CN110808367B - Ternary precursor and preparation method thereof - Google Patents
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- 239000002243 precursor Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 86
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 84
- 239000000243 solution Substances 0.000 claims abstract description 77
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 36
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 23
- 239000011572 manganese Substances 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000010955 niobium Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 4
- 150000002821 niobium Chemical class 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical group [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 4
- LDPWMGUFXYRDRG-UHFFFAOYSA-I niobium(5+) pentaacetate Chemical compound [Nb+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LDPWMGUFXYRDRG-UHFFFAOYSA-I 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229940118662 aluminum carbonate Drugs 0.000 claims description 2
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 claims description 2
- IIDYTZRUUWUVQF-UHFFFAOYSA-D niobium(5+) pentasulfate Chemical compound [Nb+5].[Nb+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IIDYTZRUUWUVQF-UHFFFAOYSA-D 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 150000003839 salts Chemical class 0.000 abstract description 13
- 239000007864 aqueous solution Substances 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000010668 complexation reaction Methods 0.000 abstract description 2
- -1 nickel-cobalt-aluminum Chemical compound 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 7
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- TYYRFZAVEXQXSN-UHFFFAOYSA-H aluminium sulfate hexadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O TYYRFZAVEXQXSN-UHFFFAOYSA-H 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- JQOREDBDOLZSJY-UHFFFAOYSA-H bis(2,2-dioxo-1,3,2,4-dioxathialumetan-4-yl) sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O JQOREDBDOLZSJY-UHFFFAOYSA-H 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention provides a ternary precursor and a preparation method thereof, belonging to the technical field of lithium ion batteries. The chemical general formula of the ternary precursor provided by the invention is { [ Ni ]x1Coy1Mz1Nb(1‑x1‑y1‑z)]n[Nix2Coy2M(1‑x2‑y2)]1‑n}(OH)2Wherein x1 is more than or equal to 0.7 and less than or equal to 0.9, y1 is more than or equal to 0.01 and less than or equal to 0.2, z1 is more than or equal to 0.01 and less than or equal to 0.4, x2 is more than or equal to 0.4 and less than or equal to 0.7, y2 is more than or equal to 0.01 and less than or equal to 0.4 and less than or equal to 0.7, M = Mn or Al, Nb-doped high-nickel hydroxide is used as an inner core, and low-nickel hydroxide is used. The preparation method of the ternary precursor comprises the following steps: preparing A, B two solutions with the same total concentration but different molar ratios of nickel, cobalt and manganese or aluminum and other solutions; in the early stage, the soluble salt aqueous solution of nickel-cobalt-manganese or nickel-cobalt-aluminum, niobium salt and sodium hydroxide aqueous solution with high nickel ratio are subjected to coprecipitation reaction in a reaction kettle under the complexation of ammonia to prepare niobium-doped ternary hydroxide with proper granularity; and growing nickel-cobalt-manganese ternary hydroxide with low nickel proportion on the basis of the later period to synthesize the precursor of the niobium-doped ternary cathode material with the concentration layered structure with high internal nickel and low external nickel. The ternary precursor material prepared by the method has a uniform and compact surface and orderly arranged structure, and provides a foundation for realizing excellent electrochemical performance of the ternary cathode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to a ternary precursor of a lithium ion battery anode material and a preparation method thereof, and particularly relates to a wet-process controllable-concentration layered Nb-doped ternary anode material precursor and a preparation method thereof.
Background
The lithium ion battery has the characteristics of high working voltage, high energy density, long cycle life, small self-discharge rate, low pollution, no memory effect and the like, and is a research and application hotspot of the current energy industry. The lithium ion battery has wide application prospect in the fields of new energy electric vehicles, digital products, mobile phones and the like, and along with the continuous development of the electric vehicle industry, people put forward higher and higher requirements on the safety, the charge-discharge specific capacity and the cycle life of the lithium ion battery. Therefore, development of novel electrode materials to meet the demand of the future electromotive market is urgently required. The layered nickel-rich ternary cathode material (NCM, NCA) is considered to be one of the most promising cathode materials due to its advantages of high charge and discharge capacity, low price, low toxicity, etc. However, the material has the problems of low coulombic efficiency, easy collapse of a laminated structure and the like for the first time, so that the material has the defects of rapid voltage platform and capacity attenuation, poor rate capability and the like in the circulating process, and the industrialization of the material is seriously hindered.
