CN113292112A - Preparation method of high-nickel ternary positive electrode precursor - Google Patents

Preparation method of high-nickel ternary positive electrode precursor Download PDF

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CN113292112A
CN113292112A CN202110556082.8A CN202110556082A CN113292112A CN 113292112 A CN113292112 A CN 113292112A CN 202110556082 A CN202110556082 A CN 202110556082A CN 113292112 A CN113292112 A CN 113292112A
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nickel
precursor
complexing agent
positive electrode
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赵尹
金枫
施利毅
王帆
袁帅
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University of Shanghai for Science and Technology
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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Abstract

The invention relates to the technical field of electrode materials, in particular to a preparation method of a high-nickel ternary positive electrode precursor. The preparation method provided by the invention comprises the following steps: mixing soluble cobalt salt, soluble manganese salt, soluble nickel salt and water to obtain a precursor solution; mixing a precipitant solution and a complexing agent solution to obtain a mixed solution of the precipitant and the complexing agent; leading the precursor solution and the mixed solution of the precipitator and the complexing agent into a microchannel reactor in parallel flow, and carrying out coprecipitation reaction to obtain primary particles; mixing the primary particles with water to obtain a slurry; spraying and granulating the slurry to obtain a nickelic ternary positive electrode precursor; the percentage of the amount of nickel in the soluble nickel salt to the total amount of cobalt in the soluble cobalt salt, manganese in the soluble manganese salt and nickel in the soluble nickel salt is more than or equal to 60%. The high-nickel ternary positive electrode precursor has the advantages of uniform distribution of the shape and size of primary particles, uniform distribution of elements and high sphericity of secondary particles.

Description

Preparation method of high-nickel ternary positive electrode precursor
Technical Field
The invention relates to the technical field of electrode materials, in particular to a preparation method of a high-nickel ternary positive electrode precursor.
Background
The layered nickelic (Ni is more than or equal to 0.6) ternary cathode material has great application potential in the field of power batteries, but a plurality of problems still need to be overcome, wherein the preparation process of the precursor of the ternary cathode material is particularly critical. At present, the preparation of the precursor of the ternary cathode material mainly adopts a hydroxide coprecipitation method, and two reversible reaction equilibrium processes exist in the coprecipitation reaction system: firstly, the complex reaction of metal cations and ammonia water is balanced; the second is the precipitation reaction equilibrium of metal ions and alkali solution. The core process parameters comprise saline-alkali concentration, ammonia water concentration, reaction liquid adding speed in the reaction kettle, reaction temperature, pH value, stirring speed, solid content and the like, and each parameter can influence the particle size, the morphology, the element proportion and the like of the precursor. Namely, in the preparation process, the pH value needs to be kept near the equilibrium point, and then the auxiliary complexing agent is used for complexing transition metal ions, so that the regulation of the number of crystal nuclei in the system is finally achieved, and the layered nickelic ternary cathode material with better performance is formed.
It is worth noting that the primary particles prepared by the traditional ternary precursor preparation process are often non-uniform in size distribution and disorderly aggregated into secondary particles, and the disorderly stacking causes anisotropic stress in the circulation process, which easily causes the deterioration of mechanical structure and electrochemical stability.
Disclosure of Invention
The invention aims to provide a preparation method of a high-nickel ternary cathode precursor, the high-nickel ternary cathode precursor prepared by the preparation method has uniform primary particle size, uniform dispersion and uniform element distribution, and the high-nickel ternary cathode precursor prepared from the primary particles of the high-nickel ternary cathode precursor has high sphericity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nickelic ternary anode precursor, which comprises the following steps:
mixing soluble cobalt salt, soluble manganese salt, soluble nickel salt and water to obtain a precursor solution;
mixing a precipitant solution and a complexing agent solution to obtain a mixed solution of the precipitant and the complexing agent;
enabling the precursor solution and the mixed solution of the precipitator and the complexing agent to flow into a microchannel reactor in parallel for coprecipitation reaction to obtain primary particles of the high-nickel ternary anode precursor;
mixing the primary particles of the high-nickel ternary positive electrode precursor with water to obtain slurry;
carrying out spray granulation on the slurry to obtain the high-nickel ternary positive electrode precursor;
the percentage of the amount of the nickel in the soluble nickel salt to the total amount of the cobalt in the soluble cobalt salt, the manganese in the soluble manganese salt and the nickel in the soluble nickel salt is more than or equal to 60%.
