiments of the technical scheme of the present application will be described in detail below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present application, and thus are merely examples, and are not intended to limit the scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having" and any variations thereof in the description of the application and the claims and the description of the drawings above are intended to cover a non-exclusive inclusion.
In the description of embodiments of the present application, the technical terms "first," "second," and the like are used merely to distinguish between different objects and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated, a particular order or a primary or secondary relationship. In the description of the embodiments of the present application, the meaning of "plurality" is two or more unless explicitly defined otherwise.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
In the description of the embodiments of the present application, the term "and/or" is merely an association relationship describing an association object, and indicates that three relationships may exist, for example, a and/or B may indicate: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
In the description of the embodiments of the present application, the term "plurality" means two or more (including two), and similarly, "plural sets" means two or more (including two), and "plural sheets" means two or more (including two).
The lithium ion battery has the advantages of high voltage, light weight, long cycle life, no memory effect, good safety and the like, and is widely applied. The lithium ion battery comprises a positive electrode, a negative electrode, a separation membrane, an electrolyte, a current collector and the like. The isolating film is used for isolating the adjacent positive electrode and the adjacent negative electrode so as to prevent the electrodes from shorting and causing the failure of the battery. In the field of positive electrode materials of lithium ion batteries, ternary positive electrode materials, lithium iron phosphate, lithium cobaltate, lithium manganate and the like are mainstream. The ternary positive electrode material is used in the field of positive electrode materials of lithium ion batteries and occupies a large area. The metal lithium contained in the ternary positive electrode material can cause damage to ecological systems such as water, soil and the like; the metal lithium belongs to valuable metals, and the resources of the metal lithium in China are scarce. Therefore, the recycling of the ternary cathode material is of great importance.
In order to solve the technical problems, the application provides a waste ternary cathode material echelon utilization method for recycling waste ternary cathode materials to form a monocrystalline structure.
The materials recovered by the non-old ternary positive electrode material echelon utilization method disclosed by the embodiment of the application can be applied to batteries, and the batteries disclosed by the embodiment of the application can be used for power utilization devices using the batteries as power sources or various energy storage systems using the batteries as energy storage elements. The power device may be, but is not limited to, a cell phone, tablet, notebook computer, electric toy, electric tool, battery car, electric car, ship, spacecraft, etc.
For convenience of description, the following embodiment will take an electric device according to an embodiment of the present application as an example of the vehicle 1000.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a vehicle 1000 according to some embodiments of the application. The vehicle 1000 may be a fuel oil vehicle, a gas vehicle or a new energy vehicle, and the new energy vehicle may be a pure electric vehicle, a hybrid vehicle or a range-extended vehicle. The battery 100 is provided in the interior of the vehicle 1000, and the battery 100 may be provided at the bottom or the head or the tail of the vehicle 1000. The battery 100 may be used for power supply of the vehicle 1000, for example, the battery 100 may be used as an operating power source of the vehicle 1000. The vehicle 1000 may also include a controller 200 and a motor 300, the controller 200 being configured to control the battery 100 to power the motor 300, for example, for operating power requirements during start-up, navigation, and travel of the vehicle 1000.
In some embodiments of the present application, battery 100 may not only serve as an operating power source for vehicle 1000, but may also serve as a driving power source for vehicle 1000, instead of or in part instead of fuel oil or natural gas, to provide driving power for vehicle 1000.
Referring to fig. 2, fig. 2 is an exploded view of a battery 100 according to some embodiments of the present application. The battery 100 includes a case 10 and a battery cell 20, and the battery cell 20 is accommodated in the case 10. The case 10 is used to provide an accommodating space for the battery cell 20, and the case 10 may have various structures. In some embodiments, the case 10 may include a first portion 11 and a second portion 12, the first portion 11 and the second portion 12 being overlapped with each other, the first portion 11 and the second portion 12 together defining an accommodating space for accommodating the battery cell 20. The second portion 12 may be a hollow structure with one end opened, the first portion 11 may be a plate-shaped structure, and the first portion 11 covers the opening side of the second portion 12, so that the first portion 11 and the second portion 12 together define a containing space; the first portion 11 and the second portion 12 may be hollow structures each having an opening at one side, and the opening side of the first portion 11 is engaged with the opening side of the second portion 12. Of course, the case 10 formed by the first portion 11 and the second portion 12 may be of various shapes, such as a cylinder, a rectangular parallelepiped, or the like.