Currently, in order to solve these problems, researchers have coated or doped foreign ions on the surface of a layered nickel-rich ternary particle. The coating material may be an inactive substance such as a metal oxide, a metal phosphate, a metal fluoride, etc., and thus a side reaction and a surface phase change of the positive electrode material with the electrolyte may be suppressed. For ion doping, the main purpose is to stabilize the layered structure.
In addition, the design of the morphology structure and the directional arrangement of the doping elements are used for improving the cycle stability and the structural stability of the high-nickel ternary cathode material, and the solution strategy is also targeted. At present, there are patents reporting doping of ion concentration gradient, so as to effectively improve the electrochemical performance of the anode material. For example, the application number CN201710762454.6 introduces a strategy of controlling the flow rate of Ni salt and uniformly doping to form a concentration gradient NCM doped with cations, which effectively improves the capacity retention rate; for example, a strategy of double-ion doping and controlling the doping flow rate is introduced in the patent with the application number of CN201910496175.9, and the formed concentration gradient double-doped NCM precursor improves the rate capability of the cathode material. However, the above two synthetic strategies have the problems that the synthetic steps are complicated, the mode of controlling the variable flow rate is not favorable for the regulation of element proportion, the repeatability is poor and the like.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the ternary positive electrode material precursor and the simple and feasible preparation method thereof are provided for overcoming the defects in the prior art and improving the cycle performance, rate capability and electrochemical performance of the layered high-nickel ternary battery material.
The solution of the invention is realized by the following steps:
a ternary precursor, characterized by: the Nb-doped high nickel hydroxide is used as an inner core, the low nickel hydroxide is used as an outer shell, and the chemical general formula is { [ Ni { [x1Coy1Mz1Nb(1-x1-y1-z)]n[Nix2Coy2M(1-x2-y2)]1-n}(OH)2Wherein x1 is more than or equal to 0.7 and less than or equal to 0.9, y1 is more than or equal to 0.01 and less than or equal to 0.2, z1 is more than or equal to 0.01 and less than or equal to 0.4, x2 is more than or equal to 0.4 and less than or equal to 0.7, y2 is more than or equal to 0.01 and less than or equal to 0.4, n is more than or equal to 0.4 and less than or equal to 0.7.
The Nb doping can improve the stability of the layered anode material, increase the conductivity of the layered anode material and further improve the rate capability of the anode material. The niobium doped with high nickel inside is beneficial to reducing Li in the subsequent calcination process for preparing the cathode material+/Ni2+Mixed drainage, the relatively high cobalt in the outer part is beneficial to stabilizing the laminated structure. As the positive electrode material continues the morphology structure of the precursor, the structure of the concentration layered doping Nb can reduce the cation mixed discharge and improve the conductivity, so that the lithium ion channel is easier to Li+Intercalation of (II) with increased Li+The diffusion rate is increased, so that the electrochemical performance of the ternary cathode material is effectively improved.
In addition, the precursor of the concentration layered Nb-doped ternary cathode material is mixed with lithium hydroxide, and the mixture is sintered in an oxygen atmosphere to prepare the concentration layered Nb-doped ternary cathode material, so that the cycle performance of the concentration layered Nb-doped ternary cathode material is obviously improved.
The invention also provides a solution of the preparation method of the ternary precursor, which is realized by the following steps:
a preparation method of a ternary precursor is characterized by comprising the following steps:
(1) preparing A, B two solutions with the same total concentration but different molar ratios of nickel, cobalt, manganese or aluminum by using soluble nickel salt, cobalt salt and manganese salt or aluminum salt, wherein the concentration of Ni in the solution A is higher than that in the solution B; preparing a niobate solution, a sodium hydroxide solution and an ammonia water solution;
(2) adding prepared ammonia water solution and sodium hydroxide solution into reaction equipment, adjusting the ammonia concentration to 5-12g/L under the stirring state, and adjusting the pH to 10-12;
(3) continuously adding the prepared solution A and the prepared niobate solution into the reaction equipment, and controlling the ammonia concentration in the reaction process to be 5-12g/L and the pH to be 10-12 by using an ammonia water solution and a sodium hydroxide solution; testing the granularity of the suspension in the reaction equipment in real time, and stirring and aging after the median particle granularity reaches 2-12 mu m;
(4) after the aging in the step (3) is finished, adding a salt solution B into the reaction equipment, and adjusting the ammonia concentration in the reaction process to be 5-10g/L and the pH value to be 10-14 by using an ammonia water solution and a sodium hydroxide solution; testing the granularity of the suspension in the reaction equipment in real time, and stirring and aging after the median particle granularity reaches 10-16 mu m;
(5) and (4) after the aging in the step (4) is finished, separating, washing and drying the solid product to obtain the ternary precursor.
