CN112939095B - Spherical high-nickel cobalt-free single crystal precursor and preparation method thereof - Google Patents

Spherical high-nickel cobalt-free single crystal precursor and preparation method thereof Download PDF

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CN112939095B
CN112939095B CN202110130581.0A CN202110130581A CN112939095B CN 112939095 B CN112939095 B CN 112939095B CN 202110130581 A CN202110130581 A CN 202110130581A CN 112939095 B CN112939095 B CN 112939095B
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张�诚
寇亮
陈微微
孙静
张超
王继峰
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Shaanxi Coal and Chemical Technology Institute Co Ltd
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Abstract

The invention discloses a spherical high-nickel cobalt-free monocrystal precursor and a preparation method thereof, wherein the low coprecipitation reaction temperature is 20-40 ℃, the crystallinity of the precursor is effectively reduced and the ratio of the precursor is improved by increasing the feeding speed section by section, changing the pH value and the like, and in addition, a long-diameter blade is adopted, the diameter of a paddle/the diameter of a kettle is 0.50-0.65, the stirring strength is improved, and the dispersity and the sphericity of the monocrystal precursor are improved. The invention has simple process and easy control of process, is suitable for large-scale production, and the prepared high-nickel cobalt-free monocrystal precursor has good dispersibility, good sphericity and a specific surface of more than or equal to 20m 2 The crystallinity is low, and the full width at half maximum FWHM of the precursor obtained by XRD test 101 Not less than 0.8, and obvious sintering single crystallization.

Description

Spherical high-nickel cobalt-free single crystal precursor and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly belongs to a spherical high-nickel cobalt-free single crystal precursor and a preparation method thereof.
Background
Because cobalt belongs to scarce resources, the fluctuation of cobalt price is larger, and the development of cobalt-free products is technically accelerated for getting rid of monopoly control of resources. The high-nickel cobalt-free material has the advantages that rare cobalt elements are removed, the material cost is reduced, the nickel content is improved, the specific capacity of the material is improved, and meanwhile, the manganese content is increased, so that the effect of stabilizing the structure can be achieved. However, the content of nickel is increased and cobalt is completely absent, which causes the adverse results of poor material conductivity, serious lithium nickel mixed discharge, poor thermal stability and the like, and particularly, when the high nickel cobalt-free material is a polycrystalline material, the Direct Current Resistance (DCR) of the material is obviously increased due to cobalt-free, the material is pulverized due to serious phase change, and the like.
The single crystal material has the advantages of good structural stability, long cycle life, high safety and the like, can effectively solve the problems of cobalt-free materials, and in addition, the precursors with small grain diameters of the single crystal also have the problems of easy agglomeration, poor sphericity, poor sintering consistency and the like. The high-nickel cobalt-free single crystal anode material is an effective strategy for solving the cobalt-free problem, so that the development of a corresponding precursor is very critical. The conventional coprecipitation method is generally adopted for preparing the precursor by 50 o C~60 o The C is used as the coprecipitation reaction temperature, the flow rate is constant by adopting an intermittent method, the prepared precursor is generally high in crystallinity and small in specific surface, sintering to form a single-crystal product is not facilitated, the precursor with small particle size is easy to agglomerate and poor in sphericity, the consistency of a positive electrode product corresponding to sintering is poor, DCR is high, the electrical property is poor, and the sintering cost is increased due to the fact that the sintering temperature is high. Therefore, the development of a precursor with large specific surface, low crystallinity and high sphericity aiming at the high-nickel cobalt-free material is particularly critical.
Disclosure of Invention
In order to solve the problems that a high-nickel cobalt-free precursor prepared by a conventional coprecipitation method has high crystallinity and a small specific surface and is not beneficial to sintering single crystallization, the invention provides a spherical high-nickel cobalt-free single crystal precursor and a preparation method thereof, which effectively improve the specific surface of the precursor, reduce the crystallinity of materials, improve the sphericity of a small-particle-size precursor and further are beneficial to the consistency of a sintering process and sintering single crystallization.
