CN111129487A - Hydrothermal lithium supplement-spray remodeling regeneration method for waste ternary cathode material - Google Patents
Hydrothermal lithium supplement-spray remodeling regeneration method for waste ternary cathode material Download PDFInfo
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- CN111129487A CN111129487A CN202010005820.5A CN202010005820A CN111129487A CN 111129487 A CN111129487 A CN 111129487A CN 202010005820 A CN202010005820 A CN 202010005820A CN 111129487 A CN111129487 A CN 111129487A
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- cathode material
- ternary cathode
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 68
- 239000002699 waste material Substances 0.000 title claims abstract description 54
- 239000010406 cathode material Substances 0.000 title claims abstract description 46
- 239000007921 spray Substances 0.000 title claims abstract description 41
- 238000007634 remodeling Methods 0.000 title claims abstract description 22
- 238000011069 regeneration method Methods 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010405 anode material Substances 0.000 claims abstract description 32
- 239000011572 manganese Substances 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000011888 foil Substances 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 239000013589 supplement Substances 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 238000005469 granulation Methods 0.000 claims abstract description 8
- 230000003179 granulation Effects 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 35
- 239000007774 positive electrode material Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 8
- 238000007599 discharging Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- 229910003002 lithium salt Inorganic materials 0.000 abstract 1
- 159000000002 lithium salts Chemical class 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910021311 NaFeO2 Inorganic materials 0.000 description 1
- 229910003618 NixCoyMn1-x-y(OH)2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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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Abstract
The invention discloses a hydrothermal lithium supplement-spray remodeling regeneration method of a waste ternary cathode material, which comprises the steps of deeply discharging, disassembling and separating a waste ternary lithium battery; placing the anode aluminum foil in a sodium hydroxide solution, drying, calcining and grinding the stripped anode material of the waste ternary lithium battery to obtain powder; adding the powder into organic acid for surface activation, adding a lithium salt solution for hydrothermal treatment, and then mixing and batching the powder serving as seed crystal with a nickel source, a manganese source and a cobalt source to obtain a suspension with uniform components; spraying, granulating and remolding the suspension to obtain an NCM precursor, and sintering the NCM precursor with oxygen in two stages to obtain a regenerated ternary cathode material; the method realizes environment-friendly short-process recycling of the waste ternary cathode material, wherein the hydrothermal lithium supplement process can quickly realize in-situ repair of lithium, the ternary cathode waste after lithium supplement is used as a crystal seed, and the structure remodeling and controllable preparation of the ternary cathode material can be realized by combining a spray granulation technology.
Description
Technical Field
The invention belongs to the technical field of secondary resource recycling and circular economy, relates to a recycling and regenerating method of a waste ternary cathode material, and particularly relates to a hydrothermal lithium supplement-spray remodeling regenerating method of the waste ternary cathode material.
Background
Since the commercialization of lithium ion batteries has been completed in the end of the 20 th century, lithium ion batteries have been widely used in portable electronic devices such as mobile phones, notebook computers, and cameras, and electric vehicles, because of their advantages such as high mass density, light weight, long life, and no memory. From the application field of domestic lithium batteries, the rapid development of industries such as power, energy storage and 3C becomes the main driving force for driving the development of the lithium ion battery industry, and the demand acceleration of the lithium batteries in the power and energy storage fields is accelerated continuously. According to the analysis and prediction of a prospective industrial research institute, the new energy automobile sales volume in China is expected to exceed 300 million by 2022 years. The reports of the power battery recycling industry (2018) predict that cumulative retired power batteries will exceed 23 million tons (21 GWH) in 2020, and the retirement scale of ternary batteries will be equal to and gradually surpass that of lithium iron phosphate batteries in 2022. The ternary lithium ion battery anode material contains various valuable metals (cobalt, nickel, manganese, lithium and the like) and has high recovery value, so that a comprehensive ternary lithium ion battery recovery technology needs to be researched. The waste ternary anode material lithium ion battery generally contains 5-20% of cobalt, 5-10% of nickel, 5-7% of lithium, 15% of organic solvent and 7% of plastic. If it can be recycled, it can not only reduce the pollution to the environment but also produce great economic benefits.
