CN115010192B - Method for regenerating element gradient manganese-rich ternary precursor by utilizing ternary precursor waste - Google Patents
Method for regenerating element gradient manganese-rich ternary precursor by utilizing ternary precursor waste Download PDFInfo
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- CN115010192B CN115010192B CN202210898666.8A CN202210898666A CN115010192B CN 115010192 B CN115010192 B CN 115010192B CN 202210898666 A CN202210898666 A CN 202210898666A CN 115010192 B CN115010192 B CN 115010192B
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- 239000002243 precursor Substances 0.000 title claims abstract description 105
- 239000011572 manganese Substances 0.000 title claims abstract description 86
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 81
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004090 dissolution Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000012716 precipitator Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 37
- 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 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- 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
- 238000005554 pickling Methods 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 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
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 3
- 230000001502 supplementing effect Effects 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 36
- 229910052744 lithium Inorganic materials 0.000 description 36
- 239000000243 solution Substances 0.000 description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 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
- 238000003756 stirring Methods 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000000975 co-precipitation Methods 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
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 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
- 238000001354 calcination Methods 0.000 description 2
- 238000005516 engineering process Methods 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
- 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
- 239000012266 salt solution Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910016366 Ni0.33Co0.33Mn0.33(OH)2 Inorganic materials 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 1
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 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
- 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
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- -1 ion salt Chemical class 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
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium 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
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 239000011800 void material Substances 0.000 description 1
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 ternary precursor waste with an acid-containing solution, carrying out dissolution reaction, filtering an obtained leaching solution, carrying out extraction separation on the leaching solution and an extracting agent to obtain a manganese-rich solution and a nickel-cobalt-rich solution, respectively supplementing materials to meet the 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 gradient layers with different metal element proportions, and the inner layer is nickel element with higher content; the outer layer has a higher proportion of manganese; the chemical composition is shown as a 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 for recycling the ternary precursor waste by using the ternary precursor waste recycling element gradient manganese-rich ternary precursor realizes the recycling of the ternary precursor waste, improves the porosity of the recycled ternary precursor particles, and improves the electrochemical performance of the material.
Description
Technical Field
The invention relates to the field of ternary precursor waste material treatment for producing ternary lithium batteries, in particular to a regenerated ternary precursor and a method for preparing the regenerated ternary precursor by using ternary precursor waste material.
Background
At present, a large amount of ternary precursor waste is generated in the production process of the positive electrode material, the recovery method is unified that strong acid is used for complete dissolution, and then alkali liquor (sodium hydroxide and ammonia water) is used for coprecipitation, so that precursors with the same metal element proportion are prepared again. The method can not regenerate high-end precursor materials, needs a large amount of acid to dissolve and a large amount of alkali to precipitate, and has large limitation of application range and great waste caused by the technical process.
Among the current power battery anode materials, the lithium-rich manganese-based material is used as a new generation of lithium battery anode materials, and is the lithium power battery anode material with the development prospect in the future. As a large amount of manganese elements are used in the material, compared with lithium cobaltate and ternary materials, the material has low price, good safety and environmental friendliness. Therefore, lithium-rich manganese-based cathode materials are considered as ideal candidates for next-generation lithium ion battery cathode materials. The lithium-rich manganese base is considered as one of the positive electrode materials of the power lithium battery with great potential of the new generation 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 positive electrode material, preparing a mixed solution a, a mixed solution B and a solution C with different manganese ion contents, sequentially adding a first reactor, a second reactor and a third reactor for reaction, and performing serial circulation reaction on the first reactor, the second reactor and the third reactor 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. According to the method, a lithium source, a nickel source, a cobalt source, a manganese source and a metal chelating agent which are soluble in water are dissolved in deionized water according to a required molar ratio, stirring and refluxing are carried out in a water bath kettle, precursor solution for atomization is obtained after stirring for 8-20 hours, then the obtained mixed solution is atomized into mist drops by an ultrasonic atomizer, the mist drops are loaded into a tube furnace under the assistance of a vacuumizing system, the mist drops are changed into precursor powder, and finally the precursor powder is calcined in the atmosphere of air or oxygen, so that porous hollow spherical lithium-rich manganese-based anode material powder is obtained.
