CN116873985A - Preparation method of nickel-based ternary cathode material precursor with large (010) crystal face area - Google Patents
Preparation method of nickel-based ternary cathode material precursor with large (010) crystal face area Download PDFInfo
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- CN116873985A CN116873985A CN202310698744.4A CN202310698744A CN116873985A CN 116873985 A CN116873985 A CN 116873985A CN 202310698744 A CN202310698744 A CN 202310698744A CN 116873985 A CN116873985 A CN 116873985A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 239000013078 crystal Substances 0.000 title claims abstract description 173
- 239000002243 precursor Substances 0.000 title claims abstract description 108
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000010406 cathode material Substances 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- 239000011164 primary particle Substances 0.000 claims abstract description 78
- 230000012010 growth Effects 0.000 claims abstract description 40
- 238000000975 co-precipitation Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000008139 complexing agent Substances 0.000 claims abstract description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 29
- 239000007774 positive electrode material Substances 0.000 claims abstract description 29
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000011163 secondary particle Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000009826 distribution Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 124
- 239000000243 solution Substances 0.000 claims description 94
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 29
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- -1 nickel cobalt aluminum Chemical compound 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical group [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000002349 favourable effect Effects 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 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
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 37
- 239000001509 sodium citrate Substances 0.000 description 25
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 25
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 230000009647 facial growth Effects 0.000 description 9
- 239000003630 growth substance Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910001429 cobalt ion Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910001437 manganese ion Inorganic materials 0.000 description 5
- 229910001453 nickel ion Inorganic materials 0.000 description 5
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 4
- 239000001433 sodium tartrate Substances 0.000 description 4
- 229960002167 sodium tartrate Drugs 0.000 description 4
- 235000011004 sodium tartrates Nutrition 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- ZYKTVIDNXTWTNS-UHFFFAOYSA-L [Co].[Mn].[Ni](O)O Chemical compound [Co].[Mn].[Ni](O)O ZYKTVIDNXTWTNS-UHFFFAOYSA-L 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 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
- 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
- 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
- C01P2004/01—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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of a nickel-based ternary cathode material precursor with a large (010) crystal face area, which takes nickel-based inorganic salt or nickel-based organic salt as a raw material, and adopts a complexing agent without ammonium to react to prepare a quasi-spherical hydroxide seed crystal which is beneficial to the growth of the large (010) crystal face area precursor, has larger flaky primary particles and is loose in distribution; and (3) taking hydroxide seed crystals as a base material to carry out coprecipitation reaction, taking nickel-based inorganic salt or nickel-based organic salt as a raw material, and adopting an ammonium-containing complexing agent to carry out reaction to prepare the nickel-based layered ternary positive electrode material precursor with large primary particles (010) crystal face area and spherical-like secondary particles. The nickel-based ternary positive electrode material precursor prepared by the method has the advantages of good quality, large primary particle (010) crystal face area occupation ratio and good secondary particle sphericity.
Description
Technical Field
The invention belongs to the technical field of modification of nickel-based layered ternary cathode materials, and particularly relates to a preparation method of a nickel-based ternary cathode material precursor with a large (010) crystal face area.
Background
The nickel-cobalt-manganese/aluminum or nickel-cobalt-manganese-aluminum layered ternary anode material has the advantages of higher volume and mass energy density, moderate price and the like, and has become the first choice anode material for producing high-energy-density batteries in various large battery enterprises. Along with the higher requirements of downstream battery manufacturers on the performance of the nickel cobalt manganese/aluminum or nickel cobalt manganese aluminum layered ternary cathode material, the synthesis of the nickel cobalt manganese/aluminum or nickel cobalt manganese aluminum layered ternary cathode material is developed towards the direction of crystal face regulation. A large number of theoretical and practical research results show that: increasing (010) crystal face (the crystal face is Li) of nickel cobalt manganese/aluminum or nickel cobalt manganese aluminum layered ternary positive electrode material particles + Vertical crystal plane of the intercalation/deintercalation channel) area can raise its Li + Conductivity, so that the electrochemical performance can be greatly improved. One method for improving the crystal face area of nickel cobalt manganese/aluminum or nickel cobalt manganese aluminum layered anode material particles (010) is as follows: firstly, synthesizing a hydroxide precursor with relatively large (010) crystal face area, and obtaining the nickel-cobalt-manganese/aluminum or nickel-cobalt-manganese-aluminum layered ternary cathode material with large (010) crystal face area by controlling a subsequent calcination process by utilizing a certain inheritance relation between the nickel-cobalt-manganese/aluminum or nickel-cobalt-manganese-aluminum layered ternary cathode material (010) crystal face area and the hydroxide precursor (010) crystal face area.
Patent document CN113023791a reports: and (3) synthesizing a high-nickel ternary positive electrode material precursor with larger (010) crystal face area on the lithium-manganese-rich precursor template by adopting the precursor of the lithium-manganese-rich positive electrode material as the crystal face induction template. The lithium-rich manganese-based precursor serving as the high-nickel ternary positive electrode material precursor induction template is relatively superior to the crystal nucleus of the high-nickel ternary positive electrode material precursor, and the calcination temperature of the high-nickel ternary positive electrode material is lower than that of the lithium-rich manganese-based positive electrode material by about 150 ℃, so that the lithium-rich manganese-based precursor serving as the crystal nucleus of the high-nickel ternary positive electrode material precursor is difficult to diffuse into the nickel-rich layer in the calcination process, and the corresponding core part of the high-nickel ternary positive electrode material is inevitably rich in manganese, so that the circulation capacity of the high-nickel ternary positive electrode material is inevitably reduced.
