CN114890482B - Ternary positive electrode precursor and preparation method and application thereof - Google Patents
Ternary positive electrode precursor and preparation method and application thereof Download PDFInfo
- Publication number
- CN114890482B CN114890482B CN202210678654.4A CN202210678654A CN114890482B CN 114890482 B CN114890482 B CN 114890482B CN 202210678654 A CN202210678654 A CN 202210678654A CN 114890482 B CN114890482 B CN 114890482B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- solution
- ternary positive
- electrode precursor
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000005406 washing Methods 0.000 claims abstract description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000008139 complexing agent Substances 0.000 claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 22
- 239000010941 cobalt Substances 0.000 claims abstract description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 claims abstract description 21
- 238000000975 co-precipitation Methods 0.000 claims abstract description 19
- 239000012266 salt solution Substances 0.000 claims abstract description 17
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 23
- 239000002585 base Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 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
- 239000010406 cathode material Substances 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 2
- 159000000021 acetate salts Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 19
- 238000003756 stirring Methods 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 229940044175 cobalt sulfate Drugs 0.000 description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229940099596 manganese sulfate Drugs 0.000 description 7
- 235000007079 manganese sulphate Nutrition 0.000 description 7
- 239000011702 manganese sulphate Substances 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 7
- 229940053662 nickel sulfate Drugs 0.000 description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- LXKIIAIRNCIFBQ-UHFFFAOYSA-N [S].[Co].[Mn].[Ni] Chemical compound [S].[Co].[Mn].[Ni] LXKIIAIRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—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
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a ternary positive electrode precursor, and a preparation method and application thereof. The preparation method comprises the following steps: adding a mixed salt solution of nickel, cobalt and manganese, a sulfate solution, a precipitant solution and a complexing agent solution into a base solution in parallel flow, performing coprecipitation reaction, and centrifugally washing a product of the coprecipitation reaction to obtain the ternary positive electrode precursor; wherein the doping amount of sulfate radical in the ternary positive electrode precursor is 2000-20000 ppm. In the process of preparing the nickel-cobalt-manganese ternary positive electrode precursor, reasonable doping of sulfate radical is effectively realized by controlling the centrifugal washing process, water consumption in the washing process is reduced, the manufacturing cost of the ternary positive electrode precursor is reduced, the structural stability of the positive electrode material is ensured, and the cyclic stability and the thermal stability of the ternary positive electrode material are improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and relates to a ternary anode precursor, a preparation method and application thereof.
Background
At present, the lithium ion battery is widely applied to the field of electric automobiles, and the positive electrode material of the lithium ion battery for the automobile mainly comprises lithium iron phosphate, ternary lithium, lithium manganate and the like. The lithium ion battery prepared from the ternary positive electrode material with the layered structure has high energy density and excellent multiplying power performance, so that the high-end electric passenger car market is almost controlled.
Nickel sulfate, cobalt sulfate, and manganese sulfate are widely used as ternary precursors for the synthesis of nickel cobalt manganese, and therefore, the residue of sulfate in the positive electrode material is unavoidable, and sulfate impurities are generally considered to have an adverse effect on the performance of lithium ion batteries, because sulfate may affect the crystallization of hydroxide precursors in the layered structure. The ternary positive electrode material industry standard YS/T798-2012 defined by the China nonferrous metal industry defines sulfate radical as an impurity, and the content of the sulfate radical is less than 0.5 weight percent. Therefore, ternary positive precursor manufacturers struggle to reduce the sulfate content of NCM to a full extent, typically washing the hydroxide precursor with large amounts of alkali and deionized water in order to remove sulfate, which also results in increased material manufacturing costs.
CN112591808A discloses a preparation method of a low-sodium sulfur nickel cobalt manganese ternary precursor, which solves the problem of high content of sodium sulfur impurities in the precursor prepared by the current coprecipitation method through the steps of seed crystal preparation, seed crystal growth, stopping reaction, increasing pH value, solution replacement, starting reaction, particle growth reaching a target value, stopping reaction, increasing pH value, solution replacement, filter pressing washing, drying and demagnetizing.
CN110817975a discloses a method for reducing sulfur content of ternary precursor, which uses sulfate as ternary salt raw material, adding ternary salt raw material, alkali liquor and complexing agent into a reaction kettle to make coprecipitation to prepare ternary precursor, after the coprecipitation reaction is carried out for 5-15 hours, continuously or intermittently adding pure water into the reaction kettle to displace the clear liquid in the reaction kettle, and at the same time adding alkali liquor and complexing agent to keep the reaction system stable. The method prevents sulfate radical from being adsorbed on the surface of the crystal in the crystal growth process and further wrapping the inside of the crystal, so that the problem that the sulfur content in the ternary precursor exceeds the standard is solved, and the sulfur content of the prepared ternary precursor is lower than 530ppm after one-time washing.
The purpose of the above methods is to minimize the sulfate content of the ternary precursor. However, none of the systematic studies demonstrate the effect of sulfate content in the ternary precursor material on the performance of the final fabricated lithium ion battery.