CN109704415a discloses and relates to a lithium-rich manganese-based precursor, a preparation method thereof and a lithium-rich manganese-based cathode 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 a mixed salt solution; (2) Adding a precipitator and a complexing agent into the mixed salt solution, and regulating the pH value to obtain a reaction precursor; (3) And carrying out intermittent ultrasonic vibration on the reaction precursor to obtain a crude product of the lithium-rich manganese-based precursor. The invention adjusts the pH value of the reaction system to ensure that the granularity of the material is in an ascending stage, adopts intermittent ultrasonic vibration to control the granularity in the reaction system, starts an ultrasonic oscillator when the granularity exceeds a control index to enable the reaction system to quickly nucleate, reduces the granularity, and closes the ultrasonic oscillator when the granularity is reduced to a qualified standard range, thereby realizing the controllable granularity of the lithium-rich manganese-based precursor.
CN112234176a provides a preparation method of a lithium-rich manganese-based precursor, and the fluorine and magnesium co-doped lithium-rich manganese-based precursor is prepared by a dual-system co-precipitation method. The invention also provides the lithium-rich manganese-based precursor prepared by the preparation method, the lithium-rich manganese-based positive electrode material prepared by the lithium-rich manganese-based precursor and a lithium ion battery containing the positive electrode material.
CN110980818A discloses a precursor of a lithium-rich manganese-based positive electrode material and a preparation method thereof. And preparing the precursor of the lithium-rich manganese-based positive electrode material through precipitation reaction in nitrogen or argon atmosphere at the pH value of 10.0-13.0. Uniformly mixing the precursor and lithium carbonate according to a molar ratio of Li: me=1.25:0.8, and calcining in 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 400-600 ℃ and preserving heat for 2-10h, heating to 700-1000 ℃ and preserving heat for 7-20h during calcining; cooling and sieving; mixing the obtained solid with 1-100g potassium dichromate solution of 0.01-0.5mol/l per liter, stirring for 20-40min, filtering, washing, and drying; and heating the obtained powder to 300-500 ℃ and preserving heat for 2-5 hours 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: (1) preparing a precursor of a lithium-rich manganese-based positive electrode material; (2) ball milling, lithium mixing and spray pelletizing; and (3) preparing the lithium-rich manganese-based anode material by high-temperature solid-phase sintering.
CN112054168A discloses a method of ternary precursor waste treatment and regeneration of ternary precursors. The regenerated ternary precursor is provided with an inner core and a shell layer wrapping the inner core, wherein the porosity of the inner core 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 inner core and the shell is shown as a 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 technology still has high regeneration cost, the regenerated product is limited by the proportion of waste elements, and a method for treating waste materials of the ternary lithium battery and the regenerated product are still needed to be provided.
Disclosure of Invention
In order to overcome the problems of high limitation of ternary precursor waste regenerated products, high regeneration cost and the like in the prior art, the invention provides a regenerated ternary precursor and a method for preparing a regenerated manganese-rich ternary precursor by using ternary precursor waste. The method can provide a convenient and pollution-free way for producing the regenerated ternary material with better electrochemical capacity and cycle performance.
In order to solve the technical problems, a first aspect of the invention provides a regenerated element gradient manganese-rich ternary precursor, the regenerated ternary precursor has an element gradient, and the porosity of the inner layer is 65-75%; the thickness of the outer layer is 1.5-2.5 mu m, and the density of the outer layer is more than 90%;
the chemical composition of the inner layer and the outer layer is shown as a general formula Ni x Co y Mn z (OH) 2 As shown, where x is 0-0.25, y is 0-0.25, and z is 0.5-1, the diameter of the inner core is preferably 0.5-2 μm.