At present, the method for regenerating and recycling the anode of the waste lithium ion battery mainly comprises the following steps: solid phase method, precipitation separation method, coprecipitation method. The solid phase method is characterized in that a certain amount of lithium source is added into the waste anode material, and then high-temperature calcination is carried out in an oxidizing atmosphere, so as to finally regenerate the ternary anode material. The precipitation separation method is to separate waste LiNixCoyMn1-x-yO2Dissolving the positive electrode material with inorganic acid or organic acid to obtain Li+、Ni2+、Co2+And Mn2+Adding relevant precipitant into the solution to selectively precipitate the ions, and recovering the ions respectively. The coprecipitation method is to mix waste LiNixCoyMn1-x-yO2Dissolving the positive electrode material with inorganic acid or organic acid, adding coprecipitator, and precipitating the ions at the same rate to obtain (Ni)xCoyMn1-x-y)CO3Or NixCoyMn1-x-y(OH)2And then lithium is supplemented and the ternary cathode material is obtained by high-temperature sintering. In conclusion, the product recovered by the precipitation separation method has high purity, but the process flow is relatively complex, the control parameters are more, various harmful gases are generated, and secondary pollution is caused; the coprecipitation method has long process for recycling and preparing the ternary cathode material, and easily generates more waste liquid, so the treatment difficulty of the waste liquid is increased, and simultaneously, a large amount of toxic gas (Cl) is generated due to inorganic acid leaching2、SO2、NO2) And a large amount of acid waste liquid is remained, which can bring secondary pollution.
Disclosure of Invention
Aiming at the defects of the prior art for treating the waste ternary lithium battery cathode material, the invention simplifies the treatment process and reduces the difficulty of waste liquid treatment, provides a hydrothermal lithium supplement-spray remodeling regeneration method for the waste ternary cathode material, and realizes great economic benefits.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hydrothermal lithium supplement-spray remodeling regeneration method for a waste ternary cathode material comprises the following specific steps:
(1) placing the waste ternary lithium battery in a sodium chloride solution with the concentration of 2mol/L for 36h, deeply discharging, and then disassembling and separating to obtain a positive aluminum foil, a negative copper foil, a shell, a diaphragm, a lug and the like;
(2) placing the anode aluminum foil obtained in the step (1) in a sodium hydroxide solution with the concentration of 1-2 mol/L, and stripping the anode material of the waste ternary lithium battery from the aluminum foil;
(3) placing the waste ternary lithium battery anode material obtained in the step (2) in a drying box for drying, then placing the drying box in a box-type furnace for calcining, separating out PVDF, and grinding to obtain powder;
(4) adding the powder obtained in the step (3) into organic acid for acid leaching pretreatment, and filtering to obtain an activated anode material;
(5) adding a lithium source solution into the activated anode material obtained in the step (4) to perform hydrothermal reaction treatment, limiting the concentration of Li within a certain range, reacting for a period of time at a certain temperature, and filtering to obtain a lithium-supplement anode material;
(6) taking the lithium-supplement positive electrode material obtained in the step (5) as a seed crystal, adding a nickel source, a manganese source and a cobalt source according to a target proportion according to the content of lithium, nickel, manganese and cobalt in the lithium-supplement positive electrode material to obtain a mixture, and adding water into the mixture to uniformly mix the mixture to obtain a seed crystal suspension with uniform components; the mass volume ratio g: mL of the mixture to water is 0.1-0.5: 1;
(7) adding the seed crystal suspension obtained in the step (6) into a spray dryer, performing spray granulation and remolding, and continuously preparing a spherical NCM precursor by controlling temperature, airflow pressure, feeding speed and the like;
(8) and (4) placing the NCM precursor prepared in the step (7) in a muffle furnace for two-stage sintering by using oxygen in the processing industry to obtain the regenerated ternary cathode material.