In order to achieve the purpose, the invention provides the following technical scheme: a spherical high-nickel cobalt-free monocrystal precursor with Ni as molecular formula x Mn y M z (OH) 2 Wherein x + y + z =1, 0.6. Ltoreq. X < 1.0,0. Ltoreq. Z0.05, M is a doping element, the ballThe specific surface area of the precursor of the high-nickel cobalt-free single crystal is 20m 2 /g~50m 2 (iv) a half-value width of 0.8 to 1.80.
The invention provides a preparation method of a spherical high-nickel cobalt-free single crystal precursor, which comprises the following steps:
s1, taking the molar ratio of Ni: preparing a nickel-manganese mixed salt solution with the concentration of 1.0 to 2.0mol/L from the nickel salt and the manganese salt with Mn = x: y;
s2, preparing a reaction base solution from the alkali solution and the ammonia solution, and adjusting the pH value of the reaction base solution to 12.5 to 13.0;
s3, introducing a nickel-manganese mixed salt solution, a doped element salt solution, an alkali solution and an ammonia solution into the reaction base solution at the same time in a nitrogen environment, and controlling the reaction temperature to be 20 o C~40 o And C, adjusting the pH value of the reaction solution and the feeding speed of the nickel-manganese mixed salt solution according to the median particle size of the reaction product in the reaction process, stopping feeding when the median particle size of the reaction product is 2.5-4.0 mu m, and then filtering, washing, drying, screening and deironing to obtain the spherical high-nickel cobalt-free single crystal precursor.
Further, in the step S3, when the median particle size of the reaction product is more than 0 and less than D50 and less than 2 μm, controlling the pH value in the reaction process to be 12.3 to 13.0; when the median particle diameter D50 of the reaction product is more than or equal to 2 mu m, controlling the pH value in the reaction process to be 11.5-12.2.
Further, in the step S3, when the median particle size of the reaction product is more than 0 and less than D50 and less than 1.5 mu m, controlling the flow of the nickel-manganese mixed salt to be 200L/h-400L/h; when the median particle size of the reaction product is not less than 1.5 mu m and not more than D50 and less than 2 mu m, controlling the flow of the nickel-manganese mixed salt to be 400-600L/h; when the median particle diameter D50 of the reaction product is more than or equal to 2 mu m, controlling the flow of the nickel-manganese mixed salt to be 600L/h-800L/h.
Further, steps S2 and S3 are performed in a reaction vessel having a long-diameter paddle.
Further, the diameter of the long diameter blade/the diameter of the kettle is 0.50 to 0.65, and the stirring speed is 300rpm to 500rpm.
Further, in step S1, the nickel salt is nickel sulfate, nickel chloride or nickel nitrate, and the manganese salt is manganese sulfate, manganese chloride or manganese nitrate.
Further, in step S1, the doping element is Al, mg, zr, fe, ti, or W.
Further, in step S2, the concentration of the ammonia solution is 13mol/L, and the alkali solution is 10mol/L sodium hydroxide solution.
Further, in the steps S2 and S3, the ammonia concentration in the reaction base solution and the reaction solution is controlled to be 4 g/L-10 g/L.
Compared with the prior art, the invention has at least the following beneficial effects:
the precursor ratio of the spherical high-nickel cobalt-free single crystal precursor provided by the invention is 20 to 50m 2 The half-peak width of the precursor is 0.8 to 1.8, which indicates that the crystallinity is low; the high-nickel cobalt-free single crystal precursor has good dispersibility, good sphericity, obviously refined primary crystal grains, lower preferred crystal orientation and larger specific surface, the structure is favorable for single crystallization and consistency of sintering, the direct-current impedance of the prepared cobalt-free anode material is obviously reduced, and the multiplying power and the cycle performance of a battery are effectively improved.
The spherical high-nickel cobalt-free single crystal precursor provided by the invention is prepared at a low coprecipitation reaction temperature of 20 DEG o C~40 o And C, according to the median particle size of the reaction product, the feeding speed is increased section by section, the pH value is changed, and the like, so that the crystallinity of the precursor is effectively reduced, the precursor ratio is improved, the single crystallization of sintering and the sintering cost are favorably reduced, the process is simple, the process is easy to control, and the method is suitable for large-scale production.