Preferably, the particle size of the regenerated ternary precursor is 2.5-4.5 μm.
The second aspect of the invention provides a method for preparing a regenerated element gradient manganese-rich ternary precursor by using ternary precursor waste, comprising the following steps:
(1) Contacting the ternary precursor waste with an acid-containing solution and performing a dissolution reaction;
(2) Filtering the leaching solution obtained in the step (1), and then extracting and back-extracting with an extracting agent to obtain a manganese-rich solution and a nickel-cobalt-rich solution;
(3) Feeding the manganese-rich solution and the nickel-cobalt-rich solution obtained in the step (2) respectively to meet the design proportion;
(4) And (3) obtaining the manganese-rich solution meeting the design proportion and the nickel-cobalt-rich solution 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 step (1) comprises an inorganic acid, a weak organic acid, a reducing agent and water, the content of the inorganic acid being 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 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, preferably, the weight ratio of the ternary precursor waste material to the acid-containing solution in the step (1) is 1:2-1:10.
According to the present invention, it is preferable that the acid reaction is completed so that the ternary precursor waste is dissolved. The dissolution reaction temperature in the step (1) is 60-85 ℃, the dissolution reaction time is 1-4h, and the pH of the dissolution reaction end point is 1-5.
According to the present invention, preferably, the extractant in the step (2) is p204, O/a=1:1 to 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 sequentially subjected to precipitation regeneration 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 nitrogen-protected reaction kettle, adding a precipitator and a complexing agent for precipitation reaction, adding the obtained manganese-rich solution into the nitrogen-protected reaction kettle 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 at least one selected from 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 meeting the design ratio in the step (4) is 1 (0.05-0.2), and the precipitant controls the reaction ph=10-12.
According to the present invention, it is preferable that the temperature of the precipitation reaction is 30-80 ℃ for 4-80 hours.
In the present invention, the separation liquid having the above composition is used, and the metal element molar ratio satisfying the design can be further achieved by the feed of step (3).
The regenerated ternary precursor provided by the invention can control the particle size of the secondary microsphere to be in a nano level, and the particle has a core-shell structure with a core with a compact shell layer and a high void ratio, so that the electrochemical capacity and the cycle performance of the ternary material can be improved when the regenerated ternary precursor is applied to a ternary lithium battery.
The method provided by the invention can be used for generating waste materials when the ternary precursor is produced, and can be used for being abandoned or unqualified in production. The chemical composition of the ternary precursor waste is substantially conventional. Preferably, the chemical composition of the inner layer and the outer layer is as shown in 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 characterized in that the ternary precursor waste is treated for multiple times to obtain the regenerated ternary precursor provided by the invention, and the regenerated ternary precursor has the structure defined above.
The invention has the beneficial effects that: through the technical scheme, the method can realize the waste or unqualified ternary precursor generated in the production process of the ternary lithium battery, obtain the manganese-rich and nickel-cobalt-rich feed liquid through short-range extraction separation, prepare the qualified and usable element gradient manganese-rich ternary precursor through a coprecipitation mode, realize the high-value reuse of ternary precursor waste, solve the defect that the waste with fixed element content cannot efficiently produce the next-generation product with high added value, and have the characteristic of flexibly treating the waste precursor. The regenerated element gradient ternary precursor provided by the invention has the advantages that the structural stability of the material is improved due to the fact that the external manganese is rich, the capacity of the material is ensured due to the fact that the internal nickel is rich, and the problem of 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 according to example 1;
FIG. 2 is a particle-size SEM image of a regenerated ternary precursor prepared according to example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that numerous insubstantial modifications and adaptations can be made by those skilled in the art in light of the foregoing disclosure.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to 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 in the embodiment comprises the following steps:
(1) Preparing acid-containing liquid: 1069g sulfuric acid, 15g citric acid, 30g sodium sulfite and 5kg deionized water; under nitrogen protection and stirring speed of 80 ℃ and 300rpm, 1kg of ternary precursor waste (Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 ) And containAcid liquor is mixed for dissolution reaction for 4 hours;
(2) Adding the leaching solution into a p 204-containing extraction tank to separate nickel, cobalt and manganese, wherein O is A=1:2, and the pH value of the obtained mixture reaches 2.5; the obtained extract is rich in nickel and cobalt; pickling the 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 to carry out precipitation reaction. The reaction temperature is 50 ℃, sodium hydroxide is added to control the pH=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 to carry out precipitation reaction. The reaction temperature is 50 ℃, sodium hydroxide is added to control pH=11, the ammonia concentration is 5g/L, the particle size reaches 4 mu m, and the reaction is stopped;
and filtering and washing the reaction product with deionized water, reducing the pH of the finally filtered washing water to 7, and then drying the obtained filter cake at 100 ℃ under the protection of nitrogen to obtain the regenerated manganese-rich ternary precursor.