Patent document CN111293305a reports: and crystal face growth regulators such as polyacrylamide, polyvinyl alcohol, polyethylene oxide, sodium polyacrylate, sodium alginate, polyvinylpyrrolidone and the like are adopted in the preparation stage and the growth process of the precursor seed crystal, so that a ternary precursor anode material precursor with a larger (010) crystal face area is synthesized. In the patent document CN106892464a, crystal face growth regulators, such as sodium dodecyl benzene sulfonate and thiobetaine, are used in the preparation stage and the growth process of the precursor seed crystal to synthesize a ternary positive electrode material precursor with a larger (010) crystal face area. In the patent document CN109742337a, a crystal face growth regulator, such as cetyltrimethylammonium bromide, is used to synthesize a ternary positive electrode material precursor with a larger crystal face area in the preparation stage and the growth process of the precursor seed crystal. In the patent document CN108269995a, crystal face growth regulators, such as CTMAB, triethanolamine, turkish red oil, are used to synthesize a ternary positive electrode material precursor with a larger crystal face area (010) in both the preparation stage and the growth process of the precursor seed crystal. In the above patent document (CN 111293305A, CN106892464A, CN109742337A, CN108269995 a), a crystal face growth regulator is used to regulate the (010) crystal face area of the ternary positive electrode material precursor, but although the effect is better, the crystal face growth regulator is used in the precursor seed crystal preparation stage and the growth process, the discharge amount of waste water is large, and the discharged waste water needs to be additionally recycled or subjected to innocent treatment, so that the environmental protection cost is relatively high.
Patent document CN112151790a adopts control of the reaction kinetics in the seed crystal preparation stage and precursor growth process, so as to regulate and control the area of each crystal face of the ternary precursor; in the preparation stage of the seed crystal and in the growth process of the precursor, the patent document CN113387399A controls the area of each crystal face of the high-nickel ternary anode material precursor by regulating and controlling the pH of key technological parameters and the dosage of the complexing agent; in the patent document CN113329975a, by a method of continuously adding seed crystals in the process of growing a precursor, the 001 peak of the crystal plane parameter in the prepared ternary cathode material precursor is lower than the 101 peak of the crystal plane parameter. In the preparation stage of the seed crystal and in the growth process of the precursor, the patent document CN112919553A obtains the ternary positive electrode material precursor with {010} crystal face family active crystal face ratio, active crystal face ratio up to 80 percent and concentrated granularity distribution by adjusting the concentration of transition metal ions and complexing agents in the coprecipitation reaction process. The method reported in the above patent document (CN 112151790A, CN113387399A, CN113329975A, CN112919553 a) can control the (010) crystal face area of the ternary cathode material precursor, but the control effect is limited.
In the seed crystal preparation stage, the patent document CN112086616A is used for preparing a flaky seed crystal which is favorable for growing a large (010) crystal face ternary positive electrode material precursor and has good dispersibility by increasing the concentration of ammonia water in a reaction solution and reducing the pH value so as to slow down the nucleation speed of hydroxide; and then growing a ternary positive electrode material precursor with primary particles of micron order and large (010) crystal face area on the seed crystal. The ternary positive electrode material precursor with a large (010) crystal face area can be prepared by adopting the method reported in the patent document, but the sphericity of secondary particles of the ternary positive electrode material precursor is poor, and the subsequent processing performance is affected.
Disclosure of Invention
Aiming at the defects of the existing preparation method of the nickel-based ternary cathode material with the large (010) crystal face area, the invention provides the preparation method of the nickel-based ternary cathode material precursor with the large (010) crystal face area, and the method is suitable for the existing production line equipment to regulate and control the crystal face area of the nickel-based ternary cathode material precursor (010), and finally the nickel-based ternary cathode material precursor with the large (010) crystal face area can be obtained.
The invention adopts the following technical proposal to solve the technical problems, and the preparation method of the nickel-based ternary positive electrode material precursor with large (010) crystal face area is characterized by comprising the following specific steps:
step S1, seed crystal preparation: the method comprises the steps of taking nickel-based inorganic salt or nickel-based organic salt as a raw material, adopting a complexing agent without ammonium to react to prepare a spherical hydroxide seed crystal which is favorable for growing a precursor with a large (010) crystal face area, wherein the spherical hydroxide seed crystal is large in flaky primary particles and loose in distribution, the spherical hydroxide seed crystal consists of flaky primary particles, the average diameter of the flaky primary particles is 0.5 mu m, the interval between the flaky primary particles is 0.1-0.5 mu m, and the complexing agent without ammonium is one or a combination of more of ethylenediamine tetraacetic acid (EDTA), citric acid, citrate, tartaric acid or tartrate;
step S2, a precursor growth stage: and (2) taking the hydroxide seed crystal obtained in the step (S1) as a base material to carry out coprecipitation reaction, taking nickel-based inorganic salt or nickel-based organic salt as a raw material, and adopting an ammonium-containing complexing agent to carry out reaction to prepare a nickel-based layered ternary positive electrode material precursor with large primary particle (010) crystal face area and spherical secondary particles, wherein the ammonium-containing complexing agent is one or a combination of more of ammonia water, ammonium sulfite, ammonium bisulfite, ammonium sulfate, ammonium bisulfate, ammonium sulfide, ammonium hydrosulfide, ammonium thiosulfate, ammonium chloride or ammonium carbonate.