In addition, the reaction kettle adopts the long-diameter blades, the diameter of the blades/the diameter of the kettle is 0.50 to 0.65, the stirring strength is improved, the dispersity and the sphericity of the single crystal precursor are improved, the consistency of the sintering process is facilitated, the DCR of the high-nickel cobalt-free single crystal product is further reduced, and the electrochemical performance of the high-nickel cobalt-free single crystal product is facilitated.
Drawings
FIG. 1 is a schematic diagram of a precursor prepared in example 1 of the present invention under a 5000-fold electron microscope;
FIG. 2 is a schematic diagram of the precursor prepared in comparative example 1 under a 5000-fold electron microscope;
FIG. 3 is a schematic view of a precursor prepared in example 1 of the present invention under a 50000 times electron microscope;
FIG. 4 is a schematic diagram of a precursor prepared in comparative example 1 under a 50000-fold electron microscope;
FIG. 5 is an XRD pattern of a precursor prepared in example 1 of the present invention;
fig. 6 is an XRD pattern of the precursor prepared in comparative example 1.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1
Step 1, preparing a raw material solution: nickel sulfate and manganese sulfate are mixed according to a molar ratio of 0.90:0.08 prepares 2mol/L solution, and also prepares 0.1mol/L sodium metaaluminate solution as doping solution, and dissolves sodium hydroxide into 10mol/L alkali liquor; an ammonia solution of 13mol/L is used as a complexing agent.
Step 2, preparing a reaction base solution: adding the prepared alkali liquor and ammonia solution into a reaction kettle filled with semi-kettle water and filled with nitrogen, wherein the reaction kettle adopts a paddle with the paddle diameter/kettle diameter =0.60, adjusting the pH value of the bottom liquid to be 13.0, controlling the ammonia concentration in the reaction bottom liquid to be 10g/L, controlling the stirring speed to be 500rpm, and controlling the temperature to be 40 ℃.
Step 3, starting the reaction, simultaneously adding the nickel-manganese mixed salt, the aluminum salt, the alkali liquor and the ammonia solution into a reaction kettle filled with reaction bottom liquid, and controlling the ammonia concentration to be 10g/L in the whole process; controlling the pH value to be 13.0 in the early stage of the reaction, and controlling the pH value in the reaction process to be 12.2 when the median particle diameter D50 of the reaction product is more than or equal to 2 mu m;
specifically, when the median particle size is more than 0 and less than D50 and less than 1.5 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 200L/h, and the pH value in the reaction process is controlled to be 13.0; when the D50 is more than or equal to 1.5 mu m and less than 2 mu m of the median particle size, controlling the flow of the nickel-manganese mixed salt to be 400L/h and controlling the pH value to be 13.0; when the median particle diameter D50 is more than or equal to 2 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 600L/h, and the pH value is controlled to be 12.2.
Step 4, when the particle size D50=3.5 μm, stopping feeding, filtering, washing, drying, screening and deironing to obtain a precursor product Ni 0.90 Mn 0.08 Al 0.02 (OH) 2 。
The specific surface area of the precursor product is 22m 2 The scanning electron microscope scanning images of the,/g are shown in FIG. 1 and FIG. 3; XRD test results FWHM101=0.88 as shown in fig. 5.
Example 2
Step 1, preparing a raw material solution: nickel sulfate and manganese sulfate are mixed according to a molar ratio of 0.60:0.35 is prepared into 2mol/L solution, 0.1mol/L magnesium sulfate solution is prepared as doping solution, and sodium hydroxide is dissolved into 10mol/L alkali liquor; an ammonia solution of 13mol/L is used as a complexing agent.
Step 2, preparing a reaction base solution: adding the prepared alkali liquor and ammonia solution into a reaction kettle filled with semi-kettle water and filled with nitrogen, wherein the reaction kettle adopts a paddle with the paddle diameter/kettle diameter =0.65, adjusting the pH value of the base liquor to 12.5, adjusting the ammonia concentration to 4g/L, controlling the stirring speed to 300rpm and controlling the temperature to 20 ℃.
