CN115010192A - Method for regenerating element gradient manganese-rich ternary precursor by using ternary precursor waste - Google Patents
Method for regenerating element gradient manganese-rich ternary precursor by using ternary precursor waste Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 110
- 239000011572 manganese Substances 0.000 title claims abstract description 93
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 84
- 239000002699 waste material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000012716 precipitator Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000013461 design Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 230000001502 supplementing effect Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000001556 precipitation Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 abstract description 9
- 238000000605 extraction Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 37
- 229910052744 lithium Inorganic materials 0.000 description 37
- 239000000243 solution Substances 0.000 description 25
- 239000007788 liquid Substances 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 229910017052 cobalt Inorganic materials 0.000 description 13
- 239000010941 cobalt Substances 0.000 description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 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 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- -1 ion salt Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- 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 invention discloses a method for regenerating an element gradient manganese-rich ternary precursor by utilizing ternary precursor waste, which comprises the steps of contacting the ternary precursor waste with an acid-containing solution, carrying out dissolution reaction, filtering the obtained leachate, carrying out extraction separation on the filtered leachate and an extracting agent to obtain a manganese-rich solution and a nickel-cobalt-rich solution, respectively supplementing materials to meet a design proportion, and obtaining the regenerated element gradient manganese-rich ternary precursor under the action of a precipitator and a complexing agent. The regenerated manganese-rich ternary precursor is provided with different metal element proportion gradient layers, and the content of nickel element in the inner layer is higher; the outer layer has a higher proportion of manganese; chemical composition is shown as general formula Ni x Co y Mn z (OH) 2 Wherein x is0 to 0.25, y is 0 to 0.25, and z is 0.5 to 1. The method for regenerating the element gradient manganese-rich ternary precursor by using the ternary precursor waste realizes the reutilization of the ternary precursor waste, improves the particle porosity of the regenerated ternary precursor, and improves the electrochemical performance of the material.
Description
Technical Field
The invention relates to the field of treatment of ternary precursor waste for producing ternary lithium batteries, in particular to a regenerated ternary precursor and a method for preparing the regenerated ternary precursor from the ternary precursor waste.
Background
At present, a large amount of ternary precursor waste is generated in the production process of the anode material, and the recovery method is uniformly that the ternary precursor waste is completely dissolved by strong acid, and then coprecipitated by alkali liquor (sodium hydroxide and ammonia water), and the precursor with the same metal element proportion is prepared again. The method can not regenerate high-end precursor materials, needs a large amount of acid dissolution and a large amount of alkali precipitation, has large limitation on application range and causes a large amount of waste in the process.
In the current power battery cathode materials, the lithium-rich manganese-based material is used as a new-generation lithium battery cathode material and is the lithium power battery cathode material with the greatest development prospect in the future. Because a large amount of manganese elements are used in the material, compared with lithium cobaltate and ternary materials, the material has the advantages of low price, good safety and environmental friendliness. Therefore, the lithium-rich manganese-based positive electrode material is considered as an ideal choice for the positive electrode material of the next generation lithium ion battery. The lithium-rich manganese base is considered to be one of the positive electrode materials of the new generation of the power lithium battery with great potential for realizing high energy density and long endurance mileage.
CN104466162B discloses a preparation method of a gradient lithium-rich manganese-based precursor and a gradient lithium-rich manganese-based anode material, wherein a mixed solution A, a mixed solution B and a solution C with different manganese ion contents are prepared, and are sequentially added into a first reactor, a second reactor and a third reactor for reaction, and the first reactor, the second reactor and the third reactor are connected in series for cyclic reaction to obtain the gradient lithium-rich manganese-based precursor.
CN107634216A discloses a method for preparing a porous hollow spherical lithium-rich manganese-based positive electrode material by adopting an ultrasonic atomization technology. Dissolving water-soluble lithium source, nickel source, cobalt source, manganese source and metal chelating agent in deionized water according to a required molar ratio, continuously stirring and refluxing in a water bath, stirring for 8-20 hours to obtain a precursor solution for atomization, atomizing the obtained mixed solution into fog drops by using an ultrasonic atomizer, loading the fog drops into a tubular furnace with the aid of a vacuum pumping system to convert the fog drops into precursor powder, and finally calcining in the air or oxygen atmosphere to obtain the porous hollow spherical lithium-rich manganese-based anode material powder.
