CN110127777B - Wet zirconium-doped nickel-cobalt-aluminum ternary precursor with gradient concentration and preparation method thereof - Google Patents
Wet zirconium-doped nickel-cobalt-aluminum ternary precursor with gradient concentration and preparation method thereof Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 93
- -1 nickel-cobalt-aluminum Chemical compound 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 44
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 19
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 117
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 114
- 239000000243 solution Substances 0.000 claims description 57
- 239000007864 aqueous solution Substances 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 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 18
- HNNOKOICROAFNK-UHFFFAOYSA-N [Ni].[Co].[Zr] Chemical compound [Ni].[Co].[Zr] HNNOKOICROAFNK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000010410 layer Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000012452 mother liquor Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 150000003754 zirconium Chemical class 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 7
- 239000002184 metal Substances 0.000 claims 7
- 239000011259 mixed solution Substances 0.000 claims 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 4
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000011229 interlayer Substances 0.000 claims 1
- 238000000975 co-precipitation Methods 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000010668 complexation reaction Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 8
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010413 mother solution Substances 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- NXBARPSOQWENKD-UHFFFAOYSA-N [Zr].[Mn].[Co].[Ni] Chemical compound [Zr].[Mn].[Co].[Ni] NXBARPSOQWENKD-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910018058 Ni-Co-Al Inorganic materials 0.000 description 1
- 229910017158 Ni0.80Co0.15Al0.05(OH)2 Inorganic materials 0.000 description 1
- 229910018144 Ni—Co—Al Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
- C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
一种湿法掺锆浓度梯度镍钴铝三元前驱体及其制备方法，该镍钴铝三元前驱体的化学通式为NixCoyAlz(OH)2，其中x+y+z=1，并且0.3≤x≤0.9，0.01≤y≤0.4，0.01≤z≤0.4，Zr元素占镍钴氢氧化物前驱体总质量的0.001%‑3%；三元前驱体由三层构成，其内层为掺锆镍钴二元前驱体，分子式为：NixCoy(OH)2，其外层为掺锆镍钴铝三元前驱体，分子式为：NixCoyAlz(OH)2，其中间层为掺锆镍钴二元前驱体和掺锆镍钴铝三元前驱体之间的浓度梯度前驱体，本发明还包括所述镍钴铝三元前驱体的制备方法。本发明掺锆镍钴铝三元前驱体粒度分布窄、颗粒形貌好；络合控制结晶共沉淀使掺杂元素均匀，用其制备的正极前驱体比容量高，循环稳定性好，加工性能好，性能稳定。
A wet zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor and a preparation method thereof. The chemical formula of the nickel-cobalt-aluminum ternary precursor is Ni x CoyAl z (OH) 2 , wherein x+y+z=1 , and 0.3≤x≤0.9, 0.01≤y≤0.4, 0.01≤z≤0.4, Zr element accounts for 0.001%-3% of the total mass of the nickel-cobalt hydroxide precursor; the ternary precursor is composed of three layers, in which The layer is a zirconium-doped nickel-cobalt binary precursor, the molecular formula is: Ni x Co y (OH) 2 , and the outer layer is a zirconium-doped nickel-cobalt aluminum ternary precursor, and the molecular formula is: Ni x Co y Al z (OH) 2 wherein the intermediate layer is a concentration gradient precursor between a zirconium-doped nickel-cobalt binary precursor and a zirconium-doped nickel-cobalt-aluminum ternary precursor, and the invention also includes a preparation method of the nickel-cobalt-aluminum ternary precursor. The zirconium-doped nickel-cobalt-aluminum ternary precursor of the invention has narrow particle size distribution and good particle morphology; complexation controls crystallization and co-precipitation to make the doping elements uniform, and the positive electrode precursor prepared by using the ternary precursor has high specific capacity, good cycle stability and processing performance. Good, stable performance.
Description
Technical Field
The invention relates to the technical field of manufacturing of a zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor, and particularly relates to a wet-method zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor and a preparation method thereof.