Preferably, the drying temperature in the step (3) is 120-150 ℃, and the time is 10-16 h; the calcining temperature is 600-700 ℃, and the time is 3-5 h.
Preferably, the organic acid in the step (4) is one or a mixture of more of malic acid, tartaric acid and citric acid in any proportion, and the concentration is 0.5-5 mol/L.
Preferably, the mass volume ratio g: mL of the powder in the step (4) to the organic acid is 0.1-0.5: 1.
Preferably, the acid leaching pretreatment in the step (4) is to react for 10-60 min at 30-80 ℃.
Preferably, the mass volume ratio g: mL of the activated positive electrode material to the lithium source solution in the step (5) is 0.1-0.5: 1, the concentration of the lithium source solution is 2-10 mol/L, and the lithium source is LiOH, lithium acetate or Li2CO3One or more of the components are mixed in any proportion.
Preferably, the temperature of the hydrothermal reaction in the step (5) is 200-300 ℃ and the time is 3-6 h.
Preferably, in the step (6), a nickel source, a cobalt source and a manganese source are added in a molar ratio of Ni to Co to Mn =6:2:2, 1:1:1, 5:2:3 or 8:1:1, and a molar ratio of Li to M (M = Ni + Co + Mn) = 1.03-1.08; the nickel source is NiC4H6O4·4H2O、Ni(NO3)2·6H2O, etc., the cobalt source is CoC4H6O4·4H2O、Co(NO3)2·6H2O, etc., the manganese source is MnC4H6O4·4H2O、Mn (NO3)2·6H2O, and the like.
Preferably, the spraying temperature of the spray dryer in the step (7) is 170-190 ℃, the feeding speed is 300-650 mL/h, the air inlet pressure is 0.1-0.5 MPa, and the outlet temperature is 120-150 ℃.
Preferably, the specific process of the two-stage sintering in the step (8) is as follows: the first-stage sintering temperature is as follows: 400-500 ℃ for the following time: 5-8 h, and the calcination temperature of the second section is as follows: 800-900 ℃, for the following time: 10 to 20 hours.
The spray remodeling regeneration of the invention takes the anode waste after the activation and lithium supplement as the crystal seed, the spheroidization of the regenerated material can be realized in a shorter time by the spray technology after the size mixing, and the sphericity is uniform step by stepMeanwhile, the hollowing problem of the traditional spray granulation can be avoided; obtaining the ternary cathode material by a two-step calcination system, and only generating CO2Or NO2And H2O, does not cause the problem of waste liquid treatment, thereby increasing economic benefits and protecting the environment.
The invention realizes the environmental protection and quick recycling of the waste ternary cathode material, wherein the ternary cathode material can be quickly restored by the hydrothermal lithium supplementation, the in-situ restoration of lithium can be quickly realized, the seed crystal spray granulation method is used for realizing the closed cycle of the recovery, the regenerated ternary cathode material can meet the preparation requirements of different series of ternary cathode materials and different gradient coating materials, and the regenerated ternary cathode material has good electrochemical performance.
The method realizes the production requirements of different series of gradient coated ternary material products by controlling the concentration and proportion of the solution, has simple operation, no pollution and obvious economic benefit, provides a new idea for recycling the ternary cathode material of the waste lithium battery, and has huge industrial application prospects.
The method combines the liquid-phase lithium supplement and spray remodeling technologies, can realize direct regeneration and high-value utilization of the ternary cathode material, simplifies the treatment process, reduces the difficulty of waste liquid treatment, and realizes environmental protection and economic win-win.
Drawings
FIG. 1 is an SEM image of an NCM precursor prepared in example 1;
FIG. 2 is a graph of the electrochemical performance of the material prepared in example 1;
FIG. 3 is an SEM image of the material prepared in example 2;
FIG. 4 is an XRD pattern of the material prepared in example 2;
figure 5 is the EDS spectrum for the element distribution of the material prepared in example 3.