CN109704415A discloses a lithium-rich manganese-based precursor, a preparation method thereof and a lithium-rich manganese-based anode material. The preparation method of the lithium-rich manganese-based precursor comprises the following steps: (1) dissolving nickel salt, cobalt salt, manganese salt and doped ion salt in water to obtain mixed salt solution; (2) adding a precipitator and a complexing agent into the mixed salt solution, and adjusting the pH value to obtain a reaction precursor; (3) and carrying out intermittent ultrasonic oscillation on the reaction precursor to obtain a lithium-rich manganese-based precursor crude product. The method adjusts the pH value of the reaction system to enable the particle size of the material to be in an ascending stage, adopts intermittent ultrasonic oscillation to control the particle size in the reaction system, starts the ultrasonic oscillator to enable the reaction system to quickly nucleate and reduce the particle size when the particle size exceeds a control index, and closes the ultrasonic oscillator when the particle size is reduced to a qualified standard range, thereby realizing the controllable particle size of the lithium-rich manganese-based precursor.
CN112234176A provides a preparation method of a lithium-rich manganese-based precursor, wherein the fluorine and magnesium co-doped lithium-rich manganese-based precursor is prepared by a binary system coprecipitation method, the preparation method is simple in process and convenient to operate, and magnesium ions and fluorine ions can be uniformly doped in a lithium-rich manganese-based material. The invention also provides the lithium-rich manganese-based precursor prepared by the preparation method, a lithium-rich manganese-based positive electrode material prepared from the lithium-rich manganese-based precursor and a lithium ion battery containing the positive electrode material.
CN110980818A discloses a lithium-rich manganese-based positive electrode material precursor and a preparation method thereof. The precursor of the lithium-rich manganese-based positive electrode material is prepared by precipitation reaction with the pH value of 10.0-13.0 in the nitrogen or argon atmosphere. Uniformly mixing the precursor and lithium carbonate according to the molar ratio of Li to Me of 1.25 to 0.8, calcining in the air, wherein Me is the total mole number of metal ions in the precursor of the lithium-rich manganese-based positive electrode material, heating to 400-plus-temperature 600 ℃ and preserving heat for 2-10h during calcining, and then heating to 700-plus-temperature 1000 ℃ and preserving heat for 7-20 h; cooling and sieving; mixing the obtained solid with potassium dichromate solution of 1-100g and 0.01-0.5 mol/l/L, stirring for 20-40min, filtering, washing, and drying; heating the obtained powder to 300-500 ℃ and preserving the heat for 2-5h to obtain the lithium-rich manganese-based anode material.
The invention discloses a method for preparing a high-capacity lithium-rich manganese-based positive electrode material by coprecipitation, which comprises the following steps of: (1) preparing a lithium-rich manganese-based positive electrode material precursor; (2) ball milling lithium mixing and spray pelletizing; (3) and (3) preparing the lithium-rich manganese-based anode material by high-temperature solid-phase sintering.
CN112054168A discloses a method for ternary precursor waste treatment and a regenerated ternary precursor. The regenerated ternary precursor is provided with a kernel and a shell layer wrapping the kernel, and the porosity of the kernel is 65-75%; the thickness of the shell layer is 40-100nm, and the density of the shell layer is more than 90%; the chemical composition of the core and the shell is shown as the general formula Ni x Co y Mn z Al w (OH) 2 Wherein x is 0.3-0.9, y is 0.05-0.4, z is 0-0.4, and w is 0-0.4.
However, the above-mentioned technology still has high regeneration cost, and the regenerated product is greatly limited by the proportion of waste elements, and there is still a need to provide a good method for treating ternary lithium battery waste and a regenerated product.
Disclosure of Invention
In order to overcome the problems of large limitation of ternary precursor waste regenerated products, high regeneration cost and the like in the prior art, the invention provides a method for preparing a regenerated manganese-rich ternary precursor by regenerating a ternary precursor and ternary precursor waste. The method can provide a convenient and low-pollution method for producing regenerated ternary materials with better electrochemical capacity and cycle performance.