Background
As a novel green battery, the lithium ion battery has many advantages such as high voltage, specific energy, and little environmental pollution, and has been widely used in the field of digital products, and gradually expanded to the fields of electric vehicles, satellites, aerospace, and the like. High energy and high density are the development directions of future lithium ion power batteries, and the development of the positive electrode precursor becomes the focus of industrial attention as an important material influencing the performance of the lithium ion power battery.
The lithium ion power battery has high requirements on the anode precursor, and the anode precursor is required to have high energy density, good cycle life and relatively low price. Although the specific capacity of the traditional positive electrode precursor, such as the nickel cobalt lithium manganate positive electrode precursor, is high, the activity and the cycle performance of the precursor are poor, the high temperature resistance is insufficient, and the requirements of the lithium ion power battery cannot be met. The nickel-cobalt-aluminum ternary positive electrode has low cost, high specific capacity and high cycling stability, and becomes a hot spot of recent research in the industry. The nickel-cobalt-aluminum ternary cathode material is prepared by doping aluminum element in a solid phase, generally preparing nickel-cobalt or nickel-cobalt-manganese hydroxide, and mixing a precursor with lithium salt and a small-particle aluminum compound at high temperature, so that homogenization is difficult to realize.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a zirconium-doped nickel-cobalt-aluminum ternary precursor with gradient concentration by a wet method and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is that the chemical general formula of the wet zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor is NixCoyAlz(OH)2Wherein x + y + z =1, x is more than or equal to 0.3 and less than or equal to 0.9, y is more than or equal to 0.01 and less than or equal to 0.4, z is more than or equal to 0.01 and less than or equal to 0.4, and Zr accounts for 0.001-3% of the total mass of the nickel-cobalt hydroxide precursor; the ternary precursor is composed of three layers, wherein the inner layer is a zirconium-doped nickel-cobalt binary precursor, and the molecular formula is as follows: nixCoy(OH)2The outer layer is a zirconium-doped nickel-cobalt-aluminum ternary precursor, and the molecular formula is as follows: nixCoyAlz(OH)2And the intermediate layer is a concentration gradient precursor between the zirconium-doped nickel-cobalt binary precursor and the zirconium-doped nickel-cobalt-aluminum ternary precursor.
The preparation method of the wet zirconium-doped nickel-cobalt-aluminum ternary precursor with gradient concentration comprises the following steps:
preparing a nickel-cobalt-zirconium soluble salt solution, a sodium hydroxide aqueous solution, an ammonia aqueous solution and a sodium metaaluminate solution; step two, adding the nickel-cobalt-zirconium soluble salt aqueous solution and the sodium hydroxide aqueous solution prepared in the step one into a reaction kettle, and mixing the nickel-cobalt-zirconium soluble salt aqueous solution and the sodium hydroxide aqueous solution according to the proportion of Ni: molar ratio of Co 0.80: 0.15 preparing a nickel-cobalt soluble salt solution with the total concentration of 2.0mol/L, wherein zirconium salt is a zirconium sulfate solution which is 0.3 percent of the total mass of the nickel-cobalt hydroxide, and preparing and generating zirconium-doped nickel-cobalt hydroxide crystal nuclei; step three, continuously adding the nickel-cobalt-zirconium soluble salt aqueous solution and the sodium hydroxide aqueous solution prepared in the step one into a reaction kettle, and simultaneously pumping an ammonia aqueous solution to prepare and generate small particles with zirconium-doped nickel-cobalt binary precursors as inner layers; step four, further adding the nickel-cobalt-zirconium soluble salt aqueous solution, the sodium hydroxide aqueous solution and the ammonia aqueous solution prepared in the step one into a reaction kettle, and simultaneously pumping a sodium metaaluminate solution to prepare and generate a ternary precursor with an outer layer of a zirconium-nickel-cobalt-aluminum doped ternary precursor; and fifthly, centrifugally washing the solid particle materials of the reaction products obtained in the fourth step, centrifugally dewatering, drying and screening to obtain the zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor, and sealing and storing.
Further, in the first step, the concentration of the prepared nickel cobalt zirconium soluble salt aqueous solution is 2-2.5mol/L, the concentration of the sodium hydroxide aqueous solution is 8-10mol/L, the concentration of the zirconium salt solution is 0.001% -5% of the total mass of the nickel cobalt hydroxide, the concentration of the ammonia aqueous solution is 8-10mol/L, and the concentration of the sodium metaaluminate solution is 0.3-0.9 mol/L.