The structure of the regenerated ternary precursor obtained was observed 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 in the embodiment comprises the following steps:
(1) Preparing acid-containing liquid: 1075g sulfuric acid, 12g malic acid, 30g sodium sulfite and 5kg deionized water; under nitrogen protection and stirring speed of 80 ℃ and 300rpm, 1kg of ternary precursor waste (Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 ) Carrying out acid reaction for 5h by contacting with an acid-containing liquid phase;
(2) Adding the leaching solution into a p 204-containing extraction tank to separate nickel, cobalt and manganese, wherein O is A=1:3, and the pH value of the obtained mixture reaches 2.5; the obtained extract is rich in nickel and cobalt; pickling the 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 manganese-rich feed liquid into a reaction kettle protected by nitrogen to carry out precipitation reaction. The reaction temperature is 55 ℃, potassium hydroxide is added to control the pH=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 to carry out precipitation reaction. The reaction temperature is 55 ℃, potassium hydroxide is added to control the pH=10.9, the ammonia concentration is 6g/L, the particle size reaches 3.7 mu m, and the reaction is stopped;
and filtering and washing the reaction product with deionized water, reducing the pH of the finally filtered washing water to 7, and then 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 in the embodiment comprises the following steps:
(1) Preparing acid-containing liquid: 1077g sulfuric acid, 30g sodium sulfite and 5kg deionized water; under nitrogen protection and stirring speed of 350rpm at 75 ℃, 1kg of ternary precursor waste (Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 ) Carrying out acid reaction for 5h by contacting with an acid-containing liquid phase;
(2) Adding the leaching solution into a p 204-containing extraction tank to separate nickel, cobalt and manganese, wherein O is A=1:2, and the pH value of the obtained mixture reaches 2.5; the obtained extract is rich in nickel and cobalt; pickling the 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 manganese-rich feed liquid into a reaction kettle protected by nitrogen to carry out precipitation reaction. The reaction temperature is 45 ℃, sodium hydroxide is added to control the pH=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 to carry out precipitation reaction. The reaction temperature is 55 ℃, sodium hydroxide is added to control pH=11.2, ammonia concentration is 5g/L, and the particle size reaches 4.2 mu m to stop the reaction;
and filtering and washing the reaction product with deionized water, reducing the pH of the finally filtered washing water to 7, and then 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 in the embodiment comprises the following steps:
(1) Preparing acid-containing liquid: 1065g sulfuric acid, 30g sodium sulfite and 5kg deionized water; under nitrogen protection and stirring speed of 80 ℃ and 300rpm, 1kg of ternary precursor waste (Ni 0.33 Co 0.33 Mn 0.33 (OH) 2 ) Carrying out acid reaction for 5h by contacting with an acid-containing liquid phase;
(2) Adding the leaching solution into a p 204-containing extraction tank to separate nickel, cobalt and manganese, wherein O is A=1:2, and the pH value of the obtained mixture reaches 2.5; the obtained extract is rich in nickel and cobalt; pickling the 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 manganese-rich feed liquid into a reaction kettle protected by nitrogen to carry out precipitation reaction. The reaction temperature is 55 ℃, sodium hydroxide is added to control the pH=12.1, the ammonia concentration is 4.3g/L, and the feeding is stopped after 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 to carry out precipitation reaction. The reaction temperature is 55 ℃, sodium hydroxide is added to control pH=11.5, ammonia concentration is 5.2g/L, and the particle size reaches 3 mu m to stop the reaction;