Further, in the above-mentioned case,
in the step (1), the total concentration of the A, B solution is 1-5mol/L, the concentration of sodium hydroxide is 10-25mol/L, and the concentration of ammonia is 28-30 wt%.
Further, in the above-mentioned case,
in the step (1), the molar weight of nickel in the solution A accounts for 0.7-0.9 of the total molar weight of nickel, cobalt, manganese or nickel, cobalt and aluminum; the molar weight of nickel in the solution B accounts for 0.4-0.6 of the total molar weight of nickel, cobalt, manganese or nickel, cobalt and aluminum;
further, in the above-mentioned case,
in the step (1), the nickel salt, the cobalt salt and the manganese salt are sulfate, carbonate or nitrate; the aluminum salt is aluminum nitrate, aluminum carbonate, aluminum sulfate or sodium metaaluminate.
Further, in the above-mentioned case,
in the step (1), the concentration of the niobate solution is 0.01-2mol/L, and the niobate is ammonium niobium oxalate, niobium nitrate, niobium sulfate or niobium acetate.
Further, in the above-mentioned case,
in the steps (2), (3) and (4), the reaction temperature is controlled to be 40-80 ℃.
Further, in the above-mentioned case,
in the step (3), the stirring speed is 200-800 rpm.
Further, in the above-mentioned case,
and (4) stirring and aging for 1-5h in the step (3).
Further, in the above-mentioned case,
in the step (4), the stirring speed is 600-1000 rpm.
According to the preparation method of the precursor, a soluble salt aqueous solution of nickel, cobalt, manganese or nickel, cobalt and aluminum, niobium salt and a sodium hydroxide aqueous solution with high nickel ratio are subjected to coprecipitation reaction in a reaction kettle at the early stage under the complexation of ammonia to prepare the niobium-doped ternary hydroxide with proper granularity; and growing nickel-cobalt-manganese ternary hydroxide with low nickel proportion on the basis of the later period to synthesize the precursor of the niobium-doped ternary cathode material with the concentration layered structure with high internal nickel and low external nickel. In the whole process, the niobium doped with high nickel in the interior is beneficial to reducing Li in the subsequent calcination process for preparing the cathode material+/Ni2+Mixed drainage, the relatively high cobalt in the outer part is beneficial to stabilizing the laminated structure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention.
FIG. 1 shows [ (Ni) prepared in example 10.8Co0.06Mn0.13Nb0.004)0.7(Ni0.5Co0.2Mn0.3)0.3](OH)2SEM image of ternary positive electrode material precursor.
FIG. 2 shows [ (Ni) prepared in example 10.8Co0.06Mn0.13Nb0.004)0.7(Ni0.5Co0.2Mn0.3)0.3](OH)2And (3) a cross-sectional view of the ternary cathode material precursor.
FIG. 3 is [ (LiNi) prepared in example 10.8Co0.06Mn0.13Nb0.004)0.7(Ni0.5Co0.2Mn0.3)0.3]O2Cycle curve of the positive electrode material.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way.
Example 1
A method for preparing a ternary precursor, comprising:
(1) nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are respectively used for preparing a mixed soluble salt A, B solution of nickel, cobalt and manganese with the total concentration of 2.0mol/L, a niobium ammonium oxalate solution with the concentration of 0.048mol/L, a sodium hydroxide solution with the concentration of 10mol/L and an ammonia water solution with the concentration of 12mol/L according to the molar ratio of Ni to Co to Mn of 0.80:0.06:0.13 and 0.50:0.20: 0.30.
(2) A50L reactor was charged with 1/2 volumes of pure water at 60 ℃ and, under stirring at 400rpm, 10mol/L aqueous ammonia solution was added to adjust the ammonia concentration to 6.5g/L, followed by addition of sodium hydroxide solution to adjust the pH to 12.