Further defined, the nickel-based inorganic salt or the nickel-based organic salt in the step S1 and the step S2 are the same, the nickel-based inorganic salt is nickel-based sulfate, nickel-based nitrate or nickel-based chloride, the nickel-based organic salt is nickel-based acetate, and the nickel base in the nickel-based inorganic salt or the nickel-based organic salt is nickel cobalt manganese, nickel cobalt aluminum or nickel cobalt manganese aluminum.
Further defined, the specific process of step S1 is: under inert gas atmosphere, respectively adding nickel-based inorganic salt or nickel-based organic salt solution, naOH solution and complexing agent without ammonium radical into a reaction kettle which takes complexing agent without ammonium radical as base water, controlling the pH value in the reaction kettle to be 10.0-12.5, simultaneously controlling the concentration of complexing agent without ammonium radical in the reaction kettle to be 0.01-1.0mol/L, and reacting for 1-5 hours at 40-60 ℃ to obtain hydroxide seed crystal.
Further limited, the molar concentration of the nickel-based inorganic salt or the nickel-based organic salt solution in the step S1 is 1.0-3.0mol/L, the molar concentration of the NaOH solution is 2.0-6.0mol/L, the molar concentration of the complexing agent without ammonium is 2.0-5.0mol/L, the feeding mass ratio of the nickel-based inorganic salt or the nickel-based organic salt solution to the NaOH solution is 1.5-3:1, the pH value in the reaction kettle is controlled to be 11.3-11.6, and the concentration of the complexing agent without ammonium in the reaction kettle is controlled to be 0.1-0.2mol/L.
Further defined, the specific process of step S2 is: and (2) respectively dropwise adding nickel-based inorganic salt or nickel-based organic salt solution, naOH solution and ammonium-containing complexing agent into the reaction kettle of which the hydroxide seed crystal is prepared in the step (S1), controlling the pH value in the reaction kettle to be 10.5-12.0, simultaneously controlling the concentration of the ammonium-containing complexing agent in the reaction kettle to be 0.1-1.0mol/L, reacting for 30-60 hours at the temperature of 40-60 ℃ to obtain slurry, and washing and drying the slurry to obtain the nickel-based layered ternary cathode material precursor.
Further limited, the molar concentration of the nickel-based inorganic salt or the nickel-based organic salt solution in the step S2 is 1.0-3.0mol/L, the molar concentration of the NaOH solution is 2.0-6.0mol/L, the molar concentration of the ammonium-containing complexing agent is 5.0-15.0mol/L, the feeding mass ratio of the nickel-based inorganic salt or the nickel-based organic salt solution to the NaOH solution is 1.5-3:1, the pH value in the reaction kettle is controlled to be 11.0-11.4, and the concentration of the ammonium-containing complexing agent in the reaction kettle is controlled to be 0.3-0.4mol/L.
In the preparation method, nickel, cobalt and manganese ions can form a complex with the complex without ammonium and the complex with ammonium, so as to play a role in reducing the concentration of the nickel, cobalt and manganese ions participating in the reaction solution; the complex formed by the complex without ammonium and nickel, cobalt and manganese ions is more stable than the complex with ammonium. In the preparation of crystal nucleus stage, the invention forms relatively stable complex with nickel, cobalt and manganese ions by using the complex free of ammonium, in the preparation process of the precursor crystal seed, the nucleation speed of hydroxide (cobalt nickel hydroxide manganese) can be slowed down, compared with the complex free of ammonium, the morphology of primary particles and secondary particles of the crystal seed can be controlled more favorably by using the complex free of ammonium, so that the quasi-spherical crystal seed which is favorable for growing into the nickel-based ternary positive electrode material precursor with large (010) crystal face area can be prepared, the morphology of the crystal seed is that the diameter of flaky primary particles is about 0.5 mu m, the interval between flaky primary particles is 0.2-0.5 mu m, the gap between flaky primary particles of the crystal seed is enough large, the space for the transverse (thickness direction) growth of primary particles in the subsequent precursor growth stage is large, and the crystal seed can be further used for growing into the nickel-based ternary positive electrode material precursor with large primary particle (010) crystal face area and the quasi-spherical secondary particles.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. compared with the method for preparing the hydroxide precursor with large primary particle (010) crystal face area and spherical secondary particle by adopting the complexing agent without ammonium radical in the seed crystal preparation stage and the growth stage, the invention adopts the complexing agent without ammonium radical in the seed crystal preparation stage, and the subsequent wastewater which needs to be treated and does not contain ammonium radical complexing agent is less, and the process cost is relatively low.
2. Compared with the method for preparing the hydroxide precursor with large primary particle (010) crystal face area and spherical secondary particle by adopting the crystal face growth regulator in the crystal seed preparation stage and the crystal face growth stage, the method does not need to adopt the surfactant with relatively high price as the crystal face growth regulator, does not need to treat the wastewater containing the surfactant in the subsequent stage, and has relatively low process cost.
3. The nickel-based ternary positive electrode material precursor prepared by the method has the advantages of good quality, large primary particle (010) crystal face area occupation ratio and good secondary particle sphericity.
Drawings
FIG. 1 is a SEM image of seed crystals prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the precursor prepared in example 1 of the present invention.
FIG. 3 is an SEM image of the seed crystal prepared in comparative example 1 of the present invention.
Fig. 4 is an SEM image of the precursor prepared in comparative example 1 of the present invention.