The percentage of the amount of the nickel in the soluble nickel salt to the total amount of the cobalt in the soluble cobalt salt, the manganese in the soluble manganese salt and the nickel in the soluble nickel salt is more than or equal to 60%.
Preferably, the concentration of soluble cobalt salt, soluble manganese salt and soluble nickel salt in the precursor solution is 0.01-2 mol/L independently.
Preferably, the concentration of the precipitator in the mixed solution of the precipitator and the complexing agent is 0.01-2 mol/L;
the concentration of the complexing agent in the mixed solution of the precipitating agent and the complexing agent is 0.01-4 mol/L.
Preferably, the precipitant in the mixed solution of precipitant and complexing agent includes sodium hydroxide and/or potassium hydroxide;
the complexing agent in the mixed solution of the precipitator and the complexing agent comprises one or more of ammonia water, citric acid and ethylene diamine tetraacetic acid;
when the complexing agent comprises ammonia water, the concentration of the complexing agent in the mixed solution of the precipitator and the complexing agent is calculated by ammonia in the ammonia water.
Preferably, when the precursor solution and the mixed solution of the precipitator and the complexing agent are introduced into the microchannel reactor in parallel, the flow rates of the precursor solution and the mixed solution of the precipitator and the complexing agent are independently 1-50 mL/min.
Preferably, the inner diameter of the microchannel reactor is 0.5-5 mm.
Preferably, the temperature of the coprecipitation reaction is 40-70 ℃ and the time is 1-60 s.
Preferably, the product obtained by the coprecipitation reaction is mixed with water by ball milling;
the rotation speed of the ball mill is 100-800 rpm, and the time is 2-6 h;
the solid content of the slurry is 2-25 wt%.
Preferably, the inlet temperature of the spray granulation is 150-250 ℃, the outlet temperature is 70-150 ℃, the air flow rate is 20-70 mL/min, and the pumping rate of the slurry is 1-15 mL/min.
The invention provides a preparation method of a nickelic ternary anode precursor, which comprises the following steps: mixing soluble cobalt salt, soluble manganese salt, soluble nickel salt and water to obtain a precursor solution; mixing a precipitant solution and a complexing agent solution to obtain a mixed solution of the precipitant and the complexing agent; enabling the precursor solution and the mixed solution of the precipitator and the complexing agent to flow into a microchannel reactor in parallel for coprecipitation reaction to obtain primary particles of the high-nickel ternary anode precursor; mixing the primary particles of the high-nickel ternary positive electrode precursor with water to obtain slurry; carrying out spray granulation on the slurry to obtain the high-nickel ternary positive electrode precursor; the percentage of the amount of the nickel in the soluble nickel salt to the total amount of the cobalt in the soluble cobalt salt, the manganese in the soluble manganese salt and the nickel in the soluble nickel salt is more than or equal to 60%. The invention utilizes the characteristics of the domain-limiting effect and the efficient mass and heat transfer of the microchannel technology, the metal salt solution and the alkali liquor mixed solution are quickly subjected to nucleation reaction after contacting, primary particles with uniform size distribution and uniform dispersion are generated, the synthesis of the primary particles can be accurately controlled by the combination of the addition of a precipitator and a complexing agent and the microchannel reaction, the regulation and control of the microstructure of the primary particles are realized, and the accurate control of the primary particles of the high-nickel ternary anode precursor and the quick preparation of secondary particles (namely the high-nickel ternary anode precursor) are efficiently realized by adopting the spray granulation technology on the basis of obtaining the primary particles with uniform element and particle sizes.