(3) And (3) on the basis of the step (2), adding a salt solution A, an ammonium niobium oxalate solution, an ammonia water solution and a sodium hydroxide solution into a 50L reaction kettle, wherein the ammonia concentration is maintained at 6-8g/L and the pH value is maintained at 11.5-12.0 in the whole process.
(4) Testing the granularity of the reaction liquid in the reaction kettle in real time, stopping the reaction when the median particle reaches 3.5-5.0 mu m, continuing stirring and aging for 2h, and then carrying out 1/2 volume percent reaction on the full kettle material.
(5) After aging is finished, introducing the salt solution B, the ammonia water solution and the sodium hydroxide solution into the reaction kettle, adjusting the ammonia concentration and the pH value under the stirring speed of 800rpm, stopping the kettle after the median particle size is stabilized to 10.5-12.5 mu m and the proportion of hydroxide formed by A, B two salts reaches 7: 3, and aging.
(6) After the reaction kettle is aged, washing a reaction product in the reaction kettle by using a centrifugal machine, controlling the temperature of washing alkali and pure water to be 70 ℃, and stopping washing until the Na and S contents of finished products are respectively less than 150ppm and 800 ppm; drying the washed solid particle material at 140 ℃; sieving with 400 mesh sieve to obtain the final product, and sealing for storage.
As shown in figure 1 of the drawings, in which,the Nb-doped ternary precursor [ (Ni) prepared in this example0.8Co0.06Mn0.13Nb0.004)0.7(Ni0.5Co0.2Mn0.3)0.3](OH)2The primary particles are fine and compact, and the crystal structures are orderly arranged.
As shown in FIG. 2, the Nb-doped ternary precursor [ (Ni) prepared in this example0.8Co0.06Mn0.13Nb0.004)0.7(Ni0.5Co0.2Mn0.3)0.3](OH)2A hierarchical structure is presented.
As shown in fig. 3, the ternary precursor prepared in example 1 was further prepared into a positive electrode material, and it can be seen that the prepared positive electrode material [ (LiNi)0.8Co0.06Mn0.13Nb0.004)0.7(Ni0.5Co0.2Mn0.3)0.3]O2Has excellent cycle performance.
Example 2
A method for preparing a ternary precursor, comprising:
(1) nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are used according to the molar ratio of Ni to Co to Mn of 0.90:0.04: 0.58 and 0.50: 0.15: 0.35 are respectively used for preparing a mixed soluble salt A, B solution of nickel, cobalt and manganese with the total concentration of 2.5mol/L, preparing a niobium oxalate solution with the concentration of 0.1mol/L, preparing a sodium hydroxide aqueous solution with the concentration of 8mol/L and preparing an ammonia aqueous solution with the concentration of 15 mol/L.
(2) A650L reactor was charged with 1/2 volumes of pure water at 60 ℃ and, with stirring at 800rpm, 15mol/L aqueous ammonia was added to adjust the ammonia concentration to 8.5g/L, followed by addition of sodium hydroxide solution to adjust the pH to 11.8.
(3) Adding a salt solution A, a niobium oxalate solution, an ammonia water solution and a sodium hydroxide solution into a reaction kettle, wherein the ammonia concentration is maintained at 6-8g/L and the pH value is maintained at 11.5-12.5 in the whole process.
(4) And (3) carrying out real-time particle size test on the reaction liquid in the reaction kettle, stopping the reaction when the median particles reach 3.5-4.3 mu m, continuously stirring and aging for 2h, and then separating the materials filled in the reaction kettle.
(5) Adding the salt solution B, the ammonia water solution and the sodium hydroxide solution into the reaction kettle, adjusting the ammonia concentration and the pH value at the stirring speed of 600rpm, and stopping the kettle when the median particle size is stabilized to 10.5-12.5 mu m and the proportion of hydroxide formed by A, B two salts reaches 8: 2.
(6) After the reaction kettle is aged, washing a reaction product in the reaction kettle by using a centrifugal machine, controlling the temperature of washing alkali and pure water to be 70 ℃, and stopping washing until the Na and S contents of finished products are respectively less than 150ppm and 800 ppm; drying the washed solid particle material; sieving with 400 mesh sieve to obtain the final product, and sealing for storage.
