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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Abstract
A zirconium concentration gradient Ni-Co-Al ternary precursor doped by a wet method and a preparation method thereof are provided, wherein the chemical general formula of the Ni-Co-Al 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)2The invention also discloses a preparation method of the nickel-cobalt-aluminum ternary precursor. The zirconium-doped nickel-cobalt-aluminum ternary precursor has narrow particle size distribution and good particle appearance; the complex control crystallization coprecipitation makes the doping elements uniform, and the positive electrode precursor prepared by the complex control crystallization coprecipitation has high specific capacity, good cycle stability, good processing performance and 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.
Claims (12)
1. A zirconium concentration gradient Ni-Co-Al ternary precursor doped by a wet method is characterized in that the chemical general formula 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)2The 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 concentration gradient nickel-cobalt-aluminum ternary precursor is characterized by comprising the following steps of:
preparing a nickel-cobalt-zirconium metal salt mixed solution, a sodium hydroxide solution, an ammonia water solution, a sodium metaaluminate solution and a reaction kettle bottom solution;
secondly, adding the nickel-cobalt-zirconium metal salt mixed solution prepared in the first step and the sodium hydroxide solution into a reaction kettle, preparing a nickel-cobalt soluble salt solution with the total concentration of 2.0mol/L according to the molar ratio of Ni to Co of 0.80: 0.15, and preparing zirconium sulfate solution which is 0.3 percent of the total mass of the nickel-cobalt hydroxide to generate zirconium-doped nickel-cobalt hydroxide crystal nuclei;
step three, continuously adding the nickel-cobalt-zirconium metal salt mixed solution prepared in the step one and the sodium hydroxide solution into a reaction kettle, and adding an ammonia water solution to prepare a small granular zirconium-doped nickel-cobalt binary precursor;
step four, further adding the nickel-cobalt-zirconium metal salt mixed solution, the sodium hydroxide solution and the ammonia water solution prepared in the step one into a reaction kettle, and adding a sodium metaaluminate solution to finally generate a large-particle ternary precursor, wherein the crystal nucleus is zirconium-doped nickel-cobalt hydroxide, the inner layer wrapping the crystal nucleus is a zirconium-doped nickel-cobalt binary precursor, the outer layer is a zirconium-doped nickel-cobalt-aluminum ternary precursor, and the intermediate layer between the inner layer of the zirconium-doped nickel-cobalt binary precursor and the outer layer of the zirconium-doped nickel-cobalt-aluminum ternary precursor has a concentration gradient precursor;
step five, centrifugally washing the large-particle ternary precursor after the reaction in the step four, centrifugally dewatering, drying, screening, and finally sealing and storing;
introducing nitrogen into the sealed reaction kettle, wherein the introduction amount of 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 12.5-13.0 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 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;
in the third step, a precise metering pump controls the flow rate of the saline solution to be 80-120L/h, controls the concentration of ammonia water to be 0.25-0.35mol/L, adjusts the flow rate of the sodium hydroxide aqueous solution, controls the pH value of the reaction solution to be =11.8-12.5, and controls the reaction temperature to be 55-65 ℃;
in the fourth step, the stirring speed of the reaction kettle is adjusted to be 700r/min, a precision metering pump keeps the flow of the nickel-cobalt-zirconium metal salt mixed solution unchanged, the flow rate of the sodium metaaluminate solution is increased progressively 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 ℃.
2. The wet zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor according to claim 1, wherein in the first step, the concentration of the prepared nickel-cobalt-zirconium metal salt mixed solution is 2.0-2.5mol/L, wherein zirconium element is 0.001-5% of the total mass of nickel-cobalt hydroxide, the concentration of the sodium hydroxide solution is 8-10mol/L, the concentration of the ammonia water solution is 8-10mol/L, and the concentration of the sodium metaaluminate solution is 0.3-0.9 mol/L.
3. The wet zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor according to claim 1 or 2, wherein in the step one, the prepared nickel-cobalt-zirconium metal salt mixed 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.
4. The wet zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor according to claim 1 or 2, wherein in step three, the median particle size of the small particles of the zirconium-doped nickel-cobalt binary precursor is 3.5-5.5 μm, and in step four, the ternary precursor is spherical or quasi-spherical in shape, and the median particle size is 10.5-11.5 μm.
5. The wet zirconium-doped concentration gradient nickel-cobalt-aluminum ternary precursor according to claim 3, wherein in step three, the median particle size of the small particles of the zirconium-doped nickel-cobalt binary precursor is 3.5-5.5 μm, and in step four, the ternary precursor is spherical or quasi-spherical in shape, and the median particle size is 10.5-11.5 μm.
6. The wet zirconium-doped nickel-cobalt-aluminum ternary precursor with concentration gradient according to claim 1 or 2, wherein the reaction kettle is a reaction kettle provided with a temperature-controlled water bath jacket, a stirring paddle and a precise filter tube, and the bottom solution of the reaction kettle is a solution with ammonia concentration of 0.15-0.25mol/L and pH =11.5-12.0 and does not pass through the stirring paddle of the reaction kettle; after the liquid level of the reaction kettle approaches to the overflow port, the mother liquid 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.
7. The wet zirconium-doped nickel-cobalt-aluminum ternary precursor with concentration gradient according to claim 3, wherein the reaction kettle is a reaction kettle provided with a temperature-controlled water bath jacket, a stirring paddle and a precise filter tube, and the bottom solution of the reaction kettle is a solution with ammonia concentration of 0.15-0.25mol/L and pH =11.5-12.0 and passes through the stirring paddle of the reaction kettle; after the liquid level of the reaction kettle approaches to the overflow port, the mother liquid 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.
8. The wet zirconium-doped nickel-cobalt-aluminum ternary precursor with concentration gradient according to claim 4, wherein the reaction kettle is a reaction kettle provided with a temperature-controlled water bath jacket, a stirring paddle and a precise filter tube, and the bottom solution of the reaction kettle is a solution with ammonia concentration of 0.15-0.25mol/L and pH =11.5-12.0 and passes through the stirring paddle of the reaction kettle; after the liquid level of the reaction kettle approaches to the overflow port, the mother liquid 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.
9. The wet zirconium-doped nickel-cobalt-aluminum ternary precursor with concentration gradient as claimed in claim 1 or 2, wherein in the fifth step, the temperature of pure water for washing is 55-80 ℃ until 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.
10. The wet zirconium-doped nickel-cobalt-aluminum ternary precursor with concentration gradient as claimed in claim 3, wherein in the step five, the temperature of pure water for washing is 55-80 ℃ until 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.
11. The wet zirconium-doped nickel-cobalt-aluminum ternary precursor with concentration gradient as claimed in claim 4, wherein in the fifth step, the temperature of pure water for washing is 55-80 ℃ until 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.
12. The wet zirconium-doped nickel-cobalt-aluminum ternary precursor with concentration gradient as claimed in claim 6, wherein in the fifth step, the temperature of pure water for washing is 55-80 ℃ until 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.
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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 |
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| CN114229922B (en) * | 2022-02-21 | 2022-05-24 | 浙江帕瓦新能源股份有限公司 | Nickel-cobalt-manganese ternary precursor, positive electrode material and preparation method |
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