Drawings
FIG. 1 is a TEM image of a primary particle of a ternary positive electrode of nickel system prepared in example 1;
FIG. 2 is an XRD pattern of the primary particles of the ternary positive electrode of nickel system prepared in example 1;
FIG. 3 is a TEM image of the primary particles of the ternary positive electrode of nickel system prepared in example 2;
FIG. 4 is an XRD pattern of the primary particles of the ternary positive electrode of nickel system prepared in example 2;
FIG. 5 is a TEM image of the primary particles of the ternary positive electrode of nickel system prepared in example 3;
FIG. 6 is an XRD pattern of the primary particles of the ternary positive electrode of nickel system prepared in example 3;
FIG. 7 is a TEM image of the primary particles of the ternary positive electrode of nickel system prepared in example 4;
FIG. 8 is a TEM image of the primary particles of the ternary positive electrode of nickel system prepared in example 5;
FIG. 9 is a TEM image of the primary particles of the ternary positive electrode of nickel system prepared in example 6;
FIG. 10 is a TEM image of the primary particles of the ternary positive electrode of nickel system prepared in example 7;
FIG. 11 is a TEM image of the primary particles of the ternary positive electrode of nickel system prepared in example 8;
FIG. 12 is an SEM image of a ternary nickel-based positive electrode precursor prepared in example 9;
FIG. 13 is an SEM image of a ternary nickel-based positive electrode precursor prepared in example 10;
FIG. 14 is an SEM image of a ternary nickel-based positive electrode precursor prepared in example 11;
FIG. 15 is an SEM image of a ternary nickel-based positive electrode precursor prepared in example 12;
FIG. 16 is an SEM image of a ternary nickel-based positive electrode precursor prepared in example 13;
FIG. 17 is an SEM image of a ternary nickel-based positive electrode precursor prepared in example 14;
FIG. 18 is a TEM image of the nickelic ternary positive electrode precursor prepared in comparative example 1;
fig. 19 is an SEM image of the nickelic ternary positive electrode precursor prepared in comparative example 2.
Detailed Description
The invention provides a preparation method of a nickelic ternary anode precursor, which comprises the following steps:
mixing soluble cobalt salt, soluble manganese salt, soluble nickel salt and water to obtain a precursor solution;
mixing a precipitant solution and a complexing agent solution to obtain a mixed solution of the precipitant and the complexing agent;
enabling the precursor solution and the mixed solution of the precipitator and the complexing agent to flow into a microchannel reactor in parallel for coprecipitation reaction to obtain primary particles of the high-nickel ternary anode precursor;
mixing the primary particles of the high-nickel ternary positive electrode precursor with water to obtain slurry;
carrying out spray granulation on the slurry to obtain the high-nickel ternary positive electrode precursor;
the percentage of the amount of the nickel in the soluble nickel salt to the total amount of the cobalt in the soluble cobalt salt, the manganese in the soluble manganese salt and the nickel in the soluble nickel salt is more than or equal to 60%.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
The method mixes soluble cobalt salt, soluble manganese salt, soluble nickel salt and water to obtain precursor solution. In the invention, the soluble cobalt salt preferably comprises one or more of cobalt sulfate, cobalt nitrate and cobalt acetate; when the soluble cobalt salt is more than two of the specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the soluble cobalt salt can be mixed according to any proportion. In the present invention, the soluble componentThe manganese salt preferably comprises one or more of manganese sulfate, manganese nitrate and manganese acetate; when the soluble manganese salt is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the soluble manganese salt can be mixed according to any proportion. In the invention, the soluble nickel salt preferably comprises one or more of nickel sulfate, nickel nitrate and nickel acetate; when the soluble nickel salt is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the soluble nickel salt can be mixed according to any proportion. In a particular embodiment of the invention, the soluble cobalt salt is in particular CoSO4·7H2O, wherein the soluble nickel salt is NiSO4·6H2O, the soluble manganese salt is MnSO4·4H2O。
The mixing process is not particularly limited, and may be performed by a method known to those skilled in the art.
In the invention, the concentration of the soluble cobalt salt, the soluble manganese salt and the soluble nickel salt in the precursor solution is preferably 0.01-2 mol/L independently, and more preferably 0.01-0.08 mol/L independently.
The preparation method also comprises the step of mixing the precipitant solution and the complexing agent solution to obtain a mixed solution of the precipitant and the complexing agent. In the invention, the precipitant in the mixed solution of the precipitant and the complexing agent preferably comprises sodium hydroxide and/or potassium hydroxide, and when the precipitant is a mixture of sodium hydroxide and potassium hydroxide, the ratio of the sodium hydroxide and the potassium hydroxide is not particularly limited, and the sodium hydroxide and the potassium hydroxide can be mixed according to any ratio. In the invention, the complexing agent in the mixed solution of the precipitator and the complexing agent comprises one or more of ammonia water, citric acid and ethylene diamine tetraacetic acid, and when the complexing agent is more than two of the specific choices, the proportion of the specific substances is not limited by any special limit, and the substances are mixed according to any proportion. In the present invention, when the complexing agent includes ammonia water, the concentration of the complexing agent in the mixed solution of the precipitant and the complexing agent is calculated as ammonia in the ammonia water.