Detailed Description
The technical solutions of the present invention are further described below with reference to specific examples, and it should be understood by those skilled in the art that the described examples are only for the understanding of the present invention, and should not be construed as specifically limiting the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making innovative efforts, belong to the scope of protection of the invention.
Example 1
A hydrothermal lithium supplement-spray remodeling regeneration method for a waste ternary cathode material comprises the following specific steps:
(1) waste NCM622 (LiNi)0.6Co0.2Mn0.22O2) Placing the ternary lithium battery in a sodium chloride solution with the concentration of 2mol/L, placing for 36h, deeply discharging, manually disassembling the battery, and separating out a positive aluminum foil, a negative copper foil, a shell, a diaphragm, a lug and the like;
(2) placing the positive aluminum foil in a sodium hydroxide solution with the concentration of 1mol/L, then stripping the positive material, and washing the stripped positive material by using the sodium hydroxide solution with the concentration of 1 mol/L;
(3) putting the waste ternary lithium battery positive electrode material obtained in the step (2) into a drying oven at 120 ℃, and drying for 12 hours; calcining the mixture for 4 hours at 650 ℃ in a box-type furnace, cooling the mixture to room temperature along with the furnace, taking the mixture out, grinding the mixture in a mortar, and filtering the mixture by using a 200-mesh sieve to obtain waste ternary lithium battery anode material powder;
(4) taking 10g of the anode material powder obtained in the step (3), putting the anode material powder into 100mL of malic acid solution with the concentration of 3mol/L, reacting for 60min at 30 ℃, and filtering the leaching solution to obtain an activated anode material;
(5) putting the activated positive electrode material obtained in the step (4) into a LiOH solution reaction kettle with the concentration of 6mol/L for hydrothermal reaction, wherein the mass volume ratio g: mL of the activated positive electrode material to the LiOH solution is 0.1:1, reacting for 6 hours at 200 ℃, and filtering to obtain a lithium-supplement positive electrode material;
(6) taking the lithium-supplementing positive electrode material obtained in the step (5) as a seed crystal, and adding NiC into filter residue according to the content of lithium, nickel, manganese and cobalt in a molar ratio of Ni: Co: Mn =6:2:2 and a molar ratio of Li: M (M = Ni + Co + Mn) =1.054H6O4·4H2O、CoC4H6O4· 4H2O、MnC4H6O4· 4H2O obtaining a mixture, adding water into the mixture, and performing ultrasonic treatment for 10min to obtain the productForming more uniform seed crystal suspension; the mass volume ratio g: mL of the mixture to the water is 0.1: 1;
(7) sucking the seed crystal suspension obtained in the step (6) into a spray dryer, controlling the temperature of the spray dryer to be 170 ℃, the feeding speed to be 650mL/h, the air inlet pressure to be 0.1MPa and the outlet temperature to be 120 ℃, carrying out spray granulation, and continuously preparing a precursor of the spherical NCM 622;
(8) putting the precursor prepared in the step (7) into a muffle furnace, and calcining the precursor in two sections by using oxygen in the processing industry, wherein the calcining in one section is as follows: and heating to 450 ℃, preserving heat for 6h, heating to 850 ℃, preserving heat for 12h, and performing secondary calcination to obtain the regenerated ternary cathode material NCM 622.
FIG. 1 is an SEM image of the prepared NCM precursor, and it can be seen that the precursor is in a sphere-like shape and the particle surface has a petal-like structure.
Fig. 2 is an electrochemical performance diagram of the prepared ternary cathode material (a half-cell prepared by taking a lithium sheet as a counter electrode is tested), the specific discharge capacity of the first circle at 0.1C can reach 176mAh/g, and the capacity retention rate is still good after 50 cycles at 1C, which indicates that the prepared material has good electrochemical performance.