In the battery 100, the plurality of battery cells 20 may be connected in series, parallel or a series-parallel connection, wherein the series-parallel connection refers to that the plurality of battery cells 20 are connected in series or parallel. The plurality of battery cells 20 can be directly connected in series or in parallel or in series-parallel, and then the whole formed by the plurality of battery cells 20 is accommodated in the box 10; of course, the battery 100 may also be a battery module formed by connecting a plurality of battery cells 20 in series or parallel or series-parallel connection, and a plurality of battery modules are then connected in series or parallel or series-parallel connection to form a whole and are accommodated in the case 10. The battery 100 may further include other structures, for example, the battery 100 may further include a bus member for making electrical connection between the plurality of battery cells 20.
Wherein each battery cell 20 may be a secondary battery or a primary battery; but not limited to, lithium sulfur batteries, sodium ion batteries, or magnesium ion batteries. The battery cell 20 may be in the shape of a cylinder, a flat body, a rectangular parallelepiped, or other shapes, etc.
The battery manufacturing mode comprises laminated type and winding type, namely, the battery is divided into laminated batteries and winding batteries. The laminated battery has uniform current collecting effect, smaller internal resistance and large specific power, but in order to ensure accuracy, the requirement on the accuracy of the die is extremely high, the equipment investment is high, the process is complex, and the production efficiency is low. The coiled battery is simple to manufacture, the requirements of the flaking and assembling processes on equipment precision are common, the production efficiency is high, and the cost is low. In terms of performance, the coiled battery has excellent high-low temperature performance, is very rapid to charge, has an ultra-long service life, is stable in high output voltage, and is firm in structure and strong in shock resistance.
Referring to fig. 3, fig. 3 is an exploded view of a battery cell 20 according to some embodiments of the present application. The battery cell 20 refers to the smallest unit constituting the battery. As shown in fig. 3, the battery cell 20 includes an end cap 21, a case 22, an electrode assembly 23, and other functional components.
The end cap 21 refers to a member that is covered at the opening of the case 22 to isolate the internal environment of the battery cell 20 from the external environment. Without limitation, the shape of the end cap 21 may be adapted to the shape of the housing 22 to fit the housing 22. Optionally, the end cover 21 may be made of a material (such as an aluminum alloy) with a certain hardness and strength, so that the end cover 21 is not easy to deform when being extruded and collided, so that the battery cell 20 can have higher structural strength, and the safety performance can be improved. The end cap 21 may be provided with a functional member such as an electrode terminal 21 a. The electrode terminal 21a may be used to be electrically connected with the electrode assembly 23 for outputting or inputting electric power of the battery cell 20. In some embodiments, the end cap 21 may also be provided with a pressure relief mechanism for relieving the internal pressure when the internal pressure or temperature of the battery cell 20 reaches a threshold. The material of the end cap 21 may be various, such as copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc., which is not particularly limited in the embodiment of the present application. In some embodiments, insulation may also be provided on the inside of the end cap 21, which may be used to isolate electrical connection components within the housing 22 from the end cap 21 to reduce the risk of short circuits. By way of example, the insulation may be plastic, rubber, or the like.
The case 22 is an assembly for cooperating with the end cap 21 to form an internal environment of the battery cell 20, wherein the formed internal environment may be used to accommodate the electrode assembly 23, the electrolyte, and other components. The case 22 and the end cap 21 may be separate members, and an opening may be provided in the case 22, and the interior of the battery cell 20 may be formed by covering the opening with the end cap 21 at the opening. It is also possible to integrate the end cap 21 and the housing 22, but specifically, the end cap 21 and the housing 22 may form a common connection surface before other components are put into the housing, and when it is necessary to encapsulate the inside of the housing 22, the end cap 21 is then put into place with the housing 22. The housing 22 may be of various shapes and sizes, such as rectangular parallelepiped, cylindrical, hexagonal prism, etc. Specifically, the shape of the case 22 may be determined according to the specific shape and size of the electrode assembly 23. The material of the housing 22 may be various, such as copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc., which is not particularly limited in the embodiment of the present application.
The electrode assembly 23 is a component in which electrochemical reactions occur in the battery cell 100. One or more electrode assemblies 23 may be contained within the housing 22. The electrode assembly 23 is mainly formed by winding or stacking a positive electrode sheet and a negative electrode sheet, and a separator is generally provided between the positive electrode sheet and the negative electrode sheet. The portions of the positive electrode sheet and the negative electrode sheet having the active material constitute the main body portion of the electrode assembly, and the portions of the positive electrode sheet and the negative electrode sheet having no active material constitute the tab 23a, respectively. The positive electrode tab and the negative electrode tab may be located at one end of the main body portion together or located at two ends of the main body portion respectively. During charge and discharge of the battery, the positive electrode active material and the negative electrode active material react with the electrolyte, and the tab 23a is connected to the electrode terminal to form a current loop.