Fig. 5 is an SEM image of the precursor prepared in comparative example 2 of the present invention.
FIG. 6 is a SEM image of seed crystals prepared in comparative example 3 of the present invention
Fig. 7 is an SEM image of the precursor prepared in comparative example 3 of the present invention.
Fig. 8 is an SEM image of the precursor prepared in comparative example 4 of the present invention.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Examples
1) Seed crystal preparation stage: under nitrogen atmosphere, MSO of 1.5mol/L is added 4 (m=ni, co, mn, wherein the molar ratio of Ni: co: mn is 0.83:0.07:0.1), 6.0mol/L NaOH solution and 2mol/L sodium citrate solution are added to a reaction vessel containing 0.1mol/L sodium citrate solution as bottom water, wherein MSO 4 The feeding speed of the solution is 50mL/min, the feeding speed of the NaOH solution is about 25mL/min, the pH value of the coprecipitation reaction is controlled to be 11.8, the temperature of the coprecipitation reaction is controlled to be 52 ℃, the sodium citrate concentration in the coprecipitation reaction kettle is controlled to be about 0.1mol/L, the continuous feeding is carried out, and Ni is obtained after 2 hours of reaction 0.83 Co 0.07 Mn 0.1 (OH) 2 As shown in FIG. 1, the seed crystal is sphere-like and consists of flaky primary particles, the diameters of the flaky primary particles are about 0.5 mu m, the distance between the flaky primary particles is about 0.2 mu m, the gaps between the flaky primary particles are larger, and the space for the transverse (thickness direction) growth of the primary particles in the subsequent precursor growth stage is larger, so that the Ni with larger crystal face area of the primary particles (010) can be prepared 0.83 Co 0.07 Mn 0.1 (OH) 2 A precursor. After filtration, the sodium citrate attached to the seed crystal was washed off with deionized water.
2) Precursor growth stage: taking the seed crystal prepared in the step 1) as a base material, and under the nitrogen atmosphere, carrying out MSO (methyl methacrylate) with the concentration of 1.5mol/L 4 (m=ni, co, mn, wherein the molar ratio of Ni: co: mn is 0.83:0.07:0.1) solution, 6.0mol/L NaOH solution and 12.0mol/L aqueous ammonia are added to a reaction vessel containing 0.3mol/L aqueous ammonia and seed crystals prepared in step 1) as base water, whichMSO in (B) 4 The feeding speed of the solution is 90mL/min, the feeding speed of the NaOH solution is about 45mL/min, the pH value in the reaction kettle is controlled to be 11.2, the coprecipitation reaction temperature is controlled to be 52 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.3mol/L, the continuous feeding is carried out, and Ni is obtained after the reaction is carried out for 70 hours 0.83 Co 0.07 Mn 0.1 (OH) 2 Washing and drying the slurry to obtain Ni with large primary particle (010) crystal face area 0.83 Co 0.07 Mn 0.1 (OH) 2 The precursor is shown in fig. 2.
Examples
1) Seed crystal preparation stage: under nitrogen atmosphere, 2.0mol/L MSO 4 (m=ni, co, mn, wherein the molar ratio of ni:co:mn:al is 0.97:0.01:0.01:0.01) solution, 5.0mol/L NaOH solution and 2mol/L sodium tartrate and 2mol/L sodium citrate mixed solution are added into a reaction kettle containing 0.05mol/L sodium tartrate and 0.05mol/L sodium citrate solution as bottom water, wherein MSO 4 The feeding speed of the solution is 30mL/min, the feeding speed of the NaOH solution is about 25mL/min, the pH value is controlled to be 11.8, the coprecipitation reaction temperature is controlled to be 55 ℃, the concentration of the mixed solution of sodium tartrate and sodium citrate in the coprecipitation reaction kettle is controlled to be about 0.1mol/L, the continuous feeding is carried out, and Ni is obtained after the reaction for 3 hours 0.97 Co 0.01 Mn 0.01 Al 0.01 (OH) 2 Seed crystals, which are sphere-like and consist of flaky primary particles having a diameter of about 0.5 μm and a spacing between the flaky primary particles of about 0.3 μm. The gaps among the flaky primary particles are larger, and the space for the transverse (thickness direction) growth of the primary particles in the subsequent precursor growth stage is larger, so that the Ni with larger crystal face area of the primary particles (010) can be prepared 0.83 Co 0.07 Mn 0.1 (OH) 2 A precursor. After filtration, the sodium tartrate and sodium citrate attached to the seed crystal were washed off with deionized water.
2) Precursor growth stage: taking the seed crystal prepared in the step 1) as a base material, and under the nitrogen atmosphere, 2.0mol/L MSO 4 (Ni: co: mn: al molar ratio of 0.97:0.01:0.01:0.01), 5.0mol/L NaOH solution and 10.0mol/LAdding ammonia water into a reaction kettle which contains 0.4mol/L ammonia water with seed crystal prepared in the step 1) as bottom water, wherein MSO 4 The feeding speed of the solution is 120mL/min, the feeding speed of the NaOH solution is about 100mL/min, the pH value in the reaction kettle is controlled to be 10.9, the coprecipitation reaction temperature is controlled to be 53 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.4mol/L, and Ni is obtained after 80 hours of reaction 0.97 Co 0.01 Mn 0.01 Al 0.01 (OH) 2 Washing and drying the slurry to obtain Ni with large primary particle (010) crystal face area 0.97 Co 0.01 Mn 0.01 Al 0.01 (OH) 2 A precursor.