Further, in the step one, the prepared nickel-cobalt-zirconium soluble salt aqueous solution is a sulfate solution of nickel, cobalt and zirconium, and the sodium metaaluminate solution is prepared by dissolving aluminum sulfate solid in an excessive sodium hydroxide solution.
Further, in the third step, the grain diameter of the small particles of the zirconium-doped nickel-cobalt binary precursor is 3.5-5.5 μm; in the fourth step, the shape of the ternary precursor is spherical or spheroidal, and the particle size of the ternary precursor is 10.5-11.5 microns.
Further, the reaction kettle is provided with a temperature-controlled water bath jacket, a stirring paddle and a precise filter tube, mother liquor is added into the reaction kettle, the concentration of ammonia in the mother liquor is 0.15-0.25mol/L, the pH is =11.5-12.0, and the mother liquor is over all the stirring paddles of the reaction kettle; after the reaction kettle is filled with the materials, the redundant mother liquor is discharged out of the reaction kettle through the precise filter pipe, and the solid content in the reaction system is controlled to be 450-plus 650 g/L.
Further, the preparation method of the wet zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor is characterized by comprising the second step of introducing nitrogen into a sealed reaction kettle, wherein the amount of the introduced nitrogen is 1/200-1/100 of the volume of the reaction kettle, starting stirring, and adjusting the pH value of a bottom solution to 12.5-13.0 by using 8-10mol/L of the sodium hydroxide aqueous solution; the stirring speed is adjusted to 400-500r/min, the flow rate of the salt solution is controlled to be 80-120L/h by using a precise metering pump, the temperature of the reaction kettle is controlled to be 50-65 ℃, the feeding time is 3-5 hours, and when the pH value is reduced to 11.8-12.5, zirconium-doped nickel cobalt hydroxide crystal nuclei are generated.
Further, the volume of the reaction kettle is 5000-7000L.
Further, in the third step, a precise metering pump controls the flow rate of the salt solution to be 80-120L/h, controls the ammonia concentration to be 0.25-0.35mol/L, adjusts the flow rate of the sodium hydroxide aqueous solution, controls the pH of the reaction solution to be =11.8-12.5, and controls the reaction temperature to be 55-65 ℃.
Further, the stirring speed of the reaction kettle is adjusted to be 700-min, the flow of the nickel-cobalt salt aqueous solution is kept unchanged by a precision metering pump, the flow rate of the sodium metaaluminate solution is increased at a constant speed, the flow of the sodium hydroxide aqueous solution is adjusted, the pH of the reaction solution is controlled to be =11.1-11.4, and the reaction temperature is controlled to be 55-65 ℃.
Further, step five, the temperature of pure water for washing is 55-80 ℃, when the Na + in the material is less than or equal to 0.0150%, the washing is stopped, the drying temperature is 100-130 ℃, and a 200-mesh screen is adopted for screening.
Further, introducing nitrogen into the two-way sealed reaction kettle, wherein the nitrogen is 1/200-1/100 of the volume of the reaction kettle, starting stirring, and adjusting the pH value of the base solution to 12.5-13 by using 8-10mol/L of the sodium hydroxide aqueous solution; the stirring speed is adjusted to 400-500r/min, the salt flow is controlled to be 80-120L/h by using a precision metering pump, the temperature of the reaction kettle is controlled to be 50-65 ℃, the feeding time is 3-5 hours, and when the pH value is reduced to 11.8-12.5, zirconium-doped nickel cobalt hydroxide crystal nuclei are generated.
Further, the three-step precise metering pump controls the salt flow to be 80-120L/h, controls the ammonia concentration to be 0.25-0.35mol/L, adjusts the flow of the sodium hydroxide water solution, controls the pH of the reaction solution to be =11.8-12.5, and controls the temperature of the reaction kettle to be 55-65 ℃.
Further, in the fourth step, the stirring speed of the reaction kettle is adjusted to 700-.