In order to solve the technical problems, the invention provides a regenerated element gradient manganese-rich ternary precursor, which has an element gradient, wherein the porosity of the inner layer is 65-75%; the thickness of the outer layer is 1.5-2.5 μm, and the density of the outer layer is more than 90%;
the chemical compositions of the inner layer and the outer layer are shown as the general formula Ni x Co y Mn z (OH) 2 Wherein x is 0-0.25, y is 0-0.25, z is 0.5-1. preferably, the inner core has a diameter of 0.5-2 μm.
Preferably, the particle size of the regenerated ternary precursor is 2.5-4.5 μm.
The invention provides a method for preparing a regenerated element gradient manganese-rich ternary precursor by using ternary precursor waste, which comprises the following steps:
(1) contacting the ternary precursor waste with an acid-containing solution and carrying out a dissolution reaction;
(2) filtering the leachate obtained in the step (1), and then extracting and back-extracting the leachate with an extracting agent to obtain a manganese-rich solution and a nickel-cobalt-rich solution;
(3) respectively supplementing the manganese-rich solution and the nickel-cobalt-rich solution obtained in the step (2) with materials to meet the design proportion;
(4) and (4) obtaining the manganese-rich solution and the nickel-cobalt-rich solution which meet the design proportion and are obtained in the step (3) under the action of a precipitator and a complexing agent to obtain the regenerated element gradient manganese-rich ternary precursor.
According to the invention, preferably, the acid-containing solution in the step (1) contains inorganic acid, weak organic acid, reducing agent and water, and the content of the inorganic acid is 5-40%, preferably 10-30% based on the total weight of the acid-containing solution; the content of weak organic acid is 0-10%, preferably 0-5%; the content of the reducing agent is 0.1-10%, preferably 0.1-0.5%; the reducing agent is selected from at least one of sodium sulfite, potassium borohydride or sodium borohydride; the weak organic acid is at least one of citric acid, acetic acid or malic acid, and the inorganic acid is at least one of oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
According to the invention, the weight ratio of the ternary precursor waste to the acid-containing solution in the step (1) is preferably 1:2 to 1: 10.
According to the present invention, preferably, the acid reaction is completed by dissolving the ternary precursor waste. The dissolving reaction temperature of the step (1) is 60-85 ℃, the dissolving reaction time is 1-4h, and the pH value at the end of the dissolving reaction is 1-5.
According to the present invention, preferably, the extractant in step (2) is p204, and O/a =1:1-1: 4.
According to the invention, preferably, the manganese-rich feed liquid and the nickel-rich and cobalt-rich feed liquid obtained in the step (4) are precipitated and regenerated in sequence under the participation of a precipitator and a complexing agent, and the specific operation steps are as follows: adding the obtained nickel-cobalt-rich solution into a reaction kettle protected by nitrogen, then adding a precipitator and a complexing agent for precipitation reaction, adding the obtained manganese-rich solution into the reaction kettle protected by nitrogen after the reaction is finished, and then adding the precipitator and the complexing agent for precipitation reaction.
According to the present invention, preferably, the precipitant in the step (4) is selected from at least one of sodium hydroxide, potassium hydroxide, sodium bicarbonate or sodium carbonate; the complexing agent is selected from at least one of ammonium bicarbonate, ammonium bisulfate, ammonia water or ammonium dihydrogen phosphate.
According to the invention, preferably, the molar ratio of the metal element to the complexing agent in the manganese-rich solution and the nickel-cobalt-rich solution which meet the designed proportion in the step (4) is 1 (0.05-0.2), and the precipitant controls the reaction pH to be = 10-12.
According to the invention, the precipitation reaction is preferably carried out at a temperature of 30 to 80 ℃ for a time of 4 to 80 hours.
In the present invention, using the separated liquid having the above composition, it is possible to further achieve a metal element molar ratio satisfying the design by the feeding of step (3).
The regenerated ternary precursor provided by the invention can control the particle size of secondary microspheres to be in a nanometer level, and the particles have a core-shell structure in which a compact shell layer wraps a core with high porosity, so that the electrochemical capacity and the cycle performance of a ternary material can be improved when the regenerated ternary precursor is applied to a ternary lithium battery.
According toThe method provided by the invention can be used for utilizing waste materials generated in the production of the ternary precursor, and can be discarded or unqualified. The chemical composition of the ternary precursor waste is essentially conventional. Preferably, the chemical composition of the inner layer and the outer layer is represented by the general formula Ni x Co y Mn z (OH) 2 Wherein x is 0-0.25, y is 0-0.25, and z is 0.5-1. The method provided by the invention is realized by processing the ternary precursor waste for multiple times through the steps to obtain the regenerated ternary precursor provided by the invention, and the regenerated ternary precursor has the limited structure.