Examples
1) Seed crystal preparation stage: under nitrogen atmosphere, MSO of 1.5mol/L is added 4 (m=ni, co, mn, wherein the molar ratio of Ni: co: mn is 0.94:0.03:0.03), 6.0mol/L NaOH solution and 3mol/L ethylenediamine tetraacetic acid solution are added to a reaction vessel containing 0.15mol/L ethylenediamine tetraacetic acid solution as a base water, the pH is controlled to 11.9, wherein the MSO 4 The feeding speed of the solution is 50mL/min, the feeding speed of the NaOH solution is about 25mL/min, the coprecipitation reaction temperature is controlled to be 55 ℃, the concentration of the ethylenediamine tetraacetic acid solution in the coprecipitation reaction kettle is controlled to be about 0.15mol/L, the continuous feeding is carried out, and the Ni is obtained after 2 hours of reaction 0.94 Co 0.03 Mn 0.03 (OH) 2 Seed crystals, which are sphere-like and consist of flaky primary particles having a diameter of about 0.5 μm and a spacing between the flaky primary particles of about 0.2 μm. The gaps among the flaky primary particles are larger, and the space for the transverse (thickness direction) growth of the primary particles in the subsequent precursor growth stage is larger, so that the Ni with larger crystal face area of the primary particles (010) can be prepared 0.83 Co 0.07 Mn 0.1 (OH) 2 A precursor. After filtration, ethylenediamine tetraacetic acid attached to the seed crystal was washed off with deionized water.
2) Precursor growth stage: taking the seed crystal prepared in the step 1) as a base material, and under the nitrogen atmosphere, carrying out MSO (methyl methacrylate) with the concentration of 1.5mol/L 4 (m=ni, co, mn, where the molar ratio of Ni: co: mn is 0.94:0.03:0.03), 6.Adding 0mol/L NaOH solution and 12.0mol/L ammonia water into a reaction kettle with 0.3mol/L ammonia water and seed crystal prepared in the step 1) as bottom water, wherein MSO 4 The feeding speed of the solution is 100mL/min, the feeding speed of the NaOH solution is about 50mL/min, the pH value in the reaction kettle is controlled to be 11.0, the coprecipitation reaction temperature is controlled to be 52 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.3mol/L, and Ni is obtained after 80 hours of reaction 0.94 Co 0.03 Mn 0.03 (OH) 2 Washing and drying the slurry to obtain Ni with large primary particle (010) crystal face area 0.94 Co 0.03 Mn 0.03 (OH) 2 The precursor, the primary particle sheet is thick, and the (010) crystal face area is large.
Examples
1) Seed crystal preparation stage: under nitrogen atmosphere, 2.0mol/L MSO 4 (m=ni, co, mn, wherein the molar ratio of Ni: co: mn is 0.65:0.15:0.2), 6.0mol/L NaOH solution and 3mol/L ethylenediamine tetraacetic acid solution are added to a reaction vessel containing 0.1mol/L ethylenediamine tetraacetic acid solution as a base water, wherein MSO 4 The feeding speed of the solution is 40mL/min, the feeding speed of the NaOH solution is about 23mL/min, the pH value is controlled to be 12.1, the coprecipitation reaction temperature is controlled to be 55 ℃, the concentration of the ethylenediamine tetraacetic acid solution in the coprecipitation reaction kettle is controlled to be about 0.1mol/L, the continuous feeding is carried out, and Ni is obtained after the reaction for 1 hour 0.65 Co 0.15 Mn 0.2 (OH) 2 Seed crystals, which are sphere-like and consist of flaky primary particles having a diameter of about 0.5 μm and a spacing between the flaky primary particles of about 0.35 μm. The gaps among the flaky primary particles are larger, and the space for the transverse (thickness direction) growth of the primary particles in the subsequent precursor growth stage is larger, so that the Ni with larger crystal face area of the primary particles (010) can be prepared 0.83 Co 0.07 Mn 0.1 (OH) 2 A precursor. After filtration, ethylenediamine tetraacetic acid attached to the seed crystal was washed off with deionized water.
2) Precursor growth stage: taking the seed crystal prepared in the step 1) as a base material, and under the nitrogen atmosphere, 2.0mol/L MSO 4 (m=ni, co, mn, where Ni: co: mnThe molar ratio of 0.65:0.15:0.2) solution, 6.0mol/L NaOH solution and 12.0mol/L ammonia water are added into a reaction kettle which takes 0.25mol/L ammonia water with the seed crystal prepared in the step 1) as bottom water, wherein MSO 4 The feeding speed of the solution is 90mL/min, the feeding speed of the NaOH solution is about 60mL/min, the pH value in the reaction kettle is controlled to be 11.3, the coprecipitation reaction temperature is controlled to be 55 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.25mol/L, and Ni is obtained after the reaction for 60 hours 0.65 Co 0.15 Mn 0.2 (OH) 2 Washing and drying the slurry to obtain Ni with large primary particle (010) crystal face area 0.65 Co 0.15 Mn 0.2 (OH) 2 A precursor.