Further, the temperature of pure water for washing in the fifth step is 55-80 ℃, the washing is stopped until the Na < + > in the material is less than or equal to 0.0150%, the drying temperature is 100 ℃ and 130 ℃, and a 200-mesh screen is adopted for screening.
The wet zirconium-doped nickel-cobalt-aluminum ternary precursor has high capacity, good cycle stability, good processing performance and stable performance.
The principle of the preparation method is that a complexation control crystallization coprecipitation method is adopted, a nickel-cobalt-zirconium soluble salt aqueous solution and a sodium hydroxide aqueous solution in a reaction kettle are subjected to coprecipitation reaction under the complexation of ammonia, zirconium-doped nickel-cobalt binary hydroxide with small particle size is prepared firstly, then sodium metaaluminate solution is added into the reaction kettle, the preferable scheme is optimized, the flow rate of the sodium metaaluminate solution is gradually increased, the solid-liquid ratio is improved, the reaction is continued to grow to the required particle size, and the proportion of the prepared zirconium-doped nickel-cobalt-aluminum ternary precursor from an inner core to an outer layer is changed in a uniform gradient manner; the solid-liquid ratio of the solution in the reaction kettle is improved, and the obtained ternary precursor has narrow particle size distribution and good particle morphology; the complex control crystallization coprecipitation ensures that the doping elements are uniform, so that the anode precursor prepared by the complex control crystallization coprecipitation has high specific capacity, good cycle stability, good processing performance and stable performance.
Drawings
FIG. 1 is a 1000 times electron microscope morphology diagram of a zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor obtained in example 1 of the present invention;
FIG. 2 is a morphology diagram of a Ni-Co-Al ternary precursor with a zirconium-doped concentration gradient obtained in example 1 of the present invention under a 5000-fold electron microscope;
fig. 3 is a morphological diagram of the zirconium-doped concentration gradient nickel cobalt aluminum ternary precursor obtained in embodiment 1 of the present invention under a 10000 times electron microscope.
Fig. 4 is a graph comparing the electrical performance of a CR2025 button cell assembled with a positive electrode of a battery made using a positive electrode precursor made from the product of example 1 of the present invention with a CR2025 button cell assembled with a positive electrode of a battery made from a positive electrode precursor made from the corresponding product of comparative example 1.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention:
the chemical general formula of the zirconium-doped nickel-cobalt-aluminum ternary precursor with the concentration gradient by the wet method in the embodiment of the invention is Ni0.80Co0.15Al0.05(OH)2: d10=6.26um, d50=10.47um, d90=18.62um, tap density =1.69g/cm3Specific surface area =20.31m2(ii) in terms of/g. The morphology is shown in fig. 1-3, and is spherical or spheroidal.
The embodiment of the preparation method of the wet zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor comprises the following steps:
the method comprises the following steps: according to the proportion of Ni: molar ratio of Co 0.80: 0.15 preparing a nickel cobalt soluble salt aqueous solution with the total concentration of 2.0mol/L, wherein zirconium salt is a zirconium sulfate solution with the mass of 0.3 percent of the total mass of nickel cobalt hydroxide, mixing the nickel cobalt soluble salt aqueous solution with the zirconium salt solution, preparing a sodium hydroxide aqueous solution with the concentration of 8mol/L, preparing an ammonia aqueous solution with the concentration of 10mol/L, and preparing a sodium metaaluminate solution with the concentration of 0.6 mol/L; the sodium metaaluminate solution is prepared by dissolving aluminum sulfate solid in excessive sodium hydroxide solution.