Therefore, how to regulate the doping amount of sulfate radical in the nickel-cobalt-manganese ternary precursor material and improve the electrochemical performance and the structural stability of the positive electrode material is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide a ternary positive electrode precursor, and a preparation method and application thereof. In the process of preparing the nickel-cobalt-manganese ternary positive electrode precursor, reasonable doping of sulfate radical is effectively realized by controlling the centrifugal washing process, water consumption in the washing process is reduced, the manufacturing cost of the ternary positive electrode precursor is reduced, the structural stability of the positive electrode material is ensured, and the cyclic stability and the thermal stability of the ternary positive electrode material are improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a ternary positive electrode precursor, the method comprising:
adding a mixed salt solution of nickel, cobalt and manganese, a sulfate solution, a precipitant solution and a complexing agent solution into a base solution in parallel flow, performing coprecipitation reaction, and centrifugally washing a product of the coprecipitation reaction to obtain the ternary positive electrode precursor;
wherein the doping amount of sulfate radical in the ternary positive electrode precursor is 2000-20000 ppm, such as 2000ppm, 3000ppm, 3500ppm, 4000ppm, 5000ppm, 6000ppm, 7000ppm, 8000ppm, 9000ppm, 10000ppm, 11000ppm, 12000ppm, 13000ppm, 14000ppm, 15000ppm, 16000ppm, 17000ppm, 18000ppm, 19000ppm or 20000ppm.
In the process of preparing the precursor, the sulfate solution is added to dope sulfate, and the regulation and control of the sulfate doping amount is realized through the centrifugal washing process, so that the performance of the ternary positive electrode material is improved, the strict standard of the sulfate content in the ternary precursor material can be relaxed, the water consumption can be reduced, the manufacturing cost of the ternary precursor is reduced, and the performance of a battery is not reduced; the doping of sulfate radical can reduce lithium nickel mixed discharge, and the doping structure can provide more ordered channels for lithium ion diffusion, so that the rate capability of the lithium ion battery is improved; in addition, the crystal formed by sulfate radical and metal ions can effectively fill the gaps among primary particles, stabilize the structure of secondary particles and remarkably improve the cycle stability and the thermal stability of ternary materials; the sulfate radical doping can inhibit the loss of active sites of the positive electrode material, so that the layered structure is more stable in the circulation process, and the circulation performance of the positive electrode material is improved; meanwhile, the sulfate radical doping can inhibit the leaching of transition metal ions in the anode material, so as to inhibit the capacity attenuation in the battery cycle process.
That is, the ternary positive electrode precursor provided by the invention is additionally doped with sulfate radical, the purpose of centrifugal washing is not to reduce the content of sulfate radical in the system, but to regulate the doping amount of the ternary positive electrode precursor, so that reasonable doping is realized, and the content of sulfate radical does not need to be reduced.
In the invention, if the doping amount of sulfate radical is too small, the high-efficiency exertion of the electrochemical performance of the anode material is not facilitated, and if the doping amount is too large, a plurality of adverse effects can be generated on the performance of the lithium battery.
Preferably, the total concentration of metal ions in the nickel cobalt manganese mixed salt solution is 0.1 to 5mol/L, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, or the like.
Preferably, the sulfate solution has a concentration of 0.5 to 5mol/L, for example, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, or the like.
In the invention, the too low concentration of sulfate can lead to the increase of yield reduction cost, which is unfavorable for large-scale production, while the too high concentration of sulfate can influence the growth of precursor crystal nucleus.
Preferably, the mixed salt solution of nickel, cobalt and manganese comprises any one or a combination of at least two of nickel, cobalt and manganese mixed chloride salt, nickel, cobalt and manganese mixed sulfate, nickel, cobalt and manganese mixed nitrate or nickel, cobalt and manganese mixed acetate.
Preferably, the sulfate solution comprises any one or a combination of at least two of sodium sulfate solution, ammonia sulfate solution or potassium sulfate solution.
Preferably, the precipitant comprises NaOH, KOH, ba (OH) 2 Or Na (or) 2 CO 3 Any one or a combination of at least two of these.
Preferably, the concentration of the precipitant solution is 2 to 15mol/L, for example, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L, 14mol/L, 15mol/L, or the like.
Preferably, the complexing agent comprises any one or a combination of at least two of hydrazine hydrate, aqueous ammonia or oxalic acid.
Preferably, the concentration of the complexing agent solution is 4 to 12mol/L, for example 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, etc.
Preferably, the pH of the base liquid is 9 to 13, for example 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5 or 13, etc.
Preferably, the concentration of the complexing agent in the base liquid is 0 to 2mol/L, for example 0mol/L, 0.3mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 1.3mol/L, 1.5mol/L, 1.8mol/L, 2mol/L or the like.
Preferably, the feeding speed of the nickel cobalt manganese mixed salt solution is 4-100L/h, for example 4L/h, 10L/h, 20L/h, 30L/h, 40L/h, 50L/h, 60L/h, 70L/h, 80L/h, 90L/h or 100L/h, etc.
Preferably, the sulfate solution is fed at a rate of 2 to 50L/h, for example 2L/h, 5L/h, 10L/h, 13L/h, 15L/h, 18L/h, 20L/h, 23L/h, 25L/h, 28L/h, 30L/h, 33L/h, 35L/h, 38L/h, 40L/h, 43L/h, 45L/h, 48L/h, 50L/h, or the like.
Preferably, the feed rate of the precipitant solution is 1 to 20L/h, for example 1L/h, 3L/h, 8L/h, 10L/h, 13L/h, 15L/h, 18L/h, 20L/h, etc.