In the invention, the concentration of the precipitant solution is preferably 0.01-2 mol/L, and more preferably 0.05-1.2 mol/L; the concentration of the complexing agent solution is preferably 0.01-4 mol/L, and more preferably 0.08-3.2 mol/L. The concentration of the precipitator in the mixed liquid of the precipitator and the complexing agent is preferably 0.01-2 mol/L, more preferably 0.05-1.2 mol/L, and most preferably 0.1-0.8 mol/L; the concentration of the complexing agent in the mixed solution of the precipitator and the complexing agent is preferably 0.01-4 mol/L, more preferably 0.08-3.2 mol/L, and most preferably 0.5-2.5 mol/L.
After a precursor solution and a mixed solution of a precipitator and a complexing agent are obtained, the precursor solution and the mixed solution of the precipitator and the complexing agent are introduced into a microchannel reactor in a parallel flow manner for coprecipitation reaction, and primary particles of a high-nickel ternary anode precursor are obtained;
in the invention, the flow rates of the precursor solution and the mixed solution of the precipitant and the complexing agent are independent, preferably 1-50 mL/min, more preferably 5-35 mL/min, and most preferably 7-20 mL/min.
In the invention, the inner diameter of the microchannel reactor is preferably 0.5-5 mm, more preferably 1.0-4.0 mm, and most preferably 2.0-3.0 mm. In the invention, the temperature of the coprecipitation reaction is preferably 40-70 ℃, and more preferably 50-60 ℃; the time is preferably 1 to 60 seconds, and more preferably 5 to 10 seconds.
In the present invention, the product of the coprecipitation reaction is preferably collected at the outlet of the microchannel reactor.
The invention also preferably carries out centrifugation, filtration, washing and drying on the collected product in sequence. The centrifugation process is not limited in any way, and can be carried out by adopting a process well known to a person skilled in the art; the filtration is not limited in any way by the present invention, and can be carried out by a process well known to those skilled in the art; after the filtration is finished, the filter residue obtained by the filtration is preferably washed; the washing is not particularly limited, and the washing may be performed by a process known to those skilled in the art; in the present invention, the number of filtration and washing is preferably not less than 1, and the filtration and washing is preferably performed so that the washing solution obtained after washing is neutral. In the invention, the drying temperature is preferably 60-120 ℃, and more preferably 80-100 ℃; the time is preferably 8 to 15 hours, and more preferably 10 to 13 hours.
After the primary particles of the high-nickel ternary positive electrode precursor are obtained, mixing the primary particles of the high-nickel ternary positive electrode precursor with water to obtain slurry; and carrying out spray granulation on the slurry to obtain the high-nickel ternary anode precursor.
Before mixing, the invention preferably grinds the primary particles of the nickelic ternary positive electrode precursor; the grinding process is not particularly limited, and may be performed by a method known to those skilled in the art.
In the present invention, the water is preferably deionized water.
In the present invention, the mixing is preferably performed by ball milling; the rotation speed of the ball milling is preferably 100-800 rpm, more preferably 200-600 rpm, and most preferably 300-500 rpm; the time is preferably 2 to 6 hours, and more preferably 3 to 5 hours.
In the invention, the solid content of the slurry is preferably 2 to 25 wt%, more preferably 5 to 20 wt%, and most preferably 10 to 15 wt%.
In the invention, the inlet temperature of the spray granulation is preferably 150-250 ℃, and more preferably 180-220 ℃; the outlet temperature is preferably 70-150 ℃, and more preferably 80-110 ℃; the air flow rate is preferably 20-70 mL/min, and more preferably 40-60 mL/min; the pumping rate of the slurry is preferably 1-15 mL/min, and more preferably 5-10 mL/min.
In the invention, the spray granulation process can quickly prepare the high-nickel ternary cathode precursor with higher sphericity, uniform element distribution and concentrated particle size distribution.
In the present invention, the particle size after the spray granulation is preferably 1 to 10um, and more preferably 3 to 8 um.