Step 3, starting the reaction, simultaneously adding the nickel-manganese mixed salt, the magnesium salt, the alkali liquor and the ammonia solution into a reaction kettle filled with reaction bottom liquid, and controlling the ammonia concentration to be 4g/L in the whole process; controlling the pH value to be 12.3 in the early stage of the reaction, and controlling the pH value to be 11.5 when the median particle diameter D50 is more than or equal to 2 mu m;
specifically, when the median particle size is more than 0 and less than D50 and less than 1.5 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 400L/h, and the pH value is controlled to be 12.3; when the D50 is less than 2 μm and the median particle size is more than or equal to 1.5 μm, controlling the flow of the nickel-manganese mixed salt to be 600L/h and the pH value to be 12.3; when the median particle diameter D50 is more than or equal to 2 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 800L/h, and the pH value is controlled to be 11.5.
Step 4, when the particle size D50=4.0 μm, stopping feeding, filtering, washing, drying, screening and deironing to obtain a precursor product Ni 0.60 Mn 0.35 Mg 0.05 (OH) 2 。
The specific surface area of the precursor product is 25m 2 (ii)/g; XRD test resultsFWHM 101 =1.0。
Example 3
Step 1, preparing a raw material solution, namely preparing a nickel nitrate and a manganese nitrate according to a molar ratio of 0.80:0.17 is prepared into 2mol/L solution, 0.1mol/L zirconium nitrate solution is prepared as doping solution, and sodium hydroxide is dissolved into 10mol/L alkali liquor; an ammonia solution of 13mol/L is used as a complexing agent.
Step 2, preparing a reaction base solution: adding the prepared alkali liquor and ammonia solution into a reaction kettle filled with semi-kettle water and filled with nitrogen, wherein the reaction kettle adopts a paddle with the paddle diameter/kettle diameter =0.55, adjusting the pH value of the base liquor to 12.5, adjusting the ammonia concentration to 6g/L, controlling the stirring speed to 400rpm and controlling the temperature to 30 ℃.
Step 3, starting the reaction, simultaneously adding the nickel-manganese mixed salt, the zirconium salt, the alkali liquor and the ammonia solution into a reaction kettle filled with reaction base liquid, and controlling the ammonia concentration to be 6g/L in the whole process; controlling the pH value to be 12.5 in the early stage of the reaction, and controlling the pH value to be 11.7 when the median particle diameter D50 of a reaction product is more than or equal to 2 mu m;
specifically, when the median particle size is more than 0 and less than D50 and less than 1.5 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 300L/h, and the pH value is controlled to be 12.5; when the D50 is less than 2 μm and the median particle size is more than or equal to 1.5 μm, controlling the flow of the nickel-manganese mixed salt to be 500L/h and the pH value to be 12.3; when the median particle diameter D50 is more than or equal to 2 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 700L/h, and the pH value is controlled to be 11.7.
Step 4, when the particle size D50=2.5 μm, stopping feeding, filtering, washing, drying, screening and deironing to obtain a precursor product Ni 0.80 Mn 0.17 Zr 0.03 (OH) 2 。
The specific surface area of the precursor product is 37m 2 (ii)/g; XRD test resultsFWHM 101 =0.13。
Example 4
Step 1, preparing a raw material solution: nickel sulfate and manganese sulfate are mixed according to a molar ratio of 0.9:0.05 is prepared into 1.5mol/L solution, 0.1mol/L magnesium sulfate solution is prepared as doping solution, sodium hydroxide is dissolved into 10mol/L alkali liquor; an ammonia solution of 13mol/L is used as a complexing agent.
Step 2, preparing a reaction base solution: adding the prepared alkali liquor and ammonia solution into a reaction kettle filled with semi-kettle water and filled with nitrogen, wherein the reaction kettle adopts a paddle with the paddle diameter/kettle diameter =0.50, adjusting the pH value of the base liquor to 12.5, adjusting the ammonia concentration to 4g/L, controlling the stirring speed to 300rpm and controlling the temperature to 20 ℃.