Step two: adding a mother solution with the ammonia water concentration of 0.15mol/L and the pH =11.78 into a 6500L reaction kettle provided with a temperature-controlled water bath jacket, a stirring paddle and a precise filter tube to serve as a base solution, enabling the base solution to submerge all the stirring paddles of the reaction kettle, and adding ammonia water and a sodium hydroxide solution into pure water with the mother solution of 55 ℃ to enable the ammonia water concentration to be 0.15mol/L and the pH = 11.78;
introducing nitrogen into the sealed reaction kettle, wherein the flow rate of the nitrogen is 2L/min, starting stirring at the rotating speed of 400r/min, and adjusting the pH value of the base solution to 12.9 by using 8mol/L sodium hydroxide aqueous solution;
starting to produce crystal nuclei: adjusting the stirring speed of the reaction kettle to 500r/min, adding 2.0mol/L nickel-cobalt-zirconium soluble saline solution and 8mol/L sodium hydroxide aqueous solution into the reaction kettle in a concurrent flow manner by using a precise metering pump, controlling the flow rate of the saline solution to be 120L/h, controlling the reaction temperature to be 55 ℃, continuously feeding, and after 3 hours, when the pH value is reduced to 11.8, generating nickel-cobalt-manganese hydroxide crystal nuclei and completing a crystal nucleus making stage;
step three: adding a 2.0mol/L nickel-cobalt-zirconium soluble salt aqueous solution, an 8mol/L sodium hydroxide aqueous solution and a 10mol/L ammonia aqueous solution into a reaction kettle in a parallel flow manner by using a precise metering pump, controlling the flow rate of the salt solution to be 120L/h, adjusting the flow rate of the sodium hydroxide aqueous solution, controlling the pH of the reaction solution to be =11.85, and controlling the reaction temperature to be 55 ℃;
along with the continuous feeding, small crystal nuclei grow gradually and the sphericity tends to be perfect, after the reaction kettle is filled with reaction materials, slurry enters the aging kettle, and crystals in the reaction kettle continue to crystallize, grow and grow;
detecting the particle size of the solid particle material obtained by one-time reaction every 1 hour by using a laser particle size analyzer, and stopping feeding when the median particle size of the small-particle nickel-cobalt-manganese hydroxide in the reaction kettle is detected to reach 4.0 +/-0.5 mu m;
discharging redundant mother liquor out of the reaction kettle through a precise filter pipe, and controlling the solid content in the reaction system to be 500 g/L;
step four: adjusting the stirring speed of a reaction kettle to 700r/min, adding 2.0mol/L nickel cobalt zirconium soluble salt aqueous solution, 8mol/L sodium hydroxide aqueous solution and 10mol/L ammonia aqueous solution into the reaction kettle by using a precision metering pump, controlling the flow rate of the salt solution to be 120L/h, adding 0.6mol/L sodium metaaluminate aqueous solution into the reaction kettle in a parallel flow manner by using the precision metering pump, controlling the flow rate of the initial sodium metaaluminate solution to be 4L/h, increasing the flow rate of the sodium metaaluminate solution at an increasing speed of 2L/h, controlling the reaction temperature to be 55 ℃, keeping the flow rate of the salt solution and the flow rate of the sodium metaaluminate solution unchanged after 8 hours along with the continuous feeding, adjusting the flow rate of the sodium hydroxide aqueous solution in real time by actually measuring the pH value, controlling the pH =11.4 of the reaction solution, continuing the reaction, gradually growing crystal nuclei, leading the sphericity to be, discharging redundant mother liquor out of the reaction kettle through a precise filter pipe, controlling the solid content in the reaction system to be 500g/L, and allowing crystals in the reaction kettle to remain in the reaction kettle for continuous crystallization, development and growth;
detecting the particle size of solid particle materials in the reaction kettle by using a laser particle size analyzer for 1 hour, stopping feeding when detecting that the median particle size of the particle nickel-cobalt-manganese hydroxide in the reaction kettle reaches 10.5-11.5 mu m, adjusting the rotating speed of a stirring paddle of the reaction kettle to 200r/min, and continuing stirring and aging for 2 hours;
step five: after the reaction kettle is aged, washing the reaction product solid particle material in the reaction kettle by using a centrifugal machine, controlling the temperature of pure water for washing to be 70 ℃ until the Na & lt + & gt in the reaction product solid particle material is less than or equal to 0.0150%, stopping washing, and dehydrating by using the centrifugal machine; drying the dehydrated solid particle material; sieving with 200 mesh sieve to obtain zirconium-doped nickel-cobalt-aluminum ternary precursor with gradient concentration, and sealing for storage.