The following examples are provided to illustrate the preparation method of the nickel-based ternary positive electrode precursor of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
2.81g of CoSO4·7H2O、1.69g MnSO4·4H2O、21.03g NiSO4·6H2Mixing O and 1000mL of deionized water to obtain a precursor solution (the concentration of nickel ions in the precursor solution is 0.08mol/L, the concentration of cobalt ions is 0.01mol/L, and the concentration of manganese ions is 0.01 mol/L);
adding 7.4g of NaOH and 14.0mL of ammonia water into a 1L volumetric flask, and using deionized water to perform constant volume to obtain 1L of mixed solution of NaOH with the concentration of 0.185mol/L and ammonia water with the concentration of 0.2 mol/L;
the precursor solution and the mixed solution of sodium hydroxide and ammonia water are introduced into a microchannel reactor in parallel flow to carry out coprecipitation reaction, wherein the flow rate of the precursor solution is 7.0mL/min, the flow rate of the mixed solution of sodium hydroxide and ammonia water is 7.0mL/min, the reaction temperature is 50 ℃, the inner diameter of the microchannel reactor is 0.75mm, and the time is 1 s; collecting the precursor at the outlet of a micro-channel reactor, centrifuging the collected product once to quickly stop reaction, washing and filtering the product for 5 times by using deionized water, and drying the product for 12 hours at the temperature of 80 ℃ to obtain primary particles of a high-nickel ternary positive precursor;
performing a TEM test on the primary particles of the high-nickel ternary cathode precursor, wherein the test result is shown in FIG. 1, and as can be seen from FIG. 1, the primary particles of the high-nickel ternary cathode precursor have uniform size distribution and an average particle size of 40.0 nm;
performing DLS (laser particle size distribution) test on the primary particles of the high-nickel ternary positive electrode precursor to obtain a primary particle size distribution index (PDI) of 0.1163, wherein the primary particle size distribution uniformity of the high-nickel ternary positive electrode precursor is good;
XRD (X-ray diffraction) testing was carried out on the primary particles of the nickel-based ternary positive electrode precursor, and the testing result is shown in figure 2, and it can be seen from figure 2 that the diffraction peak of the primary particles of the nickel-based ternary positive electrode precursor corresponds to beta-Ni (OH)2(JCPDS 14-0117), which belongs to a typical high-nickel NCM precursor.
Example 2
The preparation process is referred to example 1, except that the concentration of nickel ions in the precursor solution is 0.09mol/L, the concentration of cobalt ions is 0.005mol/L, and the concentration of manganese ions is 0.005 mol/L;
a TEM test is performed on the primary particles of the nickel-based ternary positive electrode precursor prepared in example 2, and the test result is shown in fig. 3, and it can be seen from fig. 3 that the primary particles of the nickel-based ternary positive electrode precursor have uniform size distribution and an average particle size of 62.9 nm;
performing DLS test on the primary particles of the high-nickel ternary positive electrode precursor to obtain that the particle size distribution index (PDI) of the primary particles of the high-nickel ternary positive electrode precursor is 0.638, and the particle distribution uniformity of the primary particles of the high-nickel ternary positive electrode precursor is good;
XRD (X-ray diffraction) testing was carried out on the primary particles of the nickel-based ternary positive electrode precursor, and the testing result is shown in FIG. 4. As can be seen from FIG. 4, the diffraction peak of the primary particles of the nickel-based ternary positive electrode precursor corresponds to beta-Ni (OH)2(JCPDS 14-0117), which belongs to a typical high-nickel NCM precursor.
Example 3
The preparation process is referred to example 1, and the difference is only that the concentration of nickel ions in the precursor solution is 0.06mol/L, the concentration of cobalt ions is 0.02mol/L, and the concentration of manganese ions is 0.02 mol/L;
a TEM test is performed on the primary particles of the nickel-based ternary positive electrode precursor prepared in example 3, and the test result is shown in fig. 5, and it can be seen from fig. 5 that the primary particles of the nickel-based ternary positive electrode precursor have uniform size distribution and an average particle size of 62.8 nm;
performing DLS test on the primary particles of the high-nickel ternary positive electrode precursor to obtain that the particle size distribution index (PDI) of the primary particles of the high-nickel ternary positive electrode precursor is 0.2960, and the primary particles of the high-nickel ternary positive electrode precursor have good particle distribution uniformity;
the XRD test of the primary particles of the nickel-based ternary positive electrode precursor showed that the diffraction peak of the primary particles of the nickel-based ternary positive electrode precursor corresponded to β -ni (oh) as shown in fig. 6, and as can be seen from fig. 62(JCPDS 14-0117) Belonging to typical high nickel NCM precursors.