Example 2
A hydrothermal lithium supplement-spray remodeling regeneration method for a waste ternary cathode material comprises the following specific steps:
(1) waste NCM523 (LiNi)0.5Co0.2Mn0.3O2) Placing the ternary lithium battery in a sodium chloride solution with the concentration of 2mol/L, placing for 36h, deeply discharging, manually disassembling the battery, and separating out a positive aluminum foil, a negative copper foil, a shell, a diaphragm, a lug and the like;
(2) placing the positive aluminum foil in a sodium hydroxide solution with the concentration of 2mol/L, then stripping the positive material, and washing the stripped positive material by using the sodium hydroxide solution with the concentration of 2 mol/L;
(3) putting the anode material of the waste ternary lithium battery obtained in the step (2) into a drying oven at 150 ℃, and drying for 10 hours; calcining the mixture for 5 hours at the temperature of 600 ℃ in a box-type furnace, cooling the mixture to room temperature along with the furnace, taking the mixture out, grinding the mixture in a mortar, and filtering the mixture by using a 200-mesh sieve to obtain waste ternary lithium battery anode material powder;
(4) taking 10g of the anode material powder obtained in the step (3), putting the anode material powder into 50mL of citric acid solution with the concentration of 0.5mol/L, reacting for 10min at 80 ℃, and filtering the leaching solution to obtain an activated anode material;
(5) putting the activated positive electrode material obtained in the step (4) into a lithium acetate solution reaction kettle with the concentration of 2mol/L for hydrothermal reaction, wherein the mass volume ratio g: mL of the activated positive electrode material to the lithium acetate solution is 0.5:1, reacting for 4 hours at 250 ℃, and filtering to obtain a lithium supplement positive electrode material;
(6) taking the lithium-supplementing positive electrode material obtained in the step (5) as a seed crystal, and adding NiC into the lithium-supplementing positive electrode material according to the content of lithium, nickel, manganese and cobalt in a molar ratio of Ni to Co to Mn =5 to 2 to 3 and a molar ratio of Li to M (M = Ni + Co + Mn) =1.034H6O4·4H2O、CoC4H6O4· 4H2O、MnC4H6O4· 4H2O, obtaining a mixture, adding water into the mixture, and performing ultrasonic treatment for 10min to form a relatively uniform seed crystal suspension; the mass volume ratio g: mL of the mixture to the water is 0.5: 1;
(7) sucking the seed crystal suspension obtained in the step (6) into a spray dryer, controlling the temperature of the spray dryer to be 180 ℃, the feeding speed to be 300mL/h, the air inlet pressure to be 0.5MPa and the outlet temperature to be 140 ℃, carrying out spray granulation, and continuously preparing a precursor of the spherical NCM 523;
(8) putting the precursor prepared in the step (7) into a muffle furnace, and calcining the precursor in two sections by using oxygen in the processing industry, wherein the calcining in one section is as follows: and heating to 400 ℃, preserving heat for 8h, heating to 900 ℃, preserving heat for 10h, and performing secondary calcination to obtain the regenerated ternary cathode material NCM 523.
Fig. 3 is an SEM image of the prepared ternary cathode material, and it can be seen from the SEM image that the regenerated ternary cathode material is in a sphere-like shape, the particle size is 20 μm, the primary particles on the particle surface are uniform in size, the surface is dense, and the corrosion of the electrolyte can be better prevented, so that the ternary cathode material has better cycle performance.
FIG. 4 is a view of the ternary positive electrode material preparedThe XRD pattern shows that the regenerated ternary cathode material has better α -NaFeO2The lamellar structure has no impurity phase and the crystal structure is good.