Referring to fig. 4 and 5, fig. 4 is a schematic flow chart of a method for gradient utilization of waste ternary cathode material according to the first embodiment of the present application, fig. 5 is a schematic flow chart of step S01 shown in fig. 4, fig. 6 is a scanning electron microscope image of waste ternary cathode material according to the embodiment of the present application, and fig. 7 is a scanning electron microscope image of ternary monocrystalline material formed by gradient utilization of waste ternary cathode material according to the embodiment of the present application.
The method for echelon utilization of the waste ternary cathode material provided by the embodiment of the application specifically comprises the following steps:
step S01: and (3) processing the waste ternary positive electrode plate to obtain ternary polycrystalline material powder.
The ternary material of the waste ternary positive pole piece is a polycrystalline material generally, and the application voltage is lower, so that the recycled positive pole material has a better structure and a gradient utilization basis; for example, the ternary material of the waste ternary positive electrode plate comprises N 5 C 2 M 3 （LiNi 0.5 Co 0.2 Mn 0.3 0 2 ）、N 6 C 2 M 2 （LiNi 0.6 Co 0.2 Mn 0.2 0 2 ）、N 7 C 1 M 2 （LiNi 0.7 Co 0.1 Mn 0.2 0 2 ) At least one of them.
And processing the waste ternary positive electrode plate into a powder state so as to recycle the ternary positive electrode plate material. In an embodiment, the waste ternary positive electrode sheet may be a ternary positive electrode sheet in a battery with a lifetime decay to 80% soh (state of health, which may be understood as a percentage of the current capacity of the battery to the factory capacity). In one embodiment, the spent ternary positive electrode sheet may be a ternary positive electrode sheet in a battery with a lifetime decay to 70% soh. In one embodiment, the waste ternary positive electrode sheet may be a ternary positive electrode sheet in a battery that is not used for a long time; the waste ternary positive electrode sheet may be a ternary positive electrode sheet in a battery that is not used for half a year, for example.
The step of processing the waste ternary positive electrode plate into a powder state specifically comprises the following steps:
step S011: and cleaning the waste ternary positive electrode plate to obtain a preform.
And cleaning the waste ternary positive electrode plate, removing substances which are not required to be recycled on the waste ternary positive electrode plate, and reducing the influence on the performance of the battery by adopting the ternary material formed by recycling to prepare the battery.
In one embodiment, cleaning the waste ternary positive electrode piece by using a first cleaning agent to remove electrolyte on the surface of the waste ternary positive electrode piece to obtain a precursor; and immersing the precursor in a second cleaning agent to remove the binder, thus obtaining the preform. It should be noted that, the sequence of the cleaning of the electrolyte, the binder, and the like of the waste ternary positive electrode sheet in the embodiment of the application is not limited to the above embodiment, for example, the waste ternary positive electrode sheet is soaked in the first cleaning agent and the second cleaning agent at the same time, and the electrolyte and the binder are cleaned at the same time.
Optionally, the first cleaning agent comprises one or more of dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate. The first cleaning agent can dissolve the electrolyte components on the surface of the waste ternary positive electrode plate, and the first cleaning agent can remove the electrolyte on the surface of the waste ternary positive electrode plate.
Optionally, the binder comprises polyvinylidene fluoride (PVDF) and the second cleaning agent comprises N-methylpyrrolidone (NMP). The second cleaning agent comprises, but is not limited to, polyvinylidene fluoride, and the second cleaning agent can remove the adhesive on the waste ternary positive electrode plate. The conductive agent on the waste ternary positive electrode sheet is usually carbon black, and the carbon black is removed by oxidation in the sintering process in the step S03, so that a cleaning agent is not required to clean the conductive agent in the step.
Step S012: and stripping and drying the preform to obtain ternary polycrystalline material powder.
And stripping the ternary material on the cleaned waste ternary positive electrode plate to obtain a powdery ternary material so as to facilitate the further treatment of the ternary material, thereby realizing recycling. It should be noted that, the ternary material on the waste ternary positive electrode plate in the waste battery has undergone irreversible phase change in structure, lithium-nickel mixed discharge and lithium loss occur, and the ternary material is stripped off to obtain the ternary polycrystalline material.
In one embodiment, the preform includes a current collector and a ternary material disposed on a surface of the current collector, the ternary material is peeled off from the current collector and dried to evaporate the second cleaning agent, and the dried ternary material is ground into powder to obtain ternary polycrystalline material powder. Optionally, drying at 100deg.C for 12 hr. The temperature and the duration of the drying are designed according to the requirements, and the second cleaning agent can be evaporated.
Step S02: and mixing the ternary polycrystalline material powder with a lithium supplementing agent to obtain the material to be repaired, wherein the lithium supplementing agent comprises at least one of lithium hydroxide, lithium nitrate and lithium carbonate.