Example 4
The preparation process refers to example 1, and the difference is only that the pumping flow rate of the reaction solution in the microchannel reaction process is 3 mL/min;
a TEM test is performed on the primary particles of the nickel-based ternary positive electrode precursor prepared in example 4, and the test result is shown in fig. 7, and it can be seen from fig. 7 that the primary particles of the nickel-based ternary positive electrode precursor have uniform size distribution and an average particle size of 120.0 nm;
and performing DLS test on the primary particles of the high-nickel ternary positive electrode precursor to obtain the primary particles of the high-nickel ternary positive electrode precursor with the particle size distribution index (PDI) of 0.011 and good particle distribution uniformity.
Example 5
The preparation is referred to example 1, with the only difference that the sodium hydroxide concentration in the lye is 0.19M;
a TEM test is performed on the primary particles of the nickel-based ternary positive electrode precursor prepared in example 5, and the test result is shown in fig. 8, and it can be seen from fig. 8 that the primary particles of the nickel-based ternary positive electrode precursor have uniform size distribution and an average particle size of 70.2 nm;
and performing DLS test on the primary particles of the high-nickel ternary positive electrode precursor to obtain the primary particles of the high-nickel ternary positive electrode precursor with the particle size distribution index (PDI) of 0.415 and good particle distribution uniformity.
Example 6
The preparation is referred to example 1, with the only difference that the ammonia concentration in the lye is 0.1M;
a TEM test is performed on the primary particles of the nickel-based ternary positive electrode precursor prepared in example 6, and the test result is shown in fig. 9, and it can be seen from fig. 9 that the primary particles of the nickel-based ternary positive electrode precursor have uniform size distribution and an average particle size of 85.5 nm;
and performing DLS test on the primary particles of the high-nickel ternary positive electrode precursor to obtain the primary particles of the high-nickel ternary positive electrode precursor with the particle size distribution index (PDI) of 0.364 and good particle distribution uniformity.
Example 7
The preparation is referred to example 1, with the only difference that the ammonia concentration in the lye is 0.3M;
a TEM test is performed on the primary particles of the nickel-based ternary positive electrode precursor prepared in example 7, and the test result is shown in fig. 10, and it can be seen from fig. 10 that the primary particles of the nickel-based ternary positive electrode precursor have uniform size distribution and an average particle size of 80.6 nm;
and performing DLS test on the primary particles of the high-nickel ternary positive electrode precursor to obtain the primary particles of the high-nickel ternary positive electrode precursor with a particle size distribution index (PDI) of 0.0157 and good particle distribution uniformity.
Example 8
The preparation process is referred to example 1, except that the metal salt solution concentration is 1.5mol/L, the sodium hydroxide concentration is 2.775mol/L, and the ammonia water concentration is 3 mol/L;
a TEM test is performed on the primary particles of the nickel-based ternary positive electrode precursor prepared in example 8, and the test result is shown in fig. 11, and it can be seen from fig. 11 that the primary particles of the nickel-based ternary positive electrode precursor have uniform size distribution and an average particle size of 30.1 nm;
and performing DLS test on the primary particles of the high-nickel ternary positive electrode precursor to obtain the primary particles of the high-nickel ternary positive electrode precursor with a particle size distribution index (PDI) of 0.2741, wherein the primary particles of the high-nickel ternary positive electrode precursor have good particle distribution uniformity.
Example 9
The primary particle preparation process refers to the preparation of example 1 to obtain the primary particles of the ternary cathode precursor;
grinding the primary particles of the high-nickel ternary positive electrode precursor until large particles disappear, mixing 3.33g of the primary particles with 30mL of deionized water, and carrying out ball milling in a ball milling tank, wherein the adopted milling balls are zirconia balls with the diameter of 3mm, the total mass of the zirconia balls is 100g, the rotating speed of the ball milling is 400rpm, the time is 5min, the interval time is 5min, and ball milling is carried out for 36 circles to obtain slurry with the solid content of 10 wt%;
carrying out spray granulation on the slurry, wherein the inlet temperature of the spray granulation is 220 ℃, the outlet temperature of the spray granulation is 110 ℃, the air flow rate is 50mL/min, and the pumping rate of the slurry is 9mL/min, so as to obtain a nickelic ternary anode precursor;
performing SEM test on the high-nickel ternary positive electrode precursor, wherein the test result is shown in FIG. 12, and as can be seen from FIG. 12, the particle sphericity is higher after spray granulation, and the average particle size of the high-nickel ternary positive electrode precursor is 2.9 μm;
and performing DLS test on the high-nickel ternary cathode precursor to obtain the high-nickel ternary cathode precursor with particle size distribution index (PDI) of 2.374 and good particle distribution uniformity.