Comparative example 1
1) Seed crystal preparation stage: under nitrogen atmosphere, MSO of 1.5mol/L is added 4 (M=Ni, co, mn, wherein the molar ratio of Ni to Co to Mn is 0.83:0.07:0.1), 6.0mol/L NaOH solution and 12.0mol/L ammonia water are added into a reaction kettle which takes 0.3mol/L ammonia water solution as bottom water, wherein MSO 4 The feeding speed of the solution is 50mL/min, the feeding speed of the NaOH solution is about 25mL/min, the pH value is controlled to be 11.8, the coprecipitation reaction temperature is controlled to be 52 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.3mol/L for continuous feeding, and Ni is obtained after 2 hours of reaction 0.83 Co 0.07 Mn 0.1 (OH) 2 As shown in FIG. 3, the seed crystal is of a sphere-like shape and is composed of flaky primary particles with a diameter of about 0.3 μm, a spacing between the flaky primary particles of about 0.05 μm, a smaller gap between the flaky primary particles, and a smaller space for the lateral (thickness) growth of the primary particles in the subsequent precursor growth stage, and it is difficult to prepare Ni with a larger crystal face area of the primary particles (010) 0.83 Co 0.07 Mn 0.1 (OH) 2 A precursor.
2) Precursor growth stage: taking the seed crystal prepared in the step 1) as a base material, and under the nitrogen atmosphere, carrying out MSO (methyl methacrylate) with the concentration of 1.5mol/L 4 (m=ni, co, mn, wherein the molar ratio of Ni: co: mn is 0.83:0.07:0.1) solution, 6.0mol/L NaOH solution and 12.0mol/L ammonia are added to a solution containing 0.3mol/L ammonia and 12.0mol/L ammoniaIn a reaction kettle taking seed crystal prepared in the step 1) as bottom water, MSO 4 The feeding speed of the solution is 90mL/min, the feeding speed of the NaOH solution is about 45mL/min, the pH value in the reaction kettle is controlled to be 11.2, the coprecipitation reaction temperature is controlled to be 52 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.3mol/L, and Ni is obtained after 70 hours of reaction 0.83 Co 0.07 Mn 0.1 (OH) 2 Washing and drying the slurry to obtain Ni with smaller primary particle (010) crystal face area 0.83 Co 0.07 Mn 0.1 (OH) 2 The precursor is shown in fig. 4.
Comparative example 2
1) Seed crystal preparation stage: under nitrogen atmosphere, MSO of 1.5mol/L is added 4 (m=ni, co, mn, wherein the molar ratio of Ni: co: mn is 0.83:0.07:0.1), 6.0mol/L NaOH solution and 2mol/L sodium citrate solution are added to a reaction vessel containing 0.1mol/L sodium citrate solution as bottom water, wherein MSO 4 The feeding speed of the solution is 50mL/min, the feeding speed of the NaOH solution is about 25mL/min, the pH value of the coprecipitation reaction is controlled to be 11.8, the temperature of the coprecipitation reaction is controlled to be 52 ℃, the sodium citrate concentration in the coprecipitation reaction kettle is controlled to be about 0.1mol/L, the continuous feeding is carried out, and Ni is obtained after 2 hours of reaction 0.83 Co 0.07 Mn 0.1 (OH) 2 Seed crystals, as shown in fig. 1, which are spheroid and composed of flaky primary particles having a diameter of about 0.5 μm and a spacing between the flaky primary particles of about 0.2 μm. The gaps among the flaky primary particles are larger, and the space for the transverse (thickness direction) growth of the primary particles in the subsequent precursor growth stage is larger, so that the Ni with larger crystal face area of the primary particles (010) can be prepared 0.83 Co 0.07 Mn 0.1 (OH) 2 The precursor is filtered and then washed with deionized water to remove sodium citrate attached to the seed crystal.
2) Precursor growth stage: taking the seed crystal prepared in the step 1) as a base material, and under the nitrogen atmosphere, carrying out MSO (methyl methacrylate) with the concentration of 1.5mol/L 4 (m=ni, co, mn, wherein the molar ratio of Ni: co: mn is 0.83:0.07:0.1), 6.0mol/L NaOH solution and 2mol/L sodium citrate solution are added to the mixture containing the concentrateIn a reaction kettle taking sodium citrate solution with the temperature of 0.1mol/L and seed crystal prepared in the step 1) as bottom water, MSO 4 The feeding speed of the solution is 90mL/min, the feeding speed of the NaOH solution is about 45mL/min, the pH value in the reaction kettle is controlled to be 11.0, the coprecipitation reaction temperature is controlled to be 52 ℃, the concentration of the sodium citrate solution in the coprecipitation reaction kettle is controlled to be about 0.1mol/L, the continuous feeding is carried out, and Ni is obtained after 75 hours of reaction 0.83 Co 0.07 Mn 0.1 (OH) 2 Washing and drying the slurry to obtain Ni with smaller primary particle (010) crystal face area 0.83 Co 0.07 Mn 0.1 (OH) 2 The precursor is shown in fig. 5.