In one embodiment, ternary polycrystalline material powder is mixed with a lithium supplement. And mixing the ternary polycrystalline material powder with a lithium supplementing agent to supplement lithium loss in the ternary polycrystalline material on the waste ternary positive electrode plate, so that the recycled ternary material can be used for preparing batteries. At least one of lithium hydroxide, lithium nitrate and lithium carbonate is selected as a lithium supplementing agent, so that the lithium is supplemented, the content of other elements in the ternary material is not higher, and the performance of a battery made of the recovered ternary material is not reduced. It should be noted that, with respect to lithium hydroxide hydrate, lithium nitrate hydrate, and lithium carbonate hydrate, at least one of lithium hydroxide, lithium nitrate, and lithium carbonate is used as the lithium supplementing agent, the amount of water introduced during the addition of the lithium supplementing agent can be reduced.
The addition amount of the lithium supplementing agent is calculated according to the molar ratio of the lithium element in the ternary polycrystalline material powder to the nickel cobalt manganese element in the ternary polycrystalline material powder and the target molar ratio of the lithium element to the nickel cobalt manganese element. It is understood that the step S02 of mixing the ternary polycrystalline material powder with the lithium supplementing agent may further include calculating the addition amount of the lithium supplementing agent.
The specific calculation mode of the addition amount of the lithium supplementing agent is as follows: measuring the molar ratio of the lithium element in the ternary polycrystalline material powder to the nickel cobalt manganese element in the ternary polycrystalline material powder; the addition amount of the lithium supplementing agent is calculated based on the target molar ratio of the lithium element to the nickel cobalt manganese element.
Alternatively, the ternary polycrystalline material comprises lithium nickel cobalt manganese oxide. And measuring by ICP (elemental analysis) to obtain the molar ratio of the lithium element in the ternary polycrystalline material powder to the nickel cobalt manganese element in the ternary polycrystalline material powder.
Alternatively, the ratio of the number of moles of lithium element to the sum of the number of moles of nickel, cobalt and manganese element (Li/Me) is 1.05:1 to 1.2:1 based on the sum of the number of moles of nickel, cobalt and manganese element in the lithium nickel cobalt manganese oxide. That is, the target molar ratio of lithium element to nickel cobalt manganese element is 1.05:1-1.2:1. Since lithium salts are decomposed during sintering to cause lithium loss, the addition amount of lithium elements is required to be larger than the addition amounts of nickel, cobalt and manganese elements. Meanwhile, the higher the addition amount of the lithium element is, the more favorable the primary particle development is, but the higher the addition amount of the lithium element is, the larger the primary particle development is, so that the lithium ion transmission path is prolonged, and the capacity is reduced. The target molar ratio of the lithium element to the nickel cobalt manganese element is designed to be 1.05:1-1.2:1, so that lithium loss is supplemented, primary particle development is promoted, the size of primary particles accords with the expectation, and the capacity of a battery formed after echelon utilization is higher. Illustratively, the target molar ratio of lithium element to nickel cobalt manganese element is 1.2:1; illustratively, the target molar ratio of lithium element to nickel cobalt manganese element is 1.12:1; illustratively, the target molar ratio of lithium element to nickel cobalt manganese element is 1.05:1.
In one embodiment, the ternary polycrystalline material powder is added with additives in addition to the lithium supplement, that is, the ternary polycrystalline material powder is mixed with the lithium supplement and additives. Wherein the additive comprises at least one element of zirconium (Zr), strontium (Sr) and cadmium (Cd). The lithium supplementing agent is added into the ternary polycrystalline material powder to supplement lithium loss in the ternary polycrystalline material on the waste ternary positive electrode plate. The recycled ternary polycrystalline material has smaller grains, stronger bonding force among small grains, larger grain length and weaker bonding force among grains, and is beneficial to forming the morphology of single crystals. The addition of additives to the ternary polycrystalline material powder is to promote grain growth to enable the formation of a single crystalline ternary material; meanwhile, by adding the additive, the material to be repaired can be sintered at a lower temperature to obtain a ternary material with single crystal morphology when the step S03 is carried out, namely, the sintering temperature is reduced. Illustratively, adding zirconium to the ternary polycrystalline material powder may form a stable oxide with oxygen, thereby reducing the amount of oxide in the ternary material and thereby promoting grain growth. Illustratively, adding strontium and cadmium to the ternary polycrystalline material powder, which have a high diffusivity, can form compounds at the grain boundaries, thereby promoting grain growth.
Optionally, the additive is added in an amount of 800ppm to 1200ppm. Illustratively, the additive is added in an amount of 1000ppm; illustratively, the additive is added in an amount of 1200ppm; the additive is added in an amount of 800ppm, for example. The additive amount is calculated from the amount of the ternary polycrystalline powder, and ppm indicates that 1kg of the ternary polycrystalline powder needs to be added with 1mg of the additive (for example, at least one element of zirconium, strontium, and cadmium), and the additive amount (mg) =additive amount (ppm) ×the weight (kg) of the ternary polycrystalline powder. The addition amount is less than 800ppm, which is unfavorable for the growth of crystal grains to a single crystal level, and the addition amount is more than 1200ppm, which may cause the development of primary particles to be excessively large, so that the lithium ion transmission path is lengthened, and the capacity is reduced.