Example 3
A hydrothermal lithium supplement-spray remodeling regeneration technology for a waste ternary cathode material comprises the following specific steps:
(1) waste NCM811 (LiNi)0.8Co0.1Mn0.1O2) Placing the ternary lithium battery in a sodium chloride solution with the concentration of 2mol/L, placing for 36h, deeply discharging, manually disassembling the battery, and separating out a positive aluminum foil, a negative copper foil, a shell, a diaphragm, a lug and the like;
(2) placing the positive aluminum foil in a sodium hydroxide solution with the concentration of 1.5mol/L, then stripping the positive material, and washing the stripped positive material by using the sodium hydroxide solution with the concentration of 1.5 mol/L;
(3) putting the anode material of the waste ternary lithium battery obtained in the step (2) into a drying oven at 135 ℃, and drying for 16 hours; calcining the mixture for 3 hours at 700 ℃ in a box-type furnace, cooling the mixture to room temperature along with the furnace, taking the mixture out, grinding the mixture in a mortar, and filtering the mixture by using a 200-mesh sieve to obtain waste ternary lithium battery anode material powder;
(4) taking 10g of the anode material powder obtained in the step (3), putting the anode material powder into 20mL of tartaric acid solution with the concentration of 5mol/L, reacting for 30min at 50 ℃, and filtering the leaching solution to obtain an activated anode material;
(5) putting the activated anode material obtained in the step (4) into Li with the concentration of 10mol/L2CO3Hydrothermal reaction is carried out in a solution reaction kettle to activate the anode material and Li2CO3The mass volume ratio g: mL of the solution is 0.2:1, the reaction is carried out for 3 hours at 300 ℃, and lithium supplement anode materials are obtained by filtration;
(6) taking the lithium-supplementing positive electrode material obtained in the step (5) as a seed crystal, detecting the content of lithium, nickel, manganese and cobalt in the seed crystal, adding Ni (NO) into filter residue according to the molar ratio of Ni to Co to Mn =8 to 1, and the molar ratio of Li to M (M = Ni + Co + Mn) =1.083)2·6H2O、Co(NO3)2·6H2O、Mn (NO3)2·6H2O, obtaining a mixture, adding water into the mixture, and performing ultrasonic treatment for 10min to form a relatively uniform seed crystal suspension; the mass volume ratio g: mL of the mixture to the water is 0.4: 1;
(7) sucking the seed crystal suspension obtained in the step (6) into a spray dryer, controlling the temperature of the spray dryer to be 190 ℃, the feeding speed to be 450mL/h, the air inlet pressure to be 0.4MPa and the outlet temperature to be 150 ℃, carrying out spray granulation, and continuously preparing a precursor of the spherical NCM 811;
(8) putting the precursor prepared in the step (7) into a muffle furnace, and calcining the precursor in two sections by using oxygen in the processing industry, wherein the calcining in one section is as follows: and heating to 500 ℃, preserving heat for 5h, heating to 800 ℃, preserving heat for 20h, and performing secondary calcination to obtain the regenerated ternary cathode material NCM 811.
Fig. 5 is an EDS diagram of the prepared ternary cathode material, and it can be seen from the diagram that the elements of Ni, Co, Mn, and O are uniformly distributed, which indicates that the element segregation is low and the uniformity of the material is good.
Claims (10)
1. A hydrothermal lithium supplement-spray remodeling regeneration method of a waste ternary cathode material is characterized by comprising the following specific steps:
(1) placing the waste ternary lithium battery in a sodium chloride solution with the concentration of 2mol/L for 36 hours, and then disassembling and separating to obtain a positive aluminum foil, a negative copper foil, a shell, a diaphragm and a lug;
(2) placing the anode aluminum foil obtained in the step (1) in a sodium hydroxide solution with the concentration of 1-2 mol/L, and stripping the anode material of the waste ternary lithium battery from the aluminum foil;
(3) drying, calcining and grinding the waste ternary lithium battery anode material obtained in the step (2) to obtain powder;
(4) adding the powder obtained in the step (3) into organic acid for acid leaching pretreatment, and filtering to obtain an activated anode material;
(5) adding a lithium source solution into the activated positive electrode material obtained in the step (4) for hydrothermal reaction, and filtering to obtain a lithium supplement positive electrode material;
(6) taking the lithium-supplement anode material obtained in the step (5) as a seed crystal, simultaneously adding a nickel source, a manganese source and a cobalt source according to a target proportion to obtain a mixture according to the content of lithium, nickel, manganese and cobalt in the lithium-supplement anode material, and adding water to the mixture and uniformly mixing the mixture to obtain a seed crystal suspension; the mass volume ratio g: mL of the mixture to water is 0.1-0.5: 1;
(7) adding the seed crystal suspension obtained in the step (6) into a spray dryer, performing spray granulation and remolding, and continuously preparing a spherical NCM precursor;
(8) and (4) sintering the NCM precursor prepared in the step (7) in two sections under industrial oxygen to obtain the regenerated ternary cathode material.