Comparative example 3
1) Seed crystal preparation stage: under nitrogen atmosphere, MSO of 1.5mol/L is added 4 (m=ni, co, mn, where Ni: co: mn molar ratio is 0.83:0.07:0.1) solution, 6.0mol/L NaOH solution, 12.0mol/L aqueous ammonia and 2mol/L sodium citrate solution are added to a reaction vessel containing 0.2mol/L aqueous ammonia and 0.05mol/L sodium citrate solution as bottom water, where MSO 4 The feeding speed of the solution is 50mL/min, the feeding speed of the NaOH solution is about 25mL/min, the pH value of the coprecipitation reaction is controlled to be 11.8, the temperature of the coprecipitation reaction is controlled to be 52 ℃, the concentration of ammonia water in a coprecipitation reaction kettle is controlled to be about 0.2mol/L and the concentration of sodium citrate is controlled to be about 0.05mol/L, the feeding is continued, and Ni is obtained after 2 hours of reaction 0.83 Co 0.07 Mn 0.1 (OH) 2 As shown in fig. 6, the seed crystal is of a spheroid shape and is composed of flaky primary particles having a diameter of about 0.5 μm and a spacing between the flaky primary particles of about 0.2 μm. The gaps among the flaky primary particles are larger, and the space for the transverse (thickness direction) growth of the primary particles in the subsequent precursor growth stage is larger, so that the Ni with larger crystal face area of the primary particles (010) can be prepared 0.83 Co 0.07 Mn 0.1 (OH) 2 A precursor. After filtration, sodium citrate and ammonia water attached to the seed crystal were washed off with deionized water.
2) Precursor growth stage: taking the seed crystal prepared in the step 1) as a base material, and under the nitrogen atmosphere, carrying out MSO (methyl methacrylate) with the concentration of 1.5mol/L 4 (m=ni, co, mn, wherein the molar ratio of Ni: co: mn is 0.83:0.07:0.1) solution, 6.0mol/L NaOH solution, 12.0mol/L aqueous ammonia and 2mol/L sodium citrate solution are added to a reaction vessel containing 0.2mol/L aqueous ammonia and 0.05mol/L sodium citrate solution and seed crystals prepared in step 1) as bottom water, wherein MSO 4 The feeding speed of the solution is 90mL/min, the feeding speed of the NaOH solution is about 45mL/min, the pH value in the reaction kettle is controlled to be 11.1, the coprecipitation reaction temperature is controlled to be 52 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.2mol/L and the concentration of the sodium citrate solution is controlled to be about 0.05mol/L, the continuous feeding is carried out, and the Ni is obtained after the reaction is carried out for 72 hours 0.83 Co 0.07 Mn 0.1 (OH) 2 Washing and drying the slurry to obtain Ni with smaller primary particle (010) crystal face area 0.83 Co 0.07 Mn 0.1 (OH) 2 The precursor is shown in fig. 7.
Comparative example 4
1) Seed crystal preparation stage: under nitrogen atmosphere, MSO of 1.5mol/L is added 4 (M=Ni, co, mn, wherein the molar ratio of Ni to Co to Mn is 0.83:0.07:0.1), 6.0mol/L NaOH solution and 12.0mol/L ammonia water are added into a reaction kettle which takes 0.3mol/L ammonia water solution as bottom water, wherein MSO 4 The feeding speed of the solution is 50mL/min, the feeding speed of the NaOH solution is about 25mL/min, the pH value is controlled to be 11.8, the coprecipitation reaction temperature is controlled to be 52 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be about 0.3mol/L, the continuous feeding is carried out, and Ni is obtained after 2 hours of reaction 0.83 Co 0.07 Mn 0.1 (OH) 2 Seed crystals, as shown in FIG. 3, which are spheroid and composed of flaky primary particles having a diameter of about 0.2 μm and a spacing between flaky primary particles of about 0.1. Mu.m. The gaps among the flaky primary particles are smaller, the space for the transverse (thickness direction) growth of the primary particles in the subsequent precursor growth stage is smaller, and Ni with larger crystal face area of the primary particles (010) is difficult to prepare 0.83 Co 0.07 Mn 0.1 (OH) 2 A precursor.
2) Precursor growth stage: taking the seed crystal prepared in the step 1) as a base material, and under the nitrogen atmosphere, carrying out the steps ofMSO of 1.5mol/L 4 (m=ni, co, mn, wherein the molar ratio of Ni: co: mn is 0.83:0.07:0.1) solution, 6.0mol/L NaOH solution and 2mol/L sodium citrate solution are added to a reaction vessel containing 0.1mol/L sodium citrate solution and seed crystals prepared in step 1) as bottom water, wherein MSO 4 The feeding speed of the solution is 90mL/min, the feeding speed of the NaOH solution is about 40mL/min, the pH value in the reaction kettle is controlled to be 11.0, the coprecipitation reaction temperature is controlled to be 52 ℃, the concentration of the sodium citrate solution in the coprecipitation reaction kettle is controlled to be about 0.1mol/L, the continuous feeding is carried out, and Ni is obtained after the reaction is carried out for 78 hours 0.83 Co 0.07 Mn 0.1 (OH) 2 Washing and drying the slurry to obtain Ni with smaller primary particle (010) crystal face area 0.83 Co 0.07 Mn 0.1 (OH) 2 The precursor is shown in fig. 8.
In the comparative examples and comparative examples, the morphology and arrangement density of primary particles of the seed crystal influence the crystal face area of the precursor (010) to be large, a relatively stable complex is formed by adopting a complex free of ammonium radical and nickel, cobalt and manganese ions in the preparation stage of the seed crystal, the nucleation speed of hydroxide (cobalt manganese nickel hydroxide) can be slowed down in the preparation process of the precursor seed crystal, compared with the morphology of primary particles and secondary particles of the seed crystal which are more favorable for controlling the morphology of the seed crystal by adopting the complex free of ammonium radical, the morphology of the seed crystal is similar to that of the precursor of the nickel-based ternary positive electrode material which is favorable for growing into the large (010) crystal face area, the diameter of the seed crystal is approximately 0.5 mu m, the space between the primary particles of the seed crystal is between the sheet is sufficiently large, the space between the primary particles of the seed crystal is 0.2-0.5 mu m, and the space for the lateral (thickness direction) growth of primary particles of the precursor in the subsequent growth stage is large, and the seed crystal can be further grown into the precursor of the nickel-based ternary positive electrode material which is similar to the spherical.