Step S03: sintering and crushing the material to be repaired to obtain the ternary monocrystalline material.
Sintering the material to be repaired in the oxygen atmosphere promotes the growth of crystal grains, so that the binding force among the crystal grains is weakened, the morphology of single crystals is formed, and the ternary single crystal material is obtained. It can be appreciated that the higher temperature can effectively increase the rate of ion migration, thereby promoting the growth of grains, and thus, the growth of the grains can be promoted by sintering, which is beneficial to forming the ternary material with single crystal morphology.
In one embodiment, sintering the material to be repaired at a first preset temperature for a first preset period of time; crushing the sintered material to be repaired to obtain ternary monocrystal material, wherein the primary crystal grain size is 1-5 microns and the average size is about 3 microns. And at the moment, the grains of the ternary material similar to the single crystal morphology are separated by crushing, so that dispersed primary grains are obtained, and the ternary single crystal material is obtained. Wherein, the monocrystalline-like morphology refers to a morphology between polycrystalline morphology and monocrystalline morphology. Regarding the quasi-single crystal, whether it is polycrystalline in nature or essentially, a single crystal that is geometrically perfect is a crystal having the same spatial lattice of crystal structures, and a crystal grown from one grain is sometimes referred to physically as a single crystal; in summary, the most basic condition of single crystals is that no grain boundaries exist inside them, which are one grain. Since single crystals are far superior to polycrystal in some aspects such as electrical properties, thermal properties, magnetic properties, grain boundaries are an important part of the suppression or attenuation properties, attempts have been made to increase the grain size in crystal growth, decrease the number of grains, and the ultimate goal is to be single crystals, which are called larger crystal sizes when single crystals in the positive sense are not achieved, and crystals with a small number of grains are quasi-single crystals to highlight the improvement of their properties.
Optionally, sintering the material to be repaired for a first preset time period in an oxygen atmosphere. Sintering under an oxygen atmosphere is to react the lithium salt (e.g., lithium hydroxide) to lithium oxide.
Optionally, the first preset temperature is 870 ℃ to 1000 ℃. The sintering temperature is higher than 950 ℃, and the primary particle size of the crystal grains is obviously increased. When the sintering temperature is higher than 1000 ℃, the primary grain growth is too large, and the capacity is reduced.
Optionally, the first preset time is 6-12 hours, so that the reaction is sufficient, and the material to be repaired forms a single crystal morphology.
Illustratively, in step S02, only the lithium supplement agent is added, and no additive is added, to the ternary polycrystalline material, and the ternary material having a single crystal morphology is obtained by sintering at a first preset temperature for a first preset period of time.
In one embodiment, sintering the material to be repaired at a second preset temperature for a second preset period of time; sintering the material to be repaired again for a third preset time period at a third preset temperature; and crushing the sintered material to be repaired to obtain a ternary monocrystalline material, wherein the size of primary grains is 1-5 mu m, and the average size is about 3 mu m. And sintering the material to be repaired twice, wherein part of the material forms a ternary material with a monocrystal appearance, and part of the material forms a ternary material with a monocrystal-like appearance (the definition of the monocrystal-like appearance can be referred to in the related description), and at the moment, the ternary material with the monocrystal-like appearance is separated by crushing to obtain dispersed primary grains, so that the ternary monocrystal material is obtained. Wherein the sintering at the second preset temperature for the second preset time period is to change the lithium supplementing agent (e.g., lithium hydroxide) into lithium oxide (lithium element exists as lithium oxide in the ternary material); sintering at a third preset temperature for a third preset time period to promote the growth of crystal grains so as to form a ternary material with single crystal morphology.
Optionally, sintering the material to be repaired for a second preset time period in an oxygen atmosphere, and/or sintering the material to be repaired again for a third preset time period in the oxygen atmosphere. Sintering under an oxygen atmosphere is to degrade a lithium supplementing agent (e.g., lithium hydroxide) into lithium oxide for reaction.
Optionally, the second preset temperature is 300-500 ℃; and/or, the second preset time length is 3-5 h. Determining a second preset temperature according to the degradation temperature of the lithium salt, wherein the second preset temperature is 300-500 ℃, so that the lithium supplementing agent can be degraded into lithium oxide; the second preset time period is designed to be 3-5 hours so that the lithium supplementing agent is fully degraded into lithium oxide.