Example 10
The primary particle preparation process refers to the preparation of example 1 to obtain the primary particles of the ternary cathode precursor;
the preparation process of the ternary cathode precursor refers to the preparation of the high-nickel ternary cathode precursor in example 9, and the difference is that the airflow velocity in the spray drying process is 30 mL/min;
performing SEM test on the high-nickel ternary positive electrode precursor, wherein the test result is shown in FIG. 13, and as can be seen from FIG. 13, the particle sphericity is higher after spray granulation, and the average particle size of the high-nickel ternary positive electrode precursor is 6.3 μm;
and performing DLS test on the high-nickel ternary cathode precursor, wherein the particle size distribution index (PDI) of the high-nickel ternary cathode precursor is 2.287, and the particle distribution uniformity of the high-nickel ternary cathode precursor is good.
Example 11
The primary particle preparation process refers to the preparation of example 1 to obtain the primary particles of the ternary cathode precursor;
the preparation process of the ternary cathode precursor refers to the preparation of the high-nickel ternary cathode precursor in example 9, and the difference is that the airflow velocity in the spray drying process is 60 mL/min;
performing SEM test on the high-nickel ternary cathode precursor, wherein the test result is shown in FIG. 14, and as can be seen from FIG. 14, the particle sphericity is higher after spray granulation, and the average particle size of the high-nickel ternary cathode precursor is 3.3 μm;
and performing DLS test on the high-nickel ternary cathode precursor, wherein the particle size distribution index (PDI) of the high-nickel ternary cathode precursor is 3.342, and the particle distribution uniformity of the high-nickel ternary cathode precursor is good.
Example 12
The primary particle preparation process refers to the preparation of example 1 to obtain the primary particles of the ternary cathode precursor;
the preparation process of the ternary cathode precursor refers to the preparation of the high-nickel ternary cathode precursor in example 9, and the difference is that the solid content of the slurry is 2 wt%;
performing SEM test on the high-nickel ternary positive electrode precursor, wherein the test result is shown in FIG. 15, and as can be seen from FIG. 15, the particle sphericity is higher after spray granulation, and the average particle size of the high-nickel ternary positive electrode precursor is 1.95 μm;
and performing DLS test on the high-nickel ternary cathode precursor to obtain the high-nickel ternary cathode precursor with particle size distribution index (PDI) of 2.265 and good particle distribution uniformity.
Example 13
The primary particle preparation process refers to the preparation of example 1 to obtain the primary particles of the ternary cathode precursor;
the preparation process of the ternary cathode precursor refers to the preparation of the high-nickel ternary cathode precursor in example 9, and the difference is that the solid content of the slurry is 3 wt%;
performing SEM test on the high-nickel ternary positive electrode precursor, wherein the test result is shown in FIG. 16, and as can be seen from FIG. 16, the particle sphericity is higher after spray granulation, and the average particle size of the high-nickel ternary positive electrode precursor is 2.11 μm;
and performing DLS test on the high-nickel ternary positive electrode precursor to obtain the high-nickel ternary positive electrode precursor, wherein the particle size distribution index (PDI) of the high-nickel ternary positive electrode precursor is 2.025, and the particle distribution uniformity of the high-nickel ternary positive electrode precursor is good.
Example 14
The primary particle preparation process refers to the preparation of example 1 to obtain the primary particles of the ternary cathode precursor;
the preparation process of the ternary cathode precursor refers to the preparation of the high-nickel ternary cathode precursor in example 9, and the difference is that the solid content of the slurry is 8 wt%;
performing SEM test on the high-nickel ternary cathode precursor, wherein the test result is shown in FIG. 17, and as can be seen from FIG. 17, the particle sphericity is higher after spray granulation, and the average particle size of the high-nickel ternary cathode precursor is 2.27 μm;
and performing DLS test on the high-nickel ternary cathode precursor to obtain the high-nickel ternary cathode precursor with the particle size distribution index (PDI) of 2.630 and good particle distribution uniformity.