Step 3, starting the reaction, simultaneously adding the nickel-manganese mixed salt, the magnesium salt, the alkali liquor and the ammonia solution into a reaction kettle filled with reaction bottom liquid, and controlling the ammonia concentration to be 4g/L in the whole process; controlling the pH value to be 12.3 in the early stage of the reaction, and controlling the pH value to be 11.5 when the median particle diameter D50 of a reaction product is more than or equal to 2 mu m;
specifically, when the median particle size is more than 0 and less than D50 and less than 1.5 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 400L/h, and the pH value is controlled to be 12.3; when the D50 is more than or equal to 1.5 mu m and less than 2 mu m of the median particle size, controlling the flow of the nickel-manganese mixed salt to be 600L/h and controlling the pH value to be 12.3; when the median particle diameter D50 is more than or equal to 2 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 800L/h, and the pH value is controlled to be 11.5.
Step 4, when the particle size D50=4.0 μm, stopping feeding, filtering, washing, drying, screening and deironing to obtain a precursor product Ni 0.9 Mn 0.05 Mg 0.05 (OH) 2 。
The specific surface area of the precursor product is 20m 2 (ii)/g; XRD test resultsFWHM 101 =0.8。
Example 5
Step 1, preparing a raw material solution: nickel sulfate and manganese sulfate are mixed according to a molar ratio of 0.85:0.11 is prepared into 1.75mol/L solution, 0.1mol/L ferrous sulfate solution is prepared as doping solution, and sodium hydroxide is dissolved into 10mol/L alkali liquor; an ammonia solution of 13mol/L is used as a complexing agent.
Step 2, preparing a reaction base solution: adding the prepared alkali liquor and ammonia solution into a reaction kettle filled with semi-kettle water and filled with nitrogen, wherein the reaction kettle adopts a paddle with the paddle diameter/kettle diameter =0.55, adjusting the pH value of the base liquor to 12.6, adjusting the ammonia concentration to 5g/L, controlling the stirring speed to 300rpm and controlling the temperature to 25 ℃.
Step 3, starting the reaction, simultaneously adding the nickel-manganese mixed salt, the ferric salt, the alkali liquor and the ammonia solution into a reaction kettle filled with the reaction bottom liquid, and controlling the ammonia concentration to be 5g/L in the whole process; controlling the pH value to be 12.7 in the early stage of the reaction, and controlling the pH value to be 12.0 when the median particle diameter D50 of a reaction product is more than or equal to 2 mu m;
specifically, when the median particle size is more than 0 and less than D50 and less than 1.5 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 250L/h, and the pH value is controlled to be 12.7; when the D50 is less than 2 μm and the median particle size is more than or equal to 1.5 μm, controlling the flow of the nickel-manganese mixed salt to be 600L/h and the pH value to be 12.7; when the median particle diameter D50 is more than or equal to 2 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 800L/h, and the pH value is controlled to be 12.0.
Step 4, when the particle size D50=4.0 μm, stopping feeding, filtering, washing, drying, screening and deironing to obtain a precursor product Ni 0.9 Mn 0.05 Fe 0.05 (OH) 2 。
The specific surface area of the precursor product is 50m 2 (ii)/g; XRD test resultsFWHM 101 =1.8。
The doping element can also be titanium sulfate and tungsten trioxide.
Example 6
Step 1, mixing nickel chloride and manganese chloride according to a molar ratio of 0.75:0.25 preparing 1mol/L solution, and dissolving sodium hydroxide into 10mol/L alkali liquor; a13 mol/L ammonia solution is used as a complexing agent.
And 2, adding the prepared alkali liquor and ammonia solution into a reaction kettle filled with semi-kettle water and filled with nitrogen, wherein the reaction kettle adopts a paddle with the paddle diameter/kettle diameter =0.58, the pH value of the base liquor is adjusted to 12.8, the ammonia concentration is 8g/L, the stirring speed is controlled at 350rpm, and the temperature is controlled at 35 ℃.