and filtering and washing the reaction product with deionized water, reducing the pH of the finally filtered washing water to 7, and then drying the obtained filter cake at 100 ℃ under the protection of nitrogen to obtain the regenerated manganese-rich ternary precursor.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. The method for regenerating the element gradient manganese-rich ternary precursor by utilizing the ternary precursor waste is characterized by comprising the following steps of:
(1) Contacting the ternary precursor waste with an acid-containing solution and performing a dissolution reaction;
(2) Filtering the leaching solution obtained in the step (1), and then extracting and back-extracting with an extracting agent to obtain a manganese-rich solution and a nickel-cobalt-rich solution; the extract obtained by extraction is nickel and cobalt element-rich solution; pickling the raffinate to obtain a manganese-rich solution;
(3) Feeding the manganese-rich solution and the nickel-cobalt-rich solution obtained in the step (2) respectively to meet the design proportion;
(4) The manganese-rich solution meeting the design proportion obtained in the step (3) and the nickel-rich cobalt solution are subjected to the action of a precipitator and a complexing agent to obtain a regenerated element gradient manganese-rich ternary precursor;
the precipitation reaction in the step (4) is operated 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, stopping feeding after the reaction is finished, adding the obtained manganese-rich solution into the reaction kettle protected by nitrogen, and then adding the precipitator and the complexing agent for precipitation reaction;
the molar ratio of the metal element in the manganese-rich solution and the complexing agent in the manganese-rich solution meeting the design proportion in the step (4) is 1 (0.05-0.2), and the precipitant controls the reaction pH=10-12; the temperature of the precipitation reaction is 30-80 ℃ and the time is 4-80h;
the regeneration element gradient manganese-rich ternary precursor is an inner layer nickel-rich outer layer manganese-rich gradient material, 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 mu m, the density of the outer layer is more than 90%, and the particle size of the regenerated ternary precursor is 2.5-4.5 mu m; the chemical composition of the inner layer and the outer layer is shown as a general formula Ni x Co y Mn z (OH) 2 Shown, wherein 0<x≤0.25、0<y≤0.25、0.5≤z<1。
2. The method for regenerating an elemental gradient manganese-rich ternary precursor using ternary precursor waste according to claim 1, wherein: the acid-containing solution in the step (1) comprises 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 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 for regenerating an elemental gradient manganese-rich ternary precursor using ternary precursor waste according to claim 1, wherein: and (2) 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 for regenerating an elemental gradient manganese-rich ternary precursor using ternary precursor waste according to claim 1, wherein: the dissolution reaction temperature in the step (1) is 60-85 ℃, the dissolution reaction time is 1-4h, and the pH of the dissolution reaction end point is 1-5.
5. The method for regenerating an elemental gradient manganese-rich ternary precursor using ternary precursor waste according to claim 1, wherein: the extractant in the step (2) is P204, and O/A=1:1-1:4.
6. The method for regenerating an elemental gradient manganese-rich ternary precursor using ternary precursor waste according to claim 1, wherein: the precipitant in the step (4) is at least one selected from sodium hydroxide, potassium hydroxide, sodium bicarbonate or sodium carbonate; the complexing agent is at least one selected from ammonium bicarbonate, ammonium bisulfate, ammonia water or ammonium dihydrogen phosphate.
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