Preferably, the complexing agent solution is fed at a rate of 0.5 to 10L/h, for example 0.5L/h, 1L/h, 2L/h, 3L/h, 4L/h, 5L/h, 6L/h, 7L/h, 8L/h, 9L/h or 10L/h, etc.
In the invention, the feeding speeds of the raw materials are cooperatively matched to jointly realize the controllable reaction of the nucleation and growth processes of the ternary precursor.
Preferably, the coprecipitation reaction is carried out under a protective atmosphere.
Preferably, the reaction temperature of the coprecipitation reaction is 40 to 80 ℃, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, or the like.
Preferably, the pH in the coprecipitation reaction is 9 to 13, for example 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5 or 13, etc.
Preferably, the rotational speed of the centrifugal washing is 1000 to 2000rpm, for example 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, 1600rpm, 1700rpm, 1800rpm, 1900rpm, 2000rpm or the like.
In the invention, the too high rotation speed of centrifugal washing can lead to lower doping amount of sulfate radical and increase production cost, while the too low rotation speed of centrifugal washing can lead to higher doping amount of sulfate radical and reduce production efficiency.
Preferably, the centrifugal washing includes sequentially performing alkali washing and water washing.
Preferably, the volume of the lye used per 100kg of material in the lye washing process is 1-3 m 3 For example 1m 3 、1.3m 3 、1.5m 3 、1.8m 3 、2m 3 、2.3m 3 、2.5m 3 、2.8m 3 Or 3m 3 Etc.
In the invention, the waste of raw materials can be caused by the overlarge volume of the alkali liquor, and the washing effect can be influenced by the overlarge volume of the alkali liquor.
Preferably, the volume of water used per 100kg of material in the water washing process is 1-5 m 3 For example 1m 3 、1.5m 3 、2m 3 、2.5m 3 、3m 3 、3.5m 3 、4m 3 、4.5m 3 Or 5m 3 Etc.
In the invention, the volume of water is too large, so that the content of doped sulfate radical is lower, and the volume of water is too small, thereby not achieving the washing effect.
According to the invention, by regulating and controlling each parameter range in the centrifugal washing process and coordinating various conditions, the effective removal of impurities in the ternary precursor is realized, and the content of sulfate radical can be regulated and controlled.
As a preferred technical scheme, the preparation method comprises the following steps:
adding a mixed salt solution of nickel, cobalt and manganese, a sulfate solution, a precipitant solution and a complexing agent solution into a base solution in parallel flow, wherein the feeding speed of the mixed salt solution of nickel, cobalt and manganese is 4-100L/h, the feeding speed of the sulfate solution is 2-50L/h, the feeding speed of the precipitant solution is 1-20L/h, the feeding speed of the complexing agent solution is 0.5-10L/h, performing coprecipitation reaction under the condition that the pH value is kept to be 9-13 at the reaction temperature of 40-80 ℃ in a protective atmosphere, and then sequentially performing centrifugal washing of alkali liquor and centrifugal washing of water on the product of the coprecipitation reaction at the rotating speed of 1000-2000 rpm to obtain the ternary positive electrode precursor;
wherein the total concentration of metal ions in the nickel-cobalt-manganese mixed salt solution is 0.1-5 mol/L, the concentration of sulfate solution is 0.5-5 mol/L, the concentration of precipitant solution is 2-15 mol/L, the concentration of complexing agent solution is 4-12 mol/L, the pH value of base solution is 9-13, and the concentration of complexing agent in the base solution is 0-2 mol/L; the volume of the alkali liquor used in every 100kg of materials in the centrifugal washing process of the alkali liquor is 1-3 m 3 The volume of water used per 100kg of materials in the centrifugal washing process of water is 1-5 m 3 The method comprises the steps of carrying out a first treatment on the surface of the The doping amount of sulfate radical in the ternary positive electrode precursor is 2000-to-ultra20000ppm。
In a second aspect, the invention provides a ternary positive electrode precursor, the ternary positive electrode precursor is prepared by the preparation method of the ternary positive electrode precursor according to the first aspect, the ternary positive electrode precursor is doped with sulfate radical, and the doping amount of the sulfate radical in the ternary positive electrode precursor is 2000-20000 ppm.
In a third aspect, the invention provides a ternary positive electrode material, which is obtained by mixing and sintering a ternary positive electrode precursor and a lithium source according to the second aspect.
In a fourth aspect, the present invention also provides a lithium ion battery comprising the ternary cathode material according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
in the process of preparing the ternary positive electrode precursor of nickel, cobalt and manganese, the sulfate solution is added into the raw materials for doping, and the centrifugal washing process is controlled, so that reasonable doping of sulfate radical in the ternary positive electrode precursor is effectively realized, the water consumption in the washing process is reduced, the manufacturing cost of the ternary positive electrode precursor is reduced, the structural stability of the positive electrode material obtained from the ternary positive electrode precursor is ensured, and the electrochemical performance of the ternary positive electrode material is improved. The battery obtained by the ternary precursor provided by the invention can be cycled for at least 170 times under the condition of 1C, and the battery capacity can be less than 80%.
Drawings
Fig. 1 is an SEM image of the ternary positive electrode precursor provided in example 1.