Step 3, starting the reaction, simultaneously adding the nickel-manganese mixed salt, the alkali liquor and the ammonia solution into a reaction kettle filled with the reaction bottom liquor, and controlling the ammonia concentration to be 8g/L in the whole process; controlling the pH value to be 12.4 in the early stage of the reaction, and controlling the pH value to be 11.6 when the median particle diameter D50 of a reaction product is more than or equal to 2 mu m;
specifically, when the median particle size is more than 0 and less than D50 and less than 1.5 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 350L/h, and the pH value is controlled to be 12.4; when the D50 is less than 2 μm and the median particle size is more than or equal to 1.5 μm, controlling the flow of the nickel-manganese mixed salt to be 550L/h and the pH value to be 12.4; when the median particle diameter D50 is more than or equal to 2 mu m, the flow rate of the nickel-manganese mixed salt is controlled to be 750L/h, and the pH value is controlled to be 11.6.
Step 4, when the particle size D50=3.0 μm, stopping feeding, filtering, washing, drying, screening and deironing to obtain a precursor product Ni 0.75 Mn 0.25 (OH) 2 。
The specific surface area of the precursor product is 30m 2 (ii)/g; XRD test resultsFWHM 101 =0.94。
Comparative example 1
Step 1, preparing a raw material solution: nickel sulfate and manganese sulfate are mixed according to a molar ratio of 0.90:0.08 prepares 2mol/L solution, and also prepares 0.1mol/L sodium metaaluminate solution as doping solution, and dissolves sodium hydroxide into 10mol/L alkali liquor; an ammonia solution of 13mol/L is used as a complexing agent.
Step 2, preparing a reaction base solution: adding the prepared alkali liquor and ammonia solution into a reaction kettle filled with semi-kettle water and filled with nitrogen, wherein the reaction kettle adopts a paddle with the paddle diameter/kettle diameter =0.40, adjusting the pH value of the bottom liquid to be 12.2, controlling the ammonia concentration in the reaction bottom liquid to be 10g/L, controlling the stirring speed to be 500rpm, and controlling the temperature to be 60 ℃.
And 3, starting the reaction, simultaneously adding the nickel-manganese mixed salt, the aluminum salt, the alkali liquor and the ammonia solution into a reaction kettle filled with the reaction bottom liquid, controlling the ammonia concentration to be 10g/L, the pH value to be 12.2 and controlling the flow to be 400L/h in the whole process.
Step 4, when the particle size of the reaction product is D50=3.5 μm, stopping feeding, filtering, washing, drying, screening and removing iron to obtain a precursor product Ni 0.90 Mn 0.08 Al 0.02 (OH) 2 。
The specific surface area of the precursor product is 10m 2 The scanning electron microscope scanning images of the,/g are shown in FIG. 2 and FIG. 4; XRD test results FWHM101=0.511 as shown in fig. 6.
In summary, the precursor ratios prepared according to the typical batch process are typically 15m 2 Within/g, FWHM 101 Generally lower than 0.8, and the specific surface area of the precursor prepared by 1~6 in the embodiment of the invention can reach 20m 2 /g~50m 2 Per gram, the half-peak width of the precursor can reach 0.8 ≤FWHM 101 The precursor prepared by the invention has the physicochemical indexes which are not more than 1.8, not only is beneficial to sintering single crystallization, but also effectively reduces the sintering temperature of single crystal, and is beneficial to improving the physicochemical property and the electrical property of a sintered product.
Example 6 preparation without addition of doping elementsThe specific surface area of the cobalt-free precursor is 30m 2 /g，FWHM 101 =0.94, the precursor obtained also has a high specific surface and a low material crystallinity, and also improves the sphericity of the small-particle-size precursor; compared with an undoped cobalt-free precursor, in the embodiment 1~5, the doping element is added into the precursor, and the doping element can be uniformly distributed in the material in the sintering process, so that the crystal structure is further improved, and the electrochemical performance of the material can be further optimized.