Weighing 5kg of the ternary precursor obtained in the step five and 2.2kg of lithium hydroxide monohydrate, putting the three and 2.2kg of lithium hydroxide monohydrate into a high-speed mixer, uniformly mixing, and putting the mixture into a box-type resistance furnace for sintering; in a resistance furnace, firstly carrying out heat treatment at 400 ℃ for 3h, then carrying out heat treatment at 630 ℃ for 5h, and finally carrying out heat treatment at 770-780 ℃ for 10h, keeping the oxygen atmosphere in the whole process, and dissociating and screening the obtained product to finally obtain the zirconium-doped concentration gradient nickel-cobalt-aluminum ternary cathode material.
The morphology of the obtained zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor is shown in figures 1, 2 and 3. As shown in FIGS. 1, 2 and 3, the zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor prepared by the invention has a spherical or ellipsoidal particle shape.
And uniformly mixing the zirconium-doped concentration gradient nickel-cobalt-aluminum ternary positive electrode material with carbon black and PVDF, coating the mixture on an aluminum foil to prepare a positive plate, and assembling the positive plate, a lithium metal plate, a diaphragm and electrolyte in a vacuum glove box to form the CR2025 button cell.
And (3) carrying out electrical property detection on the CR2025 button cell: the 0.1C discharge capacity is 207.35mA/g, the 1C discharge capacity is 186.55 mA/g, and the capacity retention rate at 50 cycles of 1C is 99.51%.
Comparative example 1
According to the proportion of Ni: co: molar ratio of Mn 0.80: 0.15:0.05, preparing a nickel-cobalt-manganese soluble salt aqueous solution with the total concentration of 2.0mol/L, wherein zirconium salt is a zirconium sulfate solution accounting for 0.3 percent of the total mass of the nickel-cobalt hydroxide, mixing the nickel-cobalt-manganese soluble salt solution with the zirconium salt solution, preparing a sodium hydroxide aqueous solution with the concentration of 8mol/L, and preparing an ammonia aqueous solution with the concentration of 10 mol/L.
Adding a mother solution with the ammonia water concentration of 0.15mol/L and the pH =11.78 into a 6500L reaction kettle provided with a temperature-controlled water bath jacket, a stirring paddle and a precise filter tube to serve as a base solution, enabling the base solution to submerge all the stirring paddles of the reaction kettle, and adding ammonia water and a sodium hydroxide solution into pure water with the mother solution of 55 ℃ to enable the ammonia water concentration to be 0.15mol/L and the pH = 11.78;
introducing nitrogen into the sealed reaction kettle, wherein the flow rate of the nitrogen is 2L/min, starting stirring at the rotating speed of 400r/min, and adjusting the pH value of the base solution to 12.9 by using 8mol/L sodium hydroxide aqueous solution;
starting to produce crystal nuclei: adjusting the stirring speed of a reaction kettle to 500r/min, adding 2.0mol/L of nickel-cobalt-manganese-zirconium soluble saline solution and 8mol/L of sodium hydroxide aqueous solution into the reaction kettle in a concurrent flow manner by using a precise metering pump, controlling the flow rate of the saline solution to be 120L/h, controlling the reaction temperature to be 55 ℃, continuously feeding, and after 3 hours, when the pH value is reduced to 11.8, generating nickel-cobalt-manganese hydroxide crystal nuclei and completing a crystal nucleus making stage;
step three: adding 2.0mol/L of nickel-cobalt-manganese-zirconium soluble salt aqueous solution, 8mol/L of sodium hydroxide aqueous solution and 10mol/L of ammonia aqueous solution into a reaction kettle in a parallel flow manner by using a precise metering pump, controlling the flow rate of the salt solution to be 120L/h, adjusting the flow rate of the sodium hydroxide aqueous solution, controlling the pH of the reaction solution to be =11.85, and controlling the reaction temperature to be 55 ℃;
along with the continuous feeding, small crystal nuclei grow gradually and the sphericity tends to be perfect, after the reaction kettle is filled with reaction materials, slurry enters the aging kettle, and crystals in the reaction kettle continue to crystallize, grow and grow;
detecting the particle size of the solid particle material obtained by the primary reaction for 1 hour by using a laser particle size analyzer, and stopping feeding when the median particle size of the small-particle nickel-cobalt-manganese hydroxide in the reaction kettle is detected to reach 3.5-5.5 mu m;