2. The hydrothermal lithium supplement-spray remodeling regeneration method for the waste ternary cathode material according to claim 1, characterized in that the drying temperature in the step (3) is 120-150 ℃ and the time is 10-16 h; the calcining temperature is 600-700 ℃, and the time is 3-5 h.
3. The hydrothermal lithium supplement-spray remodeling regeneration method for the waste ternary cathode material according to claim 1, characterized in that the organic acid in the step (4) is one or a mixture of more of malic acid, tartaric acid or citric acid in any proportion, and the concentration is 0.5-5 mol/L.
4. The hydrothermal lithium supplement-spray remodeling regeneration method for the waste ternary cathode material as claimed in claim 1, wherein the mass volume ratio g: mL of the powder in the step (4) to the organic acid is 0.1-0.5: 1.
5. The hydrothermal lithium supplement-spray remodeling regeneration method for the waste ternary cathode material according to claim 1, characterized in that the acid leaching pretreatment in the step (4) is a reaction at 30-80 ℃ for 10-60 min.
6. The hydrothermal lithium supplement-spray remodeling regeneration method for waste ternary cathode materials according to claim 1, characterized in that the mass volume ratio g: mL of the activated cathode material to the lithium source solution in the step (5) is 0.1-0.5: 1, the concentration of the lithium source solution is 2-10 mol/L, and the lithium source is LiOH, lithium acetate or Li2CO3One or more of them can be used arbitrarilyAnd (4) mixing the components in proportion.
7. The hydrothermal lithium supplement-spray remodeling regeneration method for the waste ternary cathode material according to claim 1, characterized in that the temperature of the hydrothermal reaction in the step (5) is 200-300 ℃ and the time is 3-6 hours.
8. The hydrothermal lithium supplement-spray remodeling regeneration method for the waste ternary cathode material as claimed in claim 1, wherein in the step (6), a nickel source, a cobalt source and a manganese source are added according to a molar ratio of Ni to Co to Mn =6 to 2, 1 to 1, 5 to 2 to 3 or 8 to 1, and a molar ratio of Li to Ni + Co + Mn = 1.03-1.08; the nickel source is NiC4H6O4·4H2O or Ni (NO)3)2·6H2O, cobalt source being CoC4H6O4·4H2O or Co (NO)3)2·6H2O, source of manganese MnC4H6O4·4H2O or Mn (NO)3)2·6H2O。
9. The hydrothermal lithium supplement-spray remodeling regeneration method for the waste ternary cathode material as claimed in claim 1, wherein the spray temperature of the spray dryer in the step (7) is 170-190 ℃, the feeding speed is 300-650 mL/h, the air inlet pressure is 0.1-0.5 MPa, and the outlet temperature is 120-150 ℃.
10. The hydrothermal lithium supplement-spray remodeling regeneration method for the waste ternary cathode material as claimed in claim 1, wherein the specific process of the two-stage sintering in the step (8) is as follows: the sintering temperature of the first section is 400-500 ℃, the sintering time is 5-8 hours, and the calcining temperature of the second section is 800-900 ℃, and the sintering time is 10-20 hours.
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