The invention has the beneficial effects that: through the technical scheme, the method can realize that the waste or unqualified ternary precursor generated in the production process of the ternary lithium battery is subjected to short-range extraction and separation to obtain manganese-rich and nickel-cobalt-rich feed liquid, and the qualified and usable element gradient manganese-rich ternary precursor is prepared in a coprecipitation mode, so that the high-value reutilization of the ternary precursor waste is realized, the defect that the high-added-value next-generation product cannot be efficiently produced by the waste with fixed element content is overcome, and the method has the characteristic of flexibly treating the waste precursor. According to the renewable element gradient ternary precursor provided by the invention, the structure stability of the material is improved due to the fact that manganese is enriched outside, the capacity of the material is ensured due to the fact that nickel is enriched inside, and the problem of limiting capacity attenuation in the industrialization of the lithium-rich manganese-based material is solved.
Drawings
FIG. 1 is a particle SEM image of a regenerated ternary precursor prepared in example 1;
fig. 2 is a large-magnification SEM image of particles of the regenerated ternary precursor prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Example 1
The method for regenerating the element gradient manganese-rich ternary precursor by using the ternary precursor waste comprises the following steps:
(1) preparing an acid-containing liquid: 1069g of sulfuric acid, 15g of citric acid, 30g of sodium sulfite and 5kg of deionized water; 1kg of ternary precursor waste (Ni) was stirred at 80 ℃ and 300rpm under nitrogen protection 0.5 Co 0.2 Mn 0.3 (OH) 2 ) Mixing with acid-containing liquid for dissolution reaction for 4 h;
(2) adding the leachate into a p 204-containing extraction tank to separate nickel, cobalt and manganese, wherein O: A =1:2, and the pH of the obtained mixture reaches 2.5; the obtained extract is rich in nickel and cobalt elements; pickling the obtained raffinate to obtain a manganese-rich solution; adding a proper amount of metal elements into the obtained solution respectively to reach the designed metal molar ratio;
(3) and sequentially adding the obtained nickel-cobalt-rich feed liquid into a reaction kettle protected by nitrogen for precipitation reaction. The reaction temperature is 50 ℃, sodium hydroxide is added to control the pH to be =11.5, the ammonia concentration is 4g/L, and the feeding is stopped after the granularity reaches 3 mu m; and then sequentially adding the obtained manganese-rich feed liquid into a reaction kettle protected by nitrogen for precipitation reaction. The reaction temperature is 50 ℃, sodium hydroxide is added to control the pH to be =11, and the reaction is stopped when the particle size of the ammonia concentration of 5g/L reaches 4 μm;
and filtering the reaction product, washing with deionized water, finally reducing the pH value of the filtered washing water to 7, and drying the obtained filter cake at 100 ℃ under the protection of nitrogen to obtain the regenerated manganese-rich ternary precursor.
The obtained regenerated ternary precursor was subjected to structural observation, as shown in fig. 1 and 2.
Example 2
The method for regenerating the element gradient manganese-rich ternary precursor by using the ternary precursor waste comprises the following steps:
(1) preparing an acid-containing liquid: 1075g sulfuric acid, 12g malic acid, 30g sodium sulfite and 5kg deionized water; 1kg of ternary precursor waste (Ni) was stirred at 80 ℃ and 300rpm under nitrogen protection 0.6 Co 0.2 Mn 0.2 (OH) 2 ) Contacting with an acid-containing liquid phase to perform acid reaction for 5 hours;
(2) adding the leachate into a p 204-containing extraction tank to separate nickel, cobalt and manganese, wherein O: A =1:3, and the pH of the obtained mixture reaches 2.5; the obtained extract is rich in nickel and cobalt elements; pickling the obtained raffinate to obtain a manganese-rich solution; adding a proper amount of metal elements into the obtained solution respectively to achieve the designed metal molar ratio;
(3) and sequentially adding the obtained manganese-rich feed liquid into a reaction kettle protected by nitrogen for precipitation reaction. The reaction temperature is 55 ℃, potassium hydroxide is added to control the pH to be =11.6, the ammonia concentration is 4.5g/L, and the feeding is stopped after the granularity reaches 2.7 mu m; and then sequentially adding the obtained nickel-rich and cobalt-rich feed liquid into a reaction kettle protected by nitrogen for precipitation reaction. The reaction temperature is 55 ℃, potassium hydroxide is added to control the pH to be =10.9, the ammonia concentration is 6g/L, and the reaction is stopped when the particle size reaches 3.7 mu m;
and filtering the reaction product, washing with deionized water, reducing the pH value of the filtered washing water to 7, and drying the obtained filter cake at 100 ℃ under the protection of nitrogen to obtain the regenerated manganese-rich ternary precursor.