Example 3
A method for preparing a ternary precursor, comprising:
(1) preparing a nickel-cobalt-manganese soluble salt A solution with the concentration of 2.0mol/L by using nickel nitrate hexahydrate, cobalt nitrate hexahydrate and manganese nitrate tetrahydrate according to the molar ratio of Ni to Co to Mn of 0.90:0.04: 0.58, and preparing a nickel-cobalt-manganese soluble salt A solution by using nickel nitrate hexahydrate, cobalt nitrate hexahydrate and aluminum sulfate hexahydrate according to the molar ratio of Ni: co: preparing a nickel, cobalt and aluminum mixed soluble salt B solution with the total concentration of 2.0mol/L and preparing a niobium ammonium oxalate solution with the concentration of 0.048mol/L according to the molar ratio of Al of 0.55: 0.15: 0.30; preparing an aqueous solution of sodium hydroxide with the concentration of 8mol/L and an aqueous solution of ammonia with the concentration of 12 mol/L.
(2) A50L reactor was charged with 1/2 volumes of pure water at 60 ℃ and, under stirring at 800rpm, 12mol/L aqueous ammonia solution was added to adjust the ammonia concentration to 8.5g/L, followed by addition of sodium hydroxide solution to adjust the pH to 11.8.
(3) Adding a salt solution A, a niobium oxalate solution, an ammonia water solution and a sodium hydroxide solution into a reaction kettle, wherein the ammonia concentration is maintained at 6-8g/L and the pH value is maintained at 11.5-12.5 in the whole process.
(4) And (3) carrying out real-time particle size test on the reaction liquid in the reaction kettle, stopping the reaction when the median particles reach 3.5-4.3 mu m, continuously stirring and aging for 2h, and then separating the materials filled in the reaction kettle.
(5) Adding the salt solution B, the ammonia water solution and the sodium hydroxide solution into a reaction kettle, adjusting the ammonia concentration and the pH value under the condition of stirring speed of 600rpm, and stopping the kettle when the granularity is stabilized to 11.5-13.5 mu m and the proportion of hydroxide formed by A, B two salts reaches 9: 1.
(6) After the reaction kettle is aged, washing a reaction product in the reaction kettle by using a centrifugal machine, controlling the amount of alkali for washing and the temperature of pure water to be 70 ℃, and stopping washing until the contents of Na and S of finished products are respectively less than 150ppm and 800 ppm; drying the washed solid particle material at 150 ℃; sieving with 400 mesh sieve to obtain pre-oxidized ternary nickel cobalt manganese precursor, and sealing for storage.
Example 4
A method for preparing a ternary precursor, comprising:
(1) respectively preparing a mixed soluble salt A, B solution of nickel, cobalt and aluminum with the total concentration of 2.0mol/L by using nickel sulfate hexahydrate, cobalt sulfate heptahydrate and aluminum sulfate hexadecahydrate according to the molar ratio of Ni, Co and Al of 0:88:0.09: 0.03 and 0.55: 0.15: 0.30; preparing a niobium acetate solution with the concentration of 0.048mol/L, and preparing a sodium hydroxide aqueous solution with the concentration of 8mol/L and an ammonia aqueous solution with the concentration of 12 mol/L.
(2) A30L reactor was charged with 1/2 volumes of pure water at 60 ℃ and, under stirring at 800rpm, 12mol/L aqueous ammonia solution was added to adjust the ammonia concentration to 8.5g/L, followed by addition of sodium hydroxide solution to adjust the pH to 11.8.
(3) And simultaneously adding a salt solution A, a niobium acetate solution, an ammonia water solution and a sodium hydroxide solution into a 30L reaction kettle, wherein the ammonia concentration is maintained at 6-8g/L and the pH is maintained at 11.5-12.5 in the whole process.
(4) And (3) carrying out real-time particle size test on the reaction liquid in the reaction kettle, stopping the reaction when the median particles reach 3.5-4.3 mu m, and continuing stirring and aging for 2 h.
(5) Subsequently, the salt solution B, the ammonia water solution and the sodium hydroxide solution are added into the reaction kettle, the ammonia concentration and the pH value are adjusted under the condition that the stirring speed is 600rpm, and the kettle is stopped when the particle size is stabilized to 11.5-13.5 mu m and the proportion of hydroxide formed by A, B two salts reaches 7.5: 2.5.