Optionally, the third preset temperature is 800-1000 ℃; and/or, the third preset time length is 5h-7h. The third preset temperature is higher than 800 ℃ and can promote the development of primary particles, and the third preset temperature is higher than 1000 ℃ and can cause the primary particles to develop too much, so that the lithium ion transmission path is lengthened and the capacity is reduced. The third preset time length is designed to be 5-7 h, so that the reaction is sufficient, and the material to be repaired is promoted to form a single crystal morphology.
The material to be repaired after sintering is crushed, and the material to be repaired needs to be crushed after being cooled to room temperature. Optionally, the sintered material to be repaired is crushed by adopting airflow crushing. The air flow crusher has crushing time of 20-30 min, fluidized bed pressure of 0.5-1 MPa and frequency of 15-25 Hz.
According to the method for gradient utilization of the waste ternary cathode material, provided by the embodiment of the application, the primary grain development is promoted by recovering the ternary polycrystalline cathode material, supplementing lithium and then sintering, the primary grain development is further promoted by doping the additive in the process, and finally the ternary monocrystalline material is obtained by crushing treatment, so that gradient utilization (transformation of polycrystal into monocrystal) of the ternary material is realized. The ternary polycrystalline anode material is recycled, so that the production cost of the battery is reduced; the recycling method provided by the embodiment of the application not only can realize recycling through sintering, but also has simple process and more advantages in cost.
It should be noted that the waste ternary cathode material has undergone irreversible phase change in structure and lithium loss. Most of the waste ternary positive electrode materials are polycrystalline, if the waste ternary positive electrode materials are recovered or the ternary polycrystalline materials are obtained, the phase change which is generated cannot be completely reversed, the original lithium nickel mixed discharge can be improved, or the structural deterioration caused by the phase change which is caused by the lithium nickel mixed discharge cannot be improved, so that the performance deterioration is caused, the performance deterioration is reflected in low capacity, and the polycrystalline materials generate cracks and are deteriorated in circulation in the circulation process.
The ternary monocrystalline material recovered by the embodiment of the application can improve the defects. In addition, as the monocrystal material has no crystal boundary, the structural deterioration caused by the expansion and contraction of crystals in the charge and discharge process can be relieved, and even if the material structure cannot be completely recovered, the risk of the structural deterioration of the material can be effectively reduced in application. The single crystal material is composed of only one crystal lattice, and the single crystal material has no crystal boundary, and can not generate cracks even if the crystal continuously contracts and expands in the charging and discharging process, so that the cycle deterioration can be improved in the application process. The battery made of the recovered ternary monocrystal material has the advantages of easier lithium ion extraction and intercalation and longer cycle life. Because the single crystal material has better structural stability, the battery made of the recovered ternary single crystal material can be applied to higher voltage, more lithium ions can be extracted, and the capacity is high, so that the problem of low capacity of the material after recycling can be solved.
The embodiment of the application also provides a preparation method of the battery, which specifically comprises the following steps:
(1) And (3) preparing a positive electrode plate.
Mixing the positive electrode active material-ternary material with conductive carbon black and a binder PVDF according to a mass ratio of 96.7:1.7:1.6, adding a proper amount of solvent NMP, and obtaining positive electrode slurry under the action of a vacuum stirrer; uniformly coating the anode slurry on two surfaces of an anode current collector aluminum foil; and then carrying out vacuum drying at 70 ℃ for 12 hours, and obtaining the positive electrode plate after slitting and cutting. The ternary material can be ternary monocrystalline material obtained by adopting the waste ternary positive electrode material echelon utilization method provided by the embodiment of the application.
(2) And (3) preparing a negative electrode plate.
Uniformly mixing artificial graphite, conductive agent carbon black, binder carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR) and solvent water according to the weight ratio of 93:2:2:3:100 to form negative electrode slurry; uniformly coating the negative electrode slurry on two surfaces of a negative electrode current collector copper foil; drying at 110 ℃, and obtaining the negative electrode plate after cold pressing treatment.
(3) And (3) preparing an electrolyte.
Mixing Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) according to a volume ratio of 1:1:1 to obtain an organic solvent; dissolving LiPF6 in the organic solvent, adding fluoroethylene carbonate (FEC), and uniformly mixing to obtain electrolyte; wherein the concentration of LiPF6 is 1mol/L.
(4) And (3) preparation of a separation film.
A PE porous film was used as a separator.
(5) And (3) preparing a lithium ion battery.
Sequentially stacking the positive electrode plate, the isolating film and the negative electrode plate, enabling the isolating film to be positioned in the middle of the positive electrode and the negative electrode to play a role of isolation, and winding to obtain an electrode assembly; and placing the electrode assembly in an outer package, injecting the prepared electrolyte, packaging, and carrying out technological processes such as formation, degassing, trimming and the like to obtain the lithium ion battery.