Fig. 2 is an EDS spectrum of elemental sulfur in the ternary positive electrode precursor provided in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a sulfate-doped ternary precursor material, which comprises the following steps:
(1) Preparing a solution: mixing nickel sulfate, cobalt sulfate and manganese sulfate with deionized water, and stirring until the nickel sulfate, the cobalt sulfate and the manganese sulfate are completely dissolved to obtain a mixed solution A (nickel-cobalt-manganese molar ratio is 6:1:3) with the total concentration of metal ions of 2mol/L; mixing sodium sulfate with water, and stirring until the sodium sulfate and the water are completely dissolved to obtain a mixed solution B with the concentration of 2mol/L; mixing sodium hydroxide with water to obtain a mixed solution C with the concentration of 10 mol/L; mixing ammonia water with water to obtain 8mol/L mixed solution D; mixing a certain amount of ammonia water, sodium hydroxide and deionized water, and regulating the concentration to obtain a reaction base solution E with the pH value of 11.5 and the ammonia concentration of 0.3 mol/L;
(2) Reaction stage: adding 120L of reaction base solution E into a reaction kettle, continuously introducing high-purity nitrogen, introducing the mixed solution A, the mixed solution B, the mixed solution C and the mixed solution D into a constant-temperature reaction kettle in a stirring state for reaction, keeping the reaction temperature at 60 ℃, respectively adding the mixed solution A and the mixed solution B into the reaction kettle at a stable and constant feeding speed of 8L/h and 4L/h, and controlling the pH value of the reaction system to be between 11.0 and 11.2 and the concentration of a complexing agent to be between 0.25 and 0.3mol/L by controlling the flow of the mixed solution C, D to obtain sulfate-doped ternary precursor mixed slurry F;
(3) And (3) slurry treatment: slurry F was filtered using 1m for every 100kg of material 3 Sodium hydroxide solution and 1m 3 Washing with water, and obtaining a precursor with the sulfate radical doping amount of 20000ppm by rotating at 1000rpm in the centrifugal washing process, and drying to obtain the sulfate radical doped ternary precursor material.
Fig. 1 shows an SEM image of the ternary positive electrode precursor provided in example 1, and as can be seen from fig. 1, the ternary precursor prepared in this case has uniform size, better sphericity, average size of 4-5 microns,
fig. 2 shows EDS spectra of elemental sulfur in the ternary positive electrode precursor provided in example 1, and fig. 2 shows that elemental sulfur is uniformly distributed in the precursor particles, illustrating uniform doping of sulfate.
Example 2
The embodiment provides a preparation method of a sulfate-doped ternary precursor material, which comprises the following steps:
(1) Preparing a solution: mixing nickel sulfate, cobalt sulfate and manganese sulfate with deionized water, and stirring until the nickel sulfate, the cobalt sulfate and the manganese sulfate are completely dissolved to obtain a mixed solution A (the molar ratio of nickel to cobalt to manganese is 8:1:1) with the total concentration of metal ions of 2mol/L; mixing sodium sulfate with water, and stirring until the sodium sulfate and the water are completely dissolved to obtain a mixed solution B with the concentration of 2mol/L; mixing sodium hydroxide with water to obtain a mixed solution C with the concentration of 10 mol/L; mixing ammonia water with water to obtain 8mol/L mixed solution D; mixing a certain amount of ammonia water, sodium hydroxide and deionized water, and regulating the concentration to obtain a reaction base solution E with the pH value of 12.5 and the ammonia concentration of 0.3 mol/L;
(2) Reaction stage: 670L of reaction base solution E is added into a reaction kettle, high-purity nitrogen is continuously introduced, the mixed solution A, the mixed solution B, the mixed solution C and the mixed solution D are introduced into a constant-temperature reaction kettle in a stirring state for reaction, the reaction temperature is 80 ℃, the mixed solution A and the mixed solution B are respectively added into the reaction kettle at a stable and constant feeding speed of 32L/h and 20L/h, and the pH value of the reaction system is controlled between 12.2 and 12.5 and the concentration of a complexing agent is controlled between 0.3 and 0.35mol/L by controlling the flow of the mixed solution C, D, so that sulfate radical doped ternary precursor mixed slurry F is obtained;
(3) And (3) slurry treatment: slurry F was filtered using 3m per 100kg of material 3 Sodium hydroxide solution and 5m 3 Washing with water, and centrifuging at 2000rpm to obtain precursor with sulfate radical doping amount of 2000ppm, and stoving to obtain the ternary precursor material doped with sulfate radical.
Example 3
The embodiment provides a preparation method of a sulfate-doped ternary precursor material, which comprises the following steps:
(1) Preparing a solution: mixing nickel sulfate, cobalt sulfate and manganese sulfate with deionized water, and stirring until the nickel sulfate, the cobalt sulfate and the manganese sulfate are completely dissolved to obtain a mixed solution A (the molar ratio of nickel to cobalt to manganese is 5:2:3) with the total concentration of metal ions of 2mol/L; mixing sodium sulfate with water, and stirring until the sodium sulfate and the water are completely dissolved to obtain a mixed solution B with the concentration of 3 mol/L; mixing sodium hydroxide with water to obtain a mixed solution C with the concentration of 10 mol/L; mixing ammonia water with water to obtain 8mol/L mixed solution D; mixing a certain amount of ammonia water, sodium hydroxide and deionized water, and regulating the concentration to obtain a reaction base solution E with the pH value of 10.8 and the ammonia concentration of 0.15 mol/L;
(2) Reaction stage: 2000L of reaction base solution E is added into a reaction kettle, high-purity nitrogen is continuously introduced, the mixed solution A, the mixed solution B, the mixed solution C and the mixed solution D are introduced into a constant-temperature reaction kettle in a stirring state for reaction, the reaction temperature is 80 ℃, the mixed solution A and the mixed solution B are respectively added into the reaction kettle at the stable and invariable feeding speeds of 50L/h and 15L/h, and the pH value of the reaction system is controlled to be between 10.6 and 11.0 and the concentration of a complexing agent is controlled to be between 0.10 and 0.15mol/L by controlling the flow of the mixed solution C, D, so that sulfate-doped ternary precursor mixed slurry F is obtained;
(3) And (3) slurry treatment: slurry F was filtered using 3m per 100kg of material 3 Sodium hydroxide solution and 5m 3 Washing with water, and obtaining a precursor with the sulfate radical doping amount of 2500ppm by rotating at 1000rpm in the centrifugal washing process, and drying to obtain the sulfate radical doped ternary precursor material.