discharging redundant mother liquor out of the reaction kettle through a precise filter pipe, and controlling the solid content in the reaction system to be 500 g/L;
step four: adjusting the stirring speed of a reaction kettle to 700r/min, adding 2.0mol/L nickel-cobalt-manganese-zirconium soluble salt aqueous solution, 8mol/L sodium hydroxide aqueous solution and 10mol/L ammonia aqueous solution into the reaction kettle by using a precision metering pump, controlling the flow rate of the salt aqueous solution to be 120L/h, controlling the reaction temperature to be 55 ℃, controlling the pH =11.4 of the reaction solution along with the continuous feeding, continuing the reaction, gradually growing crystal nuclei, leading the sphericity to be perfect, discharging redundant mother liquor out of the reaction kettle through a precision filter pipe after the reaction kettle is filled with reaction materials, controlling the solid content in the reaction system to be 500g/L, and keeping crystals in the reaction kettle for continuous crystal growth;
detecting the particle size of solid particle materials in the reaction kettle by using a laser particle size analyzer for 1 hour, stopping feeding when detecting that the median particle size of the particle nickel-cobalt-manganese hydroxide in the reaction kettle reaches 10.5-11.5 mu m, adjusting the rotating speed of a stirring paddle of the reaction kettle to 200r/min, and continuing stirring and aging for 2 hours;
step five: after the reaction kettle is aged, washing the reaction product solid particle material in the reaction kettle by using a centrifugal machine, controlling the temperature of pure water for washing to be 70 ℃ until the Na & lt + & gt in the reaction product solid particle material is less than or equal to 0.0150%, stopping washing, and dehydrating by using the centrifugal machine; drying the dehydrated solid particle material; sieving with 200 mesh sieve to obtain zirconium-doped nickel-cobalt-aluminum ternary precursor with gradient concentration, and sealing for storage.
Weighing 5kg of the ternary precursor obtained in the step five and 2.2kg of lithium hydroxide monohydrate, putting the three and 2.2kg of lithium hydroxide monohydrate into a high-speed mixer, uniformly mixing, and putting the mixture into a box-type resistance furnace for sintering; in a resistance furnace, firstly carrying out heat treatment at 400 ℃ for 3h, then carrying out heat treatment at 630 ℃ for 5h, and finally carrying out heat treatment at 770 ℃ and 780 ℃ for 10h, keeping the oxygen atmosphere in the whole process, and dissociating and screening the obtained product to finally obtain the zirconium-doped nickel-cobalt-manganese ternary cathode material.
And (3) uniformly mixing the positive electrode material with carbon black and PVDF, coating the mixture on an aluminum foil to prepare a positive plate, and assembling the positive plate, a lithium metal plate, a diaphragm and electrolyte in a vacuum glove box to form the CR2025 button cell.
The electrical property of the CR2025 button cell is detected, the 0.1C discharge capacity is 203.46mA/g, the 1C discharge capacity is 181.98 mA/g, and the capacity retention rate of 1C circulation 50 circles is 92.87%.
Fig. 4 is a graph comparing the electrical performance of a cathode assembled CR2025 button cell made using the cathode precursor made from the product of example 1 of the present invention with a cathode assembled CR2025 button cell made from the cathode precursor made from the corresponding product of comparative example 1.
As can be seen from FIG. 4, the capacity, the multiplying power and the cycle performance of the test sample of the embodiment of the invention are obviously superior to those of the test sample of the comparative example under the condition of normal temperature of 25 ℃ within the voltage range of 3.0-4.3V.
Those not described in detail in the specification are prior art known to those skilled in the art.
The foregoing is only a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, without departing from the technical principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be considered to be within the protection scope of the present invention.
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| CN112701263A (en) * | 2020-12-29 | 2021-04-23 | 中伟新材料股份有限公司 | Tantalum-doped nickel-cobalt-aluminum ternary precursor and preparation method thereof, lithium ion battery anode material and lithium ion battery |
| CN113451567B (en) * | 2021-06-25 | 2022-10-21 | 浙江帕瓦新能源股份有限公司 | Multi-element doped nickel-rich quaternary cathode material precursor and preparation method thereof |
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