The advantageous effects of the present application are further illustrated below with reference to examples.
In order to make the technical problems, technical schemes and beneficial effects solved by the embodiments of the present application more clear, the following will be described in further detail with reference to the embodiments and the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the application, its application, or uses. All other embodiments, which can be made by a person skilled in the art based on the embodiments of the application without any inventive effort, are intended to fall within the scope of the application.
Example 1:
Discharging the battery to 0% SOC (State of charge) which is used for reflecting the residual capacity of the battery, wherein the value is defined as the ratio of the residual capacity to the battery capacity, the residual capacity of the current State of the battery can be known through an SOC value, the battery is completely discharged when SOC=0, and the battery is completely full when SOC=100%, disassembling to obtain a positive electrode plate, cleaning the positive electrode plate with dimethyl carbonate for 3 times to remove the electrolyte of the positive electrode plate, immersing the positive electrode plate in NMP to remove the surface PVDF, stripping the positive electrode active material (ternary material) from the positive electrode plate, and drying the positive electrode plate in an oven at 100 ℃ for 12 hours. And grinding the dried positive electrode active material into powder, and then sending the powder to an ICP (inductively coupled plasma) to obtain the molar ratio (namely Li/Me) of the lithium element in the ternary polycrystalline material powder to the nickel cobalt manganese element in the ternary polycrystalline material powder. Li/Me was increased to 1.2 by addition of LiOH, while 0ppm of additive was added. And (3) placing the positive electrode material, the LiOH and the additive into a ball milling tank, uniformly mixing, and calcining for 9 hours at the temperature of 935 ℃ under the oxygen atmosphere. After cooling to room temperature, a single crystal material was obtained by air flow breaking, and a battery was prepared by the preparation method of a battery provided in the above examples using the single crystal material, and its capacity and cycle performance were tested.
Examples 2-24 monocrystalline materials were obtained in a similar manner to example 1, the specific target compositions of examples 2-24 being detailed in table 1.
Example 25:
discharging the battery to 0% SOC (State of charge) which is used for reflecting the residual capacity of the battery, wherein the value is defined as the ratio of the residual capacity to the battery capacity, the residual capacity of the current State of the battery can be known through an SOC value, the battery is completely discharged when SOC=0, and the battery is completely full when SOC=100%, disassembling to obtain a positive electrode plate, cleaning the positive electrode plate with dimethyl carbonate for 3 times to remove the electrolyte of the positive electrode plate, immersing the positive electrode plate in NMP to remove the surface PVDF, stripping the positive electrode active material (ternary material) from the positive electrode plate, and drying the positive electrode plate in an oven at 100 ℃ for 12 hours. And grinding the dried positive electrode active material into powder, and then sending the powder to an ICP (inductively coupled plasma) to obtain the molar ratio (namely Li/Me) of the lithium element in the ternary polycrystalline material powder to the nickel cobalt manganese element in the ternary polycrystalline material powder. Li/Me was increased to 1.12 by addition of LiOH, while 1000ppm of additive Zr was added. And (3) placing the anode material, the LiOH and the additive into a ball milling tank, uniformly mixing, calcining for 4 hours at 400 ℃ and calcining for 6 hours at 900 ℃ under an oxygen atmosphere. After cooling to room temperature, a single crystal material was obtained by air flow breaking, and a battery was prepared by the preparation method of a battery provided in the above examples using the single crystal material, and its capacity and cycle performance were tested.
Examples 26-27 monocrystalline materials were obtained in a similar manner to example 25, the specific target compositions of examples 26-27 being detailed in table 2.
The related parameter testing method in the above embodiment is specifically as follows:
1) And (5) capacity test.
Standing the battery at 25deg.C for 30min, discharging to 2.5V at 0.33C, and standing at 25deg.C for 30min; constant-current charging to 3.65V at 0.33C, constant-voltage charging, and cutoff current at 0.05C; standing at 25deg.C for 30min, discharging to 2.5V at 0.33C, standing at 25deg.C for 30min, and recording the charge and discharge capacity of the Nth cycle.
2) And (5) cyclic testing.
Step 1, the battery is kept stand at 25 ℃ for 30min,0.33C is discharged to 2.5V, and the battery is kept stand at 25 ℃ for 30min.
And 2, carrying out constant-current charging to 3.65V at 0.33C, carrying out constant-voltage charging, carrying out off-current 0.05C, standing for 30min at 25 ℃, carrying out discharging to 2.5V at 0.33C, and standing for 30min at 25 ℃. The cycle of step 2 was repeated 1000 times, and the cycle capacity retention rate after 1000 cycles of the battery was recorded.
The capacity retention CR (%) =discharge capacity of the nth cycle/discharge capacity of the 1 st cycle×100% after the battery cycle n times.