Comparative example 1
The preparation process refers to example 1, except that the coprecipitation reaction is carried out in a three-neck flask, the volume ratio of the precursor solution to the mixed solution of sodium hydroxide and ammonia water is 1:1, the coprecipitation reaction is carried out under the condition of mechanical stirring, the rotating speed of the stirring is 800rpm, the time is 1h, the temperature is 50 ℃, and the pH value is 11.0 +/-0.1;
the precursor prepared in comparative example 1 was subjected to TEM testing, and the test result is shown in fig. 18, and it can be seen from fig. 18 that the precursor prepared in comparative example 1 had a severe agglomeration phenomenon, and the average particle size thereof could not be measured.
Comparative example 2
The preparation process refers to example 4, except that the coprecipitation reaction is carried out in a three-neck flask, the reaction temperature is 50 ℃, the mechanical stirring is carried out at 800rpm, the pH value is 11.0 +/-0.2, the reaction is carried out for 20 hours under the protection of nitrogen, and after aging for 2 hours, the materials are dried for 12 hours at 80 ℃;
the precursor prepared in comparative example 2 was subjected to SEM test, and the test result is shown in fig. 19, and it can be seen from fig. 19 that the precursor was seriously agglomerated, had poor sphericity, and had an average particle size of 5 μm.
Test example
ICP test was performed on the primary particles of the ternary positive electrode precursor of nickel system prepared in examples 1 to 3, and the test results are shown in Table 1,
TABLE 1 ICP data of primary particles of nickelic ternary positive electrode precursors prepared in examples 1 to 3
Figure BDA0003077251790000121
Figure BDA0003077251790000131
As can be seen from Table 1, the proportion distribution of the elements of the ternary precursor obtained by the reaction of the method is consistent with the expected result, and the consistency is good.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A preparation method of a high-nickel ternary positive electrode precursor is characterized by comprising the following steps:
mixing soluble cobalt salt, soluble manganese salt, soluble nickel salt and water to obtain a precursor solution;
mixing a precipitant solution and a complexing agent solution to obtain a mixed solution of the precipitant and the complexing agent;
enabling the precursor solution and the mixed solution of the precipitator and the complexing agent to flow into a microchannel reactor in parallel for coprecipitation reaction to obtain primary particles of the high-nickel ternary anode precursor;
mixing the primary particles of the high-nickel ternary positive electrode precursor with water to obtain slurry;
carrying out spray granulation on the slurry to obtain the high-nickel ternary positive electrode precursor;
the percentage of the amount of the nickel in the soluble nickel salt to the total amount of the cobalt in the soluble cobalt salt, the manganese in the soluble manganese salt and the nickel in the soluble nickel salt is more than or equal to 60%.
2. The preparation method according to claim 1, wherein the concentrations of the soluble cobalt salt, the soluble manganese salt and the soluble nickel salt in the precursor solution are independently 0.01 to 2 mol/L.
3. The preparation method according to claim 1, wherein the concentration of the precipitant in the mixed solution of the precipitant and the complexing agent is 0.01 to 2 mol/L;
the concentration of the complexing agent in the mixed solution of the precipitating agent and the complexing agent is 0.01-4 mol/L.
4. The method according to claim 1 or 3, wherein the precipitant in the mixed solution of the precipitant and the complexing agent comprises sodium hydroxide and/or potassium hydroxide;
the complexing agent in the mixed solution of the precipitator and the complexing agent comprises one or more of ammonia water, citric acid and ethylene diamine tetraacetic acid;
when the complexing agent comprises ammonia water, the concentration of the complexing agent in the mixed solution of the precipitator and the complexing agent is calculated by ammonia in the ammonia water.
5. The preparation method according to claim 1, wherein when the precursor solution and the mixed solution of the precipitant and the complexing agent are introduced into the microchannel reactor in parallel, the flow rates of the precursor solution and the mixed solution of the precipitant and the complexing agent are independently 1 to 50 mL/min.
6. The process of claim 1 or 5, wherein the microchannel reactor has an internal diameter of 0.5 to 5 mm.
7. The method according to claim 1 or 5, wherein the temperature of the coprecipitation reaction is 40 to 70 ℃ and the time is 1 to 60 seconds.
8. The preparation method according to claim 1, wherein the primary particles of the high-nickel ternary positive electrode precursor are mixed with water by ball milling;
the rotation speed of the ball mill is 100-800 rpm, and the time is 2-6 h;
the solid content of the slurry is 2-25 wt%.
9. The method according to claim 1 or 8, wherein the inlet temperature of the spray granulation is 150 to 250 ℃, the outlet temperature is 70 to 150 ℃, the air flow rate is 20 to 70mL/min, and the pumping rate of the slurry is 1 to 15 mL/min.
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