Example 4
The difference between this example and example 1 is that the volume of sodium hydroxide solution in step (3) of this example is 2m 3 。
The remaining preparation methods and parameters were consistent with example 1.
Example 5
The difference between this example and example 1 is that the volume of water in step (3) of this example was 3m 3 。
The remaining preparation methods and parameters were consistent with example 1.
Example 6
The difference between this example and example 1 is that the rotational speed of the centrifugal washing in step (3) of this example was 1500rpm.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 1
The difference between this comparative example and example 1 is that the sodium sulfate mixed solution B was not prepared in the step (1) of this comparative example.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 2
The difference between this comparative example and example 1 is that the washing was not performed after centrifugation in step (3) of this comparative example.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 3
The difference between this comparative example and example 1 is that the sulfate doping amount in this comparative example was 40000ppm.
The difference between this comparative example and example 1 is that the washing with sodium hydroxide solution in step (3) of this comparative example was not performed.
The remaining preparation methods and parameters were consistent with example 1.
The ternary positive electrode precursors provided in examples 1-6 and comparative examples 1-3 were fully mixed with LiOH in a molar ratio of 1.00:1.05, sintered in a tube furnace under oxygen flow, sintered at 450 ℃ for 6 hours, then calcined at 780 ℃ for 15 hours at high temperature, and ground and sieved to obtain a ternary positive electrode material.
The positive electrode slurry was prepared by mixing 80wt% of the positive electrode material, 10wt% of the conductive carbon black, 10wt% of PVDF, and an appropriate amount of NMP. The slurry was uniformly coated on a 15 μm thick aluminum foil and dried in a vacuum oven at 120℃for 12 hours to remove the solvent and moisture. Further, the resultant was cut into a disk having a diameter of 13mm to obtain a positive electrode sheet (single-sided coating surface density=16 mg cm) -2 )。
Then, using metallic lithium as anode, 1M LiPF 6 The membrane was dissolved in EC/DMC/EMC (volume ratio 1:1:1) as electrolyte, and a 20 μm thick polyolefin film was used as separator, and the CR2032 coin cell was assembled in a glove box.
Electrochemical performance tests were performed on button cells, cycle performance was tested at 1C between 2.8 and 4.3V, and the number of cycles at which discharge capacity was reduced to 80% was as shown in table 1 (table 1 also shows the doping amount of sulfate).
TABLE 1
| Sulfate doping amount (ppm) | Cycle performance | |
| Example 1 | 20000 | 170cycles |
| Example 2 | 2000 | 170cycles |
| Example 3 | 2500 | 175cycles |
| Example 4 | 10000 | 183cycles |
| Example 5 | 16000 | 178cycles |
| Example 6 | 18000 | 172cycles |
| Comparative example 1 | 500 | 150cycles |
| Comparative example 2 | 50000 | 80cycles |
| Comparative example 3 | 40000 | 120cycles |
As is clear from the data of example 1 and comparative example 1, the addition of no sulfate to the raw materials for preparing the precursor makes it difficult to achieve the proper amount of sulfate doping because the amount of sulfate doping is too small.
From the data of example 1 and comparative example 2, it is evident that removal of excess sulfate could not be achieved without centrifugal washing.
From the data of example 1 and comparative examples 1 and 2, it is clear that the addition of sulfate and the centrifugal washing need to be combined simultaneously to obtain a precursor having a proper sulfate doping amount.
From the data of example 1 and comparative example 3, it is understood that too much sulfate doping can seriously affect the electrochemical properties of the materials.
In summary, in the process of preparing the nickel-cobalt-manganese ternary positive electrode precursor, the sulfate solution is added into the raw materials for doping, and by controlling various parameters in the centrifugal washing process, reasonable doping of sulfate radical in the ternary positive electrode precursor is effectively realized, water consumption in the washing process is reduced, the manufacturing cost of the ternary positive electrode precursor is reduced, the structural stability of the positive electrode material obtained from the ternary positive electrode precursor is ensured, and the electrochemical performance of the ternary positive electrode material is improved. The battery obtained by the ternary precursor provided by the invention can be cycled for at least 170 times under the condition of 1C, and the battery capacity can be less than 80%.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (25)
1. A method for preparing a ternary positive electrode precursor, comprising the steps of:
adding a mixed salt solution of nickel, cobalt and manganese, a sulfate solution, a precipitant solution and a complexing agent solution into a base solution in parallel flow, performing coprecipitation reaction, and centrifugally washing a product of the coprecipitation reaction to obtain the ternary positive electrode precursor;
wherein the doping amount of sulfate radical in the ternary anode precursor is 2000-20000 ppm; the centrifugal washing comprises alkali liquor washing and water washing in sequence.
2. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the total concentration of metal ions in the mixed salt solution of nickel, cobalt and manganese is 0.1-5 mol/L.
3. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the concentration of the sulfate solution is 0.5-5 mol/L.
4. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the mixed salt solution of nickel, cobalt and manganese comprises any one or a combination of at least two of a mixed chloride salt of nickel, cobalt and manganese, a mixed sulfate salt of nickel, cobalt and manganese, a mixed nitrate salt of nickel, cobalt and manganese, and a mixed acetate salt of nickel, cobalt and manganese.
5. The method for producing a ternary positive electrode precursor according to claim 1, wherein the sulfate solution comprises any one or a combination of at least two of a sodium sulfate salt solution, an ammonia sulfate salt solution, and a potassium sulfate solution.
6. The method of preparing a ternary positive electrode precursor according to claim 1, wherein the precipitant comprises NaOH, KOH, ba (OH) 2 Or Na (or) 2 CO 3 Any one or a combination of at least two of these.
7. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the concentration of the precipitant solution is 2-15 mol/L.
8. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the complexing agent comprises any one or a combination of at least two of hydrazine hydrate, ammonia water or oxalic acid.
9. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the concentration of the complexing agent solution is 4-12 mol/L.
10. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the pH value of the base solution is 9 to 13.
11. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the concentration of the complexing agent in the base solution is 0-2 mol/L and does not include 0.
12. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the feeding speed of the mixed salt solution of nickel, cobalt and manganese is 4-100L/h.
13. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the feeding rate of the sulfate solution is 2-50L/h.
14. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the feeding rate of the precipitant solution is 1-20L/h.
15. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the feeding speed of the complexing agent solution is 0.5-10L/h.
16. The method of preparing a ternary positive electrode precursor according to claim 1, wherein the co-precipitation reaction is performed under a protective atmosphere.
17. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the reaction temperature of the coprecipitation reaction is 40-80 ℃.
18. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the pH value in the coprecipitation reaction is 9 to 13.
19. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the rotational speed of the centrifugal washing is 1000-2000 rpm.
20. The method for preparing ternary positive electrode precursor according to claim 1, wherein the volume of the alkaline solution used per 100kg of material in the alkaline solution washing process is 1-3 m 3 。
21. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the volume of water used per 100kg of material in the water washing process is 1-5 m 3 。
22. The method for preparing a ternary positive electrode precursor according to claim 1, wherein the method for preparing comprises:
adding a mixed salt solution of nickel, cobalt and manganese, a sulfate solution, a precipitant solution and a complexing agent solution into a base solution in parallel flow, wherein the feeding speed of the mixed salt solution of nickel, cobalt and manganese is 4-100L/h, the feeding speed of the sulfate solution is 2-50L/h, the feeding speed of the precipitant solution is 1-20L/h, the feeding speed of the complexing agent solution is 0.5-10L/h, performing coprecipitation reaction under the condition that the pH value is kept to be 9-13 at the reaction temperature of 40-80 ℃ in a protective atmosphere, and then sequentially performing centrifugal washing of alkali liquor and centrifugal washing of water on the product of the coprecipitation reaction at the rotating speed of 1000-2000 rpm to obtain the ternary positive electrode precursor;
wherein the total concentration of metal ions in the nickel-cobalt-manganese mixed salt solution is 0.1-5 mol/L, the concentration of sulfate solution is 0.5-5 mol/L, the concentration of precipitant solution is 2-15 mol/L, the concentration of complexing agent solution is 4-12 mol/L, the pH value of base solution is 9-13, the concentration of complexing agent in the base solution is 0-2 mol/L and does not comprise 0; the volume of the alkali liquor used in every 100kg of materials in the centrifugal washing process of the alkali liquor is 1-3 m 3 The volume of water used per 100kg of materials in the centrifugal washing process of water is 1-5 m 3 The method comprises the steps of carrying out a first treatment on the surface of the The doping amount of sulfate radical in the ternary anode precursor is 2000-20000 ppm.
23. A ternary positive electrode precursor, characterized in that the ternary positive electrode precursor is prepared by the preparation method of the ternary positive electrode precursor according to any one of claims 1-22, the ternary positive electrode precursor is doped with sulfate radical, and the doping amount of the sulfate radical in the ternary positive electrode precursor is 2000-20000 ppm.
24. A ternary positive electrode material, wherein the ternary positive electrode material is obtained by mixing and sintering the ternary positive electrode precursor according to claim 23 and a lithium source.
