CN116835669A - Ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology and preparation method thereof - Google Patents

Ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology and preparation method thereof Download PDF

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CN116835669A
CN116835669A CN202310869776.6A CN202310869776A CN116835669A CN 116835669 A CN116835669 A CN 116835669A CN 202310869776 A CN202310869776 A CN 202310869776A CN 116835669 A CN116835669 A CN 116835669A
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quaternary
positive electrode
electrode material
solution
particle size
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孙建
刘国标
郭鹏
崔爽
丁嘉琪
王璐瑶
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Xinxiang Tianli Lithium Energy Co ltd
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Xinxiang Tianli Lithium Energy Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/006Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/20Particle morphology extending in two dimensions, e.g. plate-like
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/50Agglomerated particles

Abstract

The application discloses an ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology and a preparation method thereof, wherein the preparation method comprises the following steps: continuously adding a quaternary A salt solution, a first liquid alkali solution and a first nitrogen-containing complexing agent into a reaction kettle containing a mixed solution of hydroxide seed crystals with uniform particle size, regulating and controlling the pH value of a reaction system to gradually reduce, stopping feeding, aging, continuously adding the quaternary A salt solution, the first liquid alkali solution and the first nitrogen-containing complexing agent, regulating the flow of the first liquid alkali solution, gradually reducing the pH value of the reaction system to 10.0-10.5, and stopping coprecipitation reaction to obtain hydroxide slurry; and washing and drying the hydroxide slurry to obtain the target product. The primary particles of the ultra-high nickel type precursor obtained by the method are transversely stacked, and the primary particles which are transversely stacked are mutually overlapped, so that the occurrence of cracks of the precursor of the large-particle-size high nickel quaternary positive electrode material is effectively avoided.

Description

Ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology and preparation method thereof
Technical Field
The application belongs to the technical field of lithium ion battery anode materials, and particularly relates to an ultrahigh nickel quaternary anode material precursor with uniform particle size and transverse lamination morphology and a preparation method thereof.
Background
The super-high nickel (nickel element mole percentage is more than 85%) nickel cobalt manganese/aluminum (ternary) or nickel cobalt manganese aluminum (quaternary) layered anode material has the advantages of higher volume and mass energy density, moderate price and the like, and the high nickel ternary/quaternary anode material is widely applied to the fields of electronic products, outdoor power supplies, electric bicycles, new energy automobiles and the like. When the ultra-high nickel type ternary/quaternary positive electrode material is applied to a power battery of a new energy automobile, the ultra-high nickel type ternary/quaternary positive electrode material is required to have a larger secondary particle diameter (D 50 About 12 microns), a large particle diameter (D) is produced due to inheritance of the particle diameter size of the ternary/quaternary positive electrode material and the particle diameter size of its precursor 50 About 12 microns) is necessary for ultra-high nickel ternary/quaternary positive electrode material precursors.
However, at present, a conventional ultra-high nickel ternary/quaternary positive electrode material precursor with large particle size is difficult to prepare by adopting a conventional coprecipitation method, namely: the primary flaky particles are perpendicular to the circle centers of the secondary particles, the primary particles show the large-particle-size conventional ultrahigh-nickel ternary/quaternary positive electrode material precursors which are distributed in a divergent manner, and in the process of preparing the large-particle-size conventional ultrahigh-nickel ternary/quaternary positive electrode material precursors, the large-particle-size conventional ultrahigh-nickel ternary/quaternary positive electrode material precursors are easy to crack and have small particles, so that the corresponding large-particle-size ultrahigh-nickel ternary/quaternary positive electrode materials are cracked, and the corresponding small-particle ultrahigh-nickel ternary/quaternary positive electrode materials are over-burned, and the performance and the service life of the corresponding batteries are influenced.
Disclosure of Invention
In view of the above, the application provides a preparation method of an ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology, which solves the problems that the positive electrode material precursor prepared by the prior art is easy to crack and nonuniform in particle size.
The application also aims to provide the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology.
In order to achieve the above purpose, the technical scheme of the application is realized as follows: the preparation method of the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology comprises the following steps:
s1, continuously adding a quaternary A salt solution, a first liquid alkali solution and a first nitrogen-containing complexing agent into a reaction kettle containing hydroxide seed crystals with uniform particle size, ammonia water with the concentration of 0.1-1.0 mol/L and a mixed solution with the pH value of 12.5-13.0 at a certain feeding speed, stopping feeding when the pH value of a reaction system is gradually reduced to 11.5-12 by adjusting the flow rate of the first liquid alkali solution to 0.1-2.0L/h, aging for 20-120 min, continuously adding the quaternary A salt solution, the first liquid alkali solution and the first nitrogen-containing complexing agent, and stopping coprecipitation reaction when the pH value of the reaction system is gradually reduced to 10.0-10.5 by adjusting the flow rate of the first liquid alkali solution to 0.1-1.0L/h, thereby obtaining hydroxide slurry;
s2, a precursor preparation stage: and (3) washing and drying the hydroxide slurry obtained in the step (S1) to obtain the ultra-high nickel quaternary positive electrode material precursor with the transverse lamination morphology and uniform particle size.
In the above technical scheme, in S1, the temperature of the coprecipitation reaction is 50-80 ℃.
In the above technical scheme, in the step S1, the feeding speeds of the quaternary a salt solution and the first nitrogen-containing complexing agent are respectively 0.5-3L/h and 0.01-1.5L/h; the concentration of each metal element in the quaternary A salt solution is 1.0-3.0 mol/L; the concentration of the first liquid alkali solution is 2.7-14.0 mol/L; the concentration of the first nitrogen-containing complexing agent is 5.0-15.0 mol/L.
In the above technical scheme, in the step S1, the reaction kettle is a 50L reaction kettle, and the feeding speeds of the quaternary a salt solution and the first nitrogen-containing complexing agent are respectively 0.5-3L/h and 0.01-1.5L/h for the 50L reaction kettle.
In the above technical scheme, in S1, the quaternary a salt solution is a mixed solution of inorganic salts or organic salts of nickel, cobalt, manganese and aluminum; the molar ratio of Ni to Co to Mn to Al in the quaternary A salt solution is (0.9-1.0):0.01-0.05:0.01-0.04:0.01-0.02.
In the above technical scheme, in the step S1, the inorganic salt of nickel, cobalt, manganese, and aluminum is sulfate, nitrate, or chloride; the organic salt of nickel