TABLE 1 parameters and Properties for echelon utilization of examples 1-24
TABLE 2 parameters and Properties for echelon utilization of examples 25-27
According to the experimental results of examples 1-27, the battery prepared by echelon utilization of the ternary single crystal material provided by the embodiment of the application has the capacity of more than 177 and the cycle of more than 88 percent, and has good application prospect. As can be seen from the comparison of examples 2 with examples 4 to 6, examples 15 to 19 and examples 21 to 24, the cycle performance can be improved by adding additives. As is evident from comparative examples 1 to 3, the larger Li/Me is, the better the cycle performance is. As can be seen from comparative examples 6 to 8, the higher the first preset temperature and the longer the first preset time for sintering, the better the cycle performance. As can be seen from comparative examples 25 to 27, the higher the second preset temperature, the longer the second preset time, the higher the third preset temperature, and the longer the third preset time of sintering are, which is advantageous for improving the cycle performance.
The foregoing description is only of embodiments of the present application, and is not intended to limit the scope of the application, and all equivalent structures or equivalent processes using the descriptions and the drawings of the present application or directly or indirectly applied to other related technical fields are included in the scope of the present application.
Claims (7)
1. A method for gradient utilization of waste ternary cathode materials is characterized by comprising the following steps:
Treating the waste ternary positive electrode plate to obtain ternary polycrystalline material powder, wherein the ternary polycrystalline material comprises lithium nickel cobalt manganese oxide;
mixing the ternary polycrystalline material powder with a lithium supplementing agent to obtain a material to be repaired, wherein the lithium supplementing agent comprises at least one of lithium hydroxide, lithium nitrate and lithium carbonate;
sintering the material to be repaired, and carrying out airflow crushing on the sintered material to be repaired to obtain a ternary monocrystalline material;
wherein, before the step of mixing the ternary polycrystalline material powder with a lithium supplementing agent, the method comprises the following steps:
measuring the molar ratio of lithium element in the ternary polycrystalline material powder to nickel cobalt manganese element in the ternary polycrystalline material powder;
calculating the addition amount of the lithium supplementing agent based on the target molar ratio of the lithium element to the nickel cobalt manganese element; based on the sum of the mole numbers of nickel, cobalt and manganese elements in the lithium nickel cobalt manganese oxide, the ratio of the mole numbers of the lithium element to the sum of the mole numbers of the nickel, cobalt and manganese elements is 1.05:1-1.2:1;
the mixing of the ternary polycrystalline material powder with a lithium supplement further comprises:
the ternary polycrystalline material powder is mixed with the lithium supplementing agent and the additive; wherein the additive comprises at least one element of zirconium, strontium and cadmium; the addition amount of the additive is 800ppm-1200ppm.
2. The method according to claim 1, wherein the step of sintering the material to be repaired comprises:
sintering the material to be repaired for a first preset time period at a first preset temperature;
wherein the first preset temperature is 870-1000 ℃; and/or the first preset time length is 6-12 h.
3. The method according to claim 2, wherein the step of sintering the material to be repaired for a first preset period of time specifically comprises: sintering the material to be repaired for the first preset time period in an oxygen atmosphere.
4. The method according to claim 1, wherein the step of sintering the material to be repaired comprises:
sintering the material to be repaired for a second preset time period at a second preset temperature;
sintering the material to be repaired again for a third preset time period at a third preset temperature;
wherein the second preset temperature is 300-500 ℃; and/or, the second preset time length is 3-5 h; and/or, the third preset temperature is 800-1000 ℃; and/or, the third preset time length is 5h-7h.
5. The method of claim 4, wherein the step of sintering the material to be repaired for a second predetermined period of time comprises: sintering the material to be repaired for the second preset time period in an oxygen atmosphere;
And/or, the step of sintering the material to be repaired again for a third preset time length specifically includes: and sintering the material to be repaired again for the third preset time period in the oxygen atmosphere.
6. The method of claim 1, wherein the step of processing the waste ternary positive electrode sheet to obtain ternary polycrystalline material powder comprises:
cleaning the waste ternary positive electrode plate to obtain a preform;
and stripping and drying the preform to obtain the ternary polycrystalline material powder.
7. The method of claim 6, wherein the step of cleaning the waste ternary positive electrode sheet to obtain a preform specifically comprises:
cleaning the waste ternary positive pole piece by using a first cleaning agent to remove electrolyte on the surface of the waste ternary positive pole piece, so as to obtain a precursor;
immersing the precursor in a second cleaning agent to remove the binder, so as to obtain the preform;
wherein the first cleaning agent comprises one or more of dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate; and/or the binder comprises polyvinylidene fluoride, and the second cleaning agent comprises N-methyl pyrrolidone.
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