Example 3
The method for regenerating the element gradient manganese-rich ternary precursor by using the ternary precursor waste comprises the following steps:
(1) preparing an acid-containing liquid: 1077g sulfuric acid, 30g sodium sulfite and 5kg deionized water; 1kg of ternary precursor waste (Ni) was stirred at 75 ℃ and 350rpm under nitrogen protection 0.8 Co 0.1 Mn 0.1 (OH) 2 ) Contacting with an acid-containing liquid phase to perform acid reaction for 5 hours;
(2) adding the leachate into a p 204-containing extraction tank to separate nickel, cobalt and manganese, wherein O: A =1:2, and the pH of the obtained mixture reaches 2.5; the obtained extract is rich in nickel and cobalt elements; pickling the obtained raffinate to obtain a manganese-rich solution; adding a proper amount of metal elements into the obtained solution respectively to achieve the designed metal molar ratio;
(3) and sequentially adding the obtained manganese-rich feed liquid into a reaction kettle protected by nitrogen for precipitation reaction. The reaction temperature is 45 ℃, sodium hydroxide is added to control the pH to be =11.8, the ammonia concentration is 4.5g/L, and the feeding is stopped after the granularity reaches 1.8 mu m; and then sequentially adding the obtained nickel-rich and cobalt-rich feed liquid into a reaction kettle protected by nitrogen for precipitation reaction. The reaction temperature is 55 ℃, sodium hydroxide is added to control the pH to be =11.2, the ammonia concentration is 5g/L, and the reaction is stopped when the particle size reaches 4.2 mu m;
and filtering the reaction product, washing with deionized water, reducing the pH value of the filtered washing water to 7, and drying the obtained filter cake at 100 ℃ under the protection of nitrogen to obtain the regenerated manganese-rich ternary precursor.
Example 4
The method for regenerating the element gradient manganese-rich ternary precursor by using the ternary precursor waste comprises the following steps:
(1) preparing an acid-containing liquid: 1065g of sulfuric acid, 30g of sodium sulfite and 5kg of deionized water; 1kg of ternary precursor waste (Ni) was added under nitrogen protection at 80 ℃ and a stirring speed of 300rpm 0.33 Co 0.33 Mn 0.33 (OH) 2 ) Contacting with an acid-containing liquid phase to perform acid reaction for 5 hours;
(2) adding the leachate into a p 204-containing extraction tank to separate nickel, cobalt and manganese, wherein O: A =1:2, and the pH of the obtained mixture reaches 2.5; the obtained extract is rich in nickel and cobalt elements; pickling the obtained raffinate to obtain a manganese-rich solution; adding a proper amount of metal elements into the obtained solution respectively to achieve the designed metal molar ratio;
(3) and sequentially adding the obtained manganese-rich feed liquid into a reaction kettle protected by nitrogen for precipitation reaction. The reaction temperature is 55 ℃, sodium hydroxide is added to control the pH to be =12.1, the ammonia concentration is 4.3g/L, and the feeding is stopped when the granularity reaches 2 mu m; and then sequentially adding the obtained nickel-rich and cobalt-rich feed liquid into a reaction kettle protected by nitrogen for precipitation reaction. The reaction temperature is 55 ℃, sodium hydroxide is added to control the pH to be =11.5, the ammonia concentration is 5.2g/L, and the reaction is stopped when the particle size reaches 3 mu m;
and filtering the reaction product, washing with deionized water, reducing the pH value of the filtered washing water to 7, and drying the obtained filter cake at 100 ℃ under the protection of nitrogen to obtain the regenerated manganese-rich ternary precursor.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A method for regenerating an element gradient manganese-rich ternary precursor by using a ternary precursor waste is characterized by comprising the following steps:
(1) contacting the ternary precursor waste with an acid-containing solution and carrying out a dissolution reaction;
(2) filtering the leachate obtained in the step (1), extracting and back-extracting the leachate with an extracting agent to obtain a manganese-rich solution and a nickel-cobalt-rich solution;
(3) supplementing materials for the manganese-rich solution and the nickel-cobalt-rich solution obtained in the step (2) respectively to meet the design proportion;
(4) and (4) obtaining the manganese-rich solution and the nickel-cobalt-rich solution which meet the design proportion and are obtained in the step (3) under the action of a precipitator and a complexing agent to obtain the regenerated element gradient manganese-rich ternary precursor.