As can be seen from comparison of the figures 1 to 4, the spherical high-nickel cobalt-free single crystal precursor prepared by the method has the advantages that the primary crystal grains are fine, loose and porous, the sphericity of the secondary particles is good, and the sintering temperature is favorably reduced and the sintering single crystallization is favorably realized; the precursor prepared by the conventional process has thicker primary crystal grains and compact accumulation, and is not beneficial to sintering and single crystallization.
Comparing the XRD patterns of FIG. 5 and FIG. 6, it can be seen that the FWHM of the full width at half maximum of the spherical high-nickel cobalt-free single crystal precursor prepared by the present invention 101 Compared with the precursor prepared by the conventional process, the semi-peak width of the precursor is wider, which shows that the non-crystallinity is better, the primary crystal grains are more uniformly distributed, and the uniform growth of the crystal grains in the sintering process is facilitated.

Claims (4)

1. A preparation method of a spherical high-nickel cobalt-free single crystal precursor is characterized by comprising the following steps:
s1, taking the molar ratio of Ni: preparing a nickel-manganese mixed salt solution with the concentration of 1.0-2.0 mol/L from the nickel salt and the manganese salt with Mn = x: y;
s2, preparing a reaction base solution from the alkali solution and the ammonia solution, and adjusting the pH value of the reaction base solution to be 12.5-13.0;
s3, simultaneously introducing a nickel-manganese mixed salt solution, a doped element salt solution, an alkali solution and an ammonia solution into the reaction base solution to react under the nitrogen environment, controlling the reaction temperature to be 20-40 ℃ in the reaction process, adjusting the pH value of the reaction solution and the feeding speed of the nickel-manganese mixed salt solution according to the median particle size of a reaction product, stopping feeding when the median particle size of the reaction product is 2.5-4.0 mu m, filtering, washing, drying, screening and removing iron to obtain a spherical high-nickel cobalt-free single crystal precursor;
in the step S3, when the median particle size of the reaction product is more than 0 and less than D50 and less than 2 mu m, controlling the pH value in the reaction process to be 12.3-13.0; when the median particle diameter D50 of the reaction product is more than or equal to 2 mu m, controlling the pH value in the reaction process to be 11.5-12.2;
in the step S3, when the median particle size of the reaction product is more than 0 and less than D50 and less than 1.5 mu m, controlling the flow of the nickel-manganese mixed salt to be 200L/h-400L/h; when the median particle size of the reaction product is not less than 1.5 mu m and not more than D50 and less than 2 mu m, controlling the flow of the nickel-manganese mixed salt to be 400-600L/h; when the median particle diameter D50 of the reaction product is more than or equal to 2 mu m, controlling the flow of the nickel-manganese mixed salt to be 600L/h-800L/h;
in the step S3, the doping element is Al, mg, zr, fe, ti or W;
the steps S2 and S3 are carried out in a reaction kettle, and the reaction kettle is provided with a long-diameter paddle;
the diameter of the long-diameter blade/the diameter of the kettle is 0.50 to 0.65, and the stirring speed is 300rpm to 500rpm;
the molecular formula of the spherical high-nickel cobalt-free monocrystal precursor is Ni x Mn y M z (OH) 2 Wherein x + y + z =1, x is more than or equal to 0.6 and less than or equal to 1.0,0 and less than or equal to 0.05, M is a doping element, and the specific surface area of the spherical high-nickel cobalt-free single crystal precursor is 20m 2 /g~50m 2 (iv) a half-value width of 0.8 to 1.80.
2. The method according to claim 1, wherein in step S1, the nickel salt is nickel sulfate, nickel chloride or nickel nitrate, and the manganese salt is manganese sulfate, manganese chloride or manganese nitrate.
3. The method according to claim 1, wherein the concentration of the ammonia solution is 13mol/L and the alkali solution is 10mol/L sodium hydroxide solution in steps S2 and S3.
4. The method according to claim 1, wherein the ammonia concentration in the reaction base solution and the reaction solution is controlled to be 4 to 10g/L in steps S2 and S3.
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