(6) After the reaction kettle is aged, washing a reaction product in the reaction kettle by using a centrifugal machine, controlling the amount of alkali for washing and the temperature of pure water to be 70 ℃, and stopping washing until the contents of Na and S of finished products are respectively less than 150ppm and 800 ppm; drying the washed solid particle material at 140 ℃; sieving with 400 mesh sieve to obtain ternary nickel cobalt aluminum precursor, sealing and storing.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A ternary precursor, characterized by: the Nb-doped high nickel hydroxide is used as an inner core, the low nickel hydroxide is used as an outer shell, and the chemical general formula is { [ Ni { [x1Coy1Mz1Nb(1-x1-y1-z1)]n[Nix2Coy2M(1-x2-y2)]1-n}(OH)2Wherein x1 is more than or equal to 0.7 and less than or equal to 0.9, y1 is more than or equal to 0.01 and less than or equal to 0.2, z1 is more than or equal to 0.01 and less than or equal to 0.4, x2 is more than or equal to 0.4 and less than or equal to 0.7, y2 is more than or equal to 0.01 and less than or equal to 0.4, n is more than or equal to 0.4 and less than or equal to 0.7, and.
2. A method of preparing the ternary precursor of claim 1, comprising the steps of:
(1) preparing A, B two solutions with the same total concentration but different molar ratios of nickel, cobalt, manganese or aluminum by using soluble nickel salt, cobalt salt and manganese salt or aluminum salt, wherein the concentration of Ni in the solution A is higher than that in the solution B; preparing a niobate solution, a sodium hydroxide solution and an ammonia water solution;
(2) adding prepared ammonia water solution and sodium hydroxide solution into reaction equipment, adjusting the ammonia concentration to 5-12g/L under the stirring state, and adjusting the pH to 10-12;
(3) continuously adding the prepared solution A and the prepared niobate solution into the reaction equipment, and controlling the ammonia concentration in the reaction process to be 5-12g/L and the pH to be 10-12 by using an ammonia water solution and a sodium hydroxide solution; testing the granularity of the suspension in the reaction equipment in real time, and stirring and aging after the median particle granularity reaches 2-12 mu m;
(4) after the aging in the step (3) is finished, adding a salt solution B into the reaction equipment, and adjusting the ammonia concentration in the reaction process to be 5-10g/L and the pH value to be 10-14 by using an ammonia water solution and a sodium hydroxide solution; testing the granularity of the suspension in the reaction equipment in real time, and stirring and aging after the median particle granularity reaches 10-16 mu m;
(5) and (4) after the aging in the step (4) is finished, separating, washing and drying the solid product to obtain the ternary precursor.
3. The method according to claim 2, wherein in the step (1), the A, B solution has a total concentration of 1 to 5mol/L, the niobate solution has a concentration of 0.01 to 2mol/L, the sodium hydroxide has a concentration of 10 to 25mol/L, and the ammonia has a concentration of 28 to 30 wt%.
4. The method according to claim 2, wherein in the step (1), the molar amount of nickel in the solution A is 0.7 to 0.9 based on the total molar amount of nickel, cobalt, manganese or nickel, cobalt and aluminum; the molar weight of the nickel in the solution B accounts for 0.4-0.6 of the total molar weight of the nickel, cobalt, manganese or nickel, cobalt and aluminum.
5. The method according to any one of claims 2 to 4, wherein in the step (1), the nickel salt, the cobalt salt, and the manganese salt are sulfate, carbonate, or nitrate; the aluminum salt is aluminum nitrate, aluminum carbonate, aluminum sulfate or sodium metaaluminate; the niobium salt is ammonium niobium oxalate, niobium nitrate, niobium sulfate or niobium acetate.
6. The process according to claim 2, wherein in the steps (2), (3) and (4), the reaction temperature is controlled to 40 to 80 ℃.
7. The preparation method according to claim 2, wherein in the step (3), the stirring rate is 200-800 rpm; stirring and aging for 1-5 h.
8. The preparation process as claimed in claim 2, wherein in the step (4), the stirring rate is 600-1000 rpm.
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| CN114853072B (en) * | 2022-03-18 | 2023-05-16 | 浙江帕瓦新能源股份有限公司 | Precursor material of nickel-cobalt-manganese ternary positive electrode material and preparation method thereof |
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| CN115732659A (en) * | 2022-11-21 | 2023-03-03 | 格林美股份有限公司 | Modified positive electrode material and preparation method and application thereof |
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