2. The method of regenerating an elemental gradient manganese-rich ternary precursor using a ternary precursor waste according to claim 1, characterized in that: the acid-containing solution in the step (1) contains inorganic acid, weak organic acid, a reducing agent and water, wherein the content of the inorganic acid is 5-40%, the content of the weak organic acid is 0-10% and the content of the reducing agent is 0.1-10% based on the total weight of the acid-containing solution; the reducing agent is selected from at least one of sodium sulfite, potassium borohydride or sodium borohydride; the weak organic acid is at least one of citric acid, acetic acid or malic acid, and the inorganic acid is at least one of oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
3. The method of regenerating an elemental gradient manganese-rich ternary precursor using a ternary precursor waste according to claim 1, characterized in that: the weight ratio of the ternary precursor waste to the acid-containing solution in the step (1) is 1:2-1: 10.
4. The method of regenerating an elemental gradient manganese-rich ternary precursor using a ternary precursor waste according to claim 1, characterized in that: the dissolving reaction temperature of the step (1) is 60-85 ℃, the dissolving reaction time is 1-4h, and the pH value at the end of the dissolving reaction is 1-5.
5. The method of regenerating an elemental gradient manganese-rich ternary precursor using a ternary precursor waste according to claim 1, characterized in that: the extractant in the step (2) is p204, and O/A =1:1-1: 4.
6. The method of regenerating an elemental gradient manganese-rich ternary precursor using a ternary precursor waste according to claim 1, characterized in that: the operation steps of the precipitation reaction in the step (4) are as follows: adding the obtained nickel-cobalt-rich solution into a reaction kettle protected by nitrogen, then adding a precipitator and a complexing agent for precipitation reaction, adding the obtained manganese-rich solution into the reaction kettle protected by nitrogen after the reaction is finished, and then adding the precipitator and the complexing agent for precipitation reaction.
7. The method of regenerating an elemental gradient manganese-rich ternary precursor using a ternary precursor waste according to claim 1, characterized in that: the precipitator in the step (4) is at least one selected from sodium hydroxide, potassium hydroxide, sodium bicarbonate or sodium carbonate; the complexing agent is selected from at least one of ammonium bicarbonate, ammonium bisulfate, ammonia water or ammonium dihydrogen phosphate.
8. The method of regenerating an elemental gradient manganese-rich ternary precursor using a ternary precursor waste according to claim 1, characterized in that: the molar ratio of the metal elements to the complexing agent in the manganese-rich solution and the nickel-cobalt-rich solution which meet the design proportion in the step (4) is 1 (0.05-0.2), and the reaction pH is controlled to be 10-12 by the precipitator.
9. The method of regenerating an elemental gradient manganese-rich ternary precursor using a ternary precursor waste according to claim 1, wherein: the temperature of the precipitation reaction is 30-80 ℃, and the time is 4-80 h.
10. The regenerated element gradient manganese-rich ternary precursor prepared by the method of any one of claims 1 to 9, which is characterized in that: the regenerated element gradient manganese-rich ternary precursor is a nickel-rich gradient material with an inner layer and a manganese-rich outer layer, the diameter of the inner layer is 0.5-2 mu m, and the porosity of the inner layer is 65-75%; the thickness of the outer layer is 1.5-2.5 μm, the density of the outer layer is more than 90%, and the particle size of the regenerated ternary precursor is 2.5-4.5 μm; the chemical compositions of the inner layer and the outer layer are shown as the general formula Ni x Co y Mn z (OH) 2 Wherein x is 0-0.25, y is 0-0.25, and z is 0.5-1.
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