While the basic principles, principal features and advantages of the present invention have been described in the foregoing examples, it will be appreciated by those skilled in the art that the present invention is not limited by the foregoing examples, but is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the scope of the invention, which is defined by the appended claims.
Claims (6)
1. The preparation method of the nickel-based ternary cathode material precursor with large (010) crystal face area is characterized by comprising the following specific steps:
step S1, seed crystal preparation: the method comprises the steps of taking nickel-based inorganic salt or nickel-based organic salt as a raw material, adopting a complexing agent without ammonium to react to prepare a spherical hydroxide seed crystal which is favorable for growing a precursor with large (010) crystal face area, wherein the spherical hydroxide seed crystal is large in flaky primary particles and loose in distribution, the spherical hydroxide seed crystal consists of flaky primary particles, the average diameter of the flaky primary particles is 0.5 mu m, the interval between the flaky primary particles is 0.1-0.5 mu m, and the complexing agent without ammonium is one or a combination of more of ethylenediamine tetraacetic acid, citric acid, citrate, tartaric acid and tartrate;
step S2, a precursor growth stage: and (2) taking the hydroxide seed crystal obtained in the step (S1) as a base material to carry out coprecipitation reaction, taking nickel-based inorganic salt or nickel-based organic salt as a raw material, and adopting an ammonium-containing complexing agent to carry out reaction to prepare a nickel-based layered ternary positive electrode material precursor with large primary particle (010) crystal face area and spherical secondary particles, wherein the ammonium-containing complexing agent is one or a combination of more of ammonia water, ammonium sulfite, ammonium bisulfite, ammonium sulfate, ammonium bisulfate, ammonium sulfide, ammonium hydrosulfide, ammonium thiosulfate, ammonium chloride or ammonium carbonate.
2. The method for preparing a nickel-based ternary cathode material precursor with a large (010) crystal face area according to claim 1, wherein the method comprises the following steps: the nickel-based inorganic salt or the nickel-based organic salt in the step S1 and the step S2 are the same, wherein the nickel-based inorganic salt is nickel-based sulfate, nickel-based nitrate or nickel-based chloride, the nickel-based organic salt is nickel-based acetate, and the nickel base in the nickel-based inorganic salt or the nickel-based organic salt is nickel cobalt manganese, nickel cobalt aluminum or nickel cobalt manganese aluminum.
3. The method for preparing a nickel-based ternary cathode material precursor with a large (010) crystal face area according to claim 1, wherein the specific process of step S1 is as follows: under inert gas atmosphere, respectively adding nickel-based inorganic salt or nickel-based organic salt solution, naOH solution and complexing agent without ammonium radical into a reaction kettle which takes complexing agent without ammonium radical as base water, controlling the pH value in the reaction kettle to be 10.0-12.5, simultaneously controlling the concentration of complexing agent without ammonium radical in the reaction kettle to be 0.01-1.0mol/L, and reacting for 1-5 hours at 40-60 ℃ to obtain hydroxide seed crystal.
4. The method for preparing a nickel-based ternary cathode material precursor with a large (010) crystal face area according to claim 1, wherein the method comprises the following steps: the molar concentration of the nickel-based inorganic salt or the nickel-based organic salt solution in the step S1 is 1.0-3.0mol/L, the molar concentration of the NaOH solution is 2.0-6.0mol/L, the molar concentration of the complexing agent without ammonium is 2.0-5.0mol/L, the feeding mass ratio of the nickel-based inorganic salt or the nickel-based organic salt solution to the NaOH solution is 1.5-3:1, the pH value in the reaction kettle is controlled to be 11.3-11.6, and the concentration of the complexing agent without ammonium in the reaction kettle is controlled to be 0.1-0.2mol/L.
5. The method for preparing a nickel-based ternary cathode material precursor with a large (010) crystal face area according to claim 1, wherein the specific process of step S2 is as follows: and (2) respectively dropwise adding nickel-based inorganic salt or nickel-based organic salt solution, naOH solution and ammonium-containing complexing agent into the reaction kettle of which the hydroxide seed crystal is prepared in the step (S1), controlling the pH value in the reaction kettle to be 10.5-12.0, simultaneously controlling the concentration of the ammonium-containing complexing agent in the reaction kettle to be 0.1-1.0mol/L, reacting for 30-60 hours at the temperature of 40-60 ℃ to obtain slurry, and washing and drying the slurry to obtain the nickel-based layered ternary cathode material precursor.
6. The method for preparing a nickel-based ternary cathode material precursor with a large (010) crystal face area according to claim 1, wherein the method comprises the following steps: the molar concentration of the nickel-based inorganic salt or the nickel-based organic salt solution in the step S2 is 1.0-3.0mol/L, the molar concentration of the NaOH solution is 2.0-6.0mol/L, the molar concentration of the ammonium-containing complexing agent is 5.0-15.0mol/L, the feeding mass ratio of the nickel-based inorganic salt or the nickel-based organic salt solution to the NaOH solution is 1.5-3:1, the pH value in the reaction kettle is controlled to be 11.0-11.4, and the concentration of the ammonium-containing complexing agent in the reaction kettle is controlled to be 0.3-0.4mol/L.
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