25. A lithium ion battery comprising the ternary cathode material of claim 24.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210678654.4A CN114890482B (en) | 2022-06-15 | 2022-06-15 | Ternary positive electrode precursor and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210678654.4A CN114890482B (en) | 2022-06-15 | 2022-06-15 | Ternary positive electrode precursor and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114890482A CN114890482A (en) | 2022-08-12 |
| CN114890482B true CN114890482B (en) | 2023-11-03 |
Family
ID=82728641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210678654.4A Active CN114890482B (en) | 2022-06-15 | 2022-06-15 | Ternary positive electrode precursor and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114890482B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102086A (en) * | 2023-02-27 | 2023-05-12 | 荆门市格林美新材料有限公司 | Modified sodium ion battery anode precursor and preparation method and application thereof |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09245787A (en) * | 1996-03-07 | 1997-09-19 | Kansai Shokubai Kagaku Kk | Positive electrode active material for lithium secondary battery |
| JP2008251191A (en) * | 2007-03-29 | 2008-10-16 | Sumitomo Metal Mining Co Ltd | Positive active material for nonaqueous electrolyte secondary battery, its manufacturing method and nonaqueous electrolyte secondary battery using it |
| CN107108266A (en) * | 2014-12-22 | 2017-08-29 | 住友金属矿山株式会社 | Nickel cobalt manganese composite hydroxide and its manufacture method |
| CN109616658A (en) * | 2018-12-17 | 2019-04-12 | 中科廊坊过程工程研究院 | A kind of selenium, the nickelic positive electrode of sulfate radical codope and its preparation method and application |
| CN110817975A (en) * | 2019-09-19 | 2020-02-21 | 宜宾光原锂电材料有限公司 | Method for reducing sulfur content of ternary precursor |
| CN111170375A (en) * | 2020-01-07 | 2020-05-19 | 万华化学集团股份有限公司 | Ternary positive electrode material precursor and preparation method thereof |
| CN111370686A (en) * | 2020-03-20 | 2020-07-03 | 昆明理工大学 | Anion-cation co-doped modified lithium-rich manganese composite cathode material and preparation method thereof |
| CN111377487A (en) * | 2020-03-26 | 2020-07-07 | 江苏海基新能源股份有限公司 | Preparation method of Al and F co-doped high-nickel ternary cathode material |
| WO2020152910A1 (en) * | 2019-01-21 | 2020-07-30 | Ｊｘ金属株式会社 | Oxide-based positive electrode active material for solid-state lithium-ion batteries, method for producing precursor of oxide-based positive electrode active material for solid-state lithium-ion batteries, method for producing oxide-based positive electrode active material for solid-state lithium-ion batteries, and solid-state lithium-ion battery |
| CN111807421A (en) * | 2020-06-23 | 2020-10-23 | 湖南邦普循环科技有限公司 | Method for reducing sulfur content of precursor of nickel-cobalt-manganese ternary positive electrode material |
| CN111874958A (en) * | 2020-08-10 | 2020-11-03 | 浙江帕瓦新能源股份有限公司 | Wet synthesis method of NCMA high-nickel quaternary precursor |
| CN112194202A (en) * | 2020-10-19 | 2021-01-08 | 荆门市格林美新材料有限公司 | Method for reducing sulfur content of large-particle impurities of nickel-cobalt-manganese ternary precursor |
| CN112479261A (en) * | 2020-11-03 | 2021-03-12 | 北京科技大学 | Modification method for lithium-rich manganese-based material precursor through nickel sulfate solution hydrothermal treatment |
| CN113571696A (en) * | 2021-07-30 | 2021-10-29 | 浙江帕瓦新能源股份有限公司 | Quaternary doped ternary positive electrode material precursor, preparation method thereof and positive electrode material |
| CN113582249A (en) * | 2021-07-26 | 2021-11-02 | 广东佳纳能源科技有限公司 | Ternary precursor doped with metal elements, and preparation method and application thereof |
| WO2022007663A1 (en) * | 2020-07-07 | 2022-01-13 | 巴斯夫杉杉电池材料有限公司 | Lithium ion battery positive electrode active material and preparation method therefor |
| WO2022022198A1 (en) * | 2020-07-30 | 2022-02-03 | 巴斯夫杉杉电池材料有限公司 | Modified high-nickel positive electrode material and preparation method therefor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602004017798D1 (en) * | 2003-02-21 | 2009-01-02 | Toyota Motor Co Ltd | Active material for the positive electrode of a nonaqueous electrolyte secondary battery |
| JP6427921B2 (en) * | 2013-06-28 | 2018-11-28 | 日亜化学工業株式会社 | Cathode active material for non-aqueous secondary battery and method for producing the same |
-
2022
- 2022-06-15 CN CN202210678654.4A patent/CN114890482B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09245787A (en) * | 1996-03-07 | 1997-09-19 | Kansai Shokubai Kagaku Kk | Positive electrode active material for lithium secondary battery |
| JP2008251191A (en) * | 2007-03-29 | 2008-10-16 | Sumitomo Metal Mining Co Ltd | Positive active material for nonaqueous electrolyte secondary battery, its manufacturing method and nonaqueous electrolyte secondary battery using it |
| CN107108266A (en) * | 2014-12-22 | 2017-08-29 | 住友金属矿山株式会社 | Nickel cobalt manganese composite hydroxide and its manufacture method |
| CN109616658A (en) * | 2018-12-17 | 2019-04-12 | 中科廊坊过程工程研究院 | A kind of selenium, the nickelic positive electrode of sulfate radical codope and its preparation method and application |
| WO2020152910A1 (en) * | 2019-01-21 | 2020-07-30 | Ｊｘ金属株式会社 | Oxide-based positive electrode active material for solid-state lithium-ion batteries, method for producing precursor of oxide-based positive electrode active material for solid-state lithium-ion batteries, method for producing oxide-based positive electrode active material for solid-state lithium-ion batteries, and solid-state lithium-ion battery |
| CN110817975A (en) * | 2019-09-19 | 2020-02-21 | 宜宾光原锂电材料有限公司 | Method for reducing sulfur content of ternary precursor |
| CN111170375A (en) * | 2020-01-07 | 2020-05-19 | 万华化学集团股份有限公司 | Ternary positive electrode material precursor and preparation method thereof |
| CN111370686A (en) * | 2020-03-20 | 2020-07-03 | 昆明理工大学 | Anion-cation co-doped modified lithium-rich manganese composite cathode material and preparation method thereof |
| CN111377487A (en) * | 2020-03-26 | 2020-07-07 | 江苏海基新能源股份有限公司 | Preparation method of Al and F co-doped high-nickel ternary cathode material |
| CN111807421A (en) * | 2020-06-23 | 2020-10-23 | 湖南邦普循环科技有限公司 | Method for reducing sulfur content of precursor of nickel-cobalt-manganese ternary positive electrode material |
| WO2022007663A1 (en) * | 2020-07-07 | 2022-01-13 | 巴斯夫杉杉电池材料有限公司 | Lithium ion battery positive electrode active material and preparation method therefor |
| WO2022022198A1 (en) * | 2020-07-30 | 2022-02-03 | 巴斯夫杉杉电池材料有限公司 | Modified high-nickel positive electrode material and preparation method therefor |
| CN114068911A (en) * | 2020-07-30 | 2022-02-18 | 巴斯夫杉杉电池材料有限公司 | Modified high-nickel cathode material and preparation method thereof |
| CN111874958A (en) * | 2020-08-10 | 2020-11-03 | 浙江帕瓦新能源股份有限公司 | Wet synthesis method of NCMA high-nickel quaternary precursor |
| CN112194202A (en) * | 2020-10-19 | 2021-01-08 | 荆门市格林美新材料有限公司 | Method for reducing sulfur content of large-particle impurities of nickel-cobalt-manganese ternary precursor |
| CN112479261A (en) * | 2020-11-03 | 2021-03-12 | 北京科技大学 | Modification method for lithium-rich manganese-based material precursor through nickel sulfate solution hydrothermal treatment |
| CN113582249A (en) * | 2021-07-26 | 2021-11-02 | 广东佳纳能源科技有限公司 | Ternary precursor doped with metal elements, and preparation method and application thereof |
| CN113571696A (en) * | 2021-07-30 | 2021-10-29 | 浙江帕瓦新能源股份有限公司 | Quaternary doped ternary positive electrode material precursor, preparation method thereof and positive electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114890482A (en) | 2022-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101794097B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and positive electrode for rechargeable lithium battery and rechargeable lithium battery including the same | |
| CN113363492B (en) | Composite coating modified high-nickel NCA positive electrode material and preparation method thereof | |
| CN109546123B (en) | Vanadium pentoxide-coated core-shell structure gradient nickel-cobalt-manganese positive electrode material and preparation method thereof | |
| CN111916727B (en) | Dual-ion wet-doped ternary high-nickel cathode material and preparation method thereof | |
| KR20160149162A (en) | Positive electrode active material for secondary battery, method for preparing the same, and secondary battery comprising the same | |
| CN111653756B (en) | Positive active material precursor, preparation method thereof and positive active material | |
| CN110690416A (en) | High-nickel ternary positive electrode material for lithium secondary battery and preparation method thereof | |
| KR101051066B1 (en) | Method for manufacturing a metal composite oxide for a lithium secondary battery and a cathode active material comprising the same | |
| WO2009120019A1 (en) | Olivine-type cathode active material precursor for lithium battery, olivine-type cathode active material for lithium battery, method for preparing the same and lithium battery with the same | |
| CN107482192B (en) | Single crystal ternary positive electrode material, preparation method thereof and lithium ion battery | |
| CN111276688B (en) | Cerium-zirconium co-doped porous structure cathode material and preparation method thereof | |
| CN115224254B (en) | Cu, zn and Mg co-doped layered oxide sodium ion battery positive electrode material, and preparation method and application thereof | |
| KR20170076088A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| CN114243014A (en) | Single crystal ternary cathode material and preparation method and application thereof | |
| CN113479944A (en) | Preparation method of modified high-nickel ternary cathode material | |
| CN113651369A (en) | Spherical high-nickel ternary precursor material, preparation method thereof and high-nickel ternary cathode material | |
| CN114890482B (en) | Ternary positive electrode precursor and preparation method and application thereof | |
| CN116706048A (en) | Nickel-cobalt-manganese ternary positive electrode material, preparation method thereof and lithium ion battery | |
| CN115732674A (en) | Sodium anode precursor material and preparation method and application thereof | |
| CN114132911B (en) | Doped regenerated lithium iron phosphate material and preparation method and application thereof | |
| CN111807425A (en) | Method for preparing high-performance ternary positive electrode material of lithium ion battery under low ammonia concentration | |
| KR20140039651A (en) | Method for preparing nickel-manganese complex hydroxides for cathode materials in lithium batteries, nickel-manganese complex hydroxides prepared by the method and cathode materials in lithium batteries comprising the same | |
| CN116375111B (en) | Sodium ion battery, positive electrode material and precursor thereof and preparation method | |
| JP2012018832A (en) | Cathode active material for lithium secondary battery, manufacturing method thereof, precursor of cathode active material, manufacturing method thereof, and lithium secondary battery using cathode active material | |
| CN115231629B (en) | Preparation method of lithium-passing layered manganese-based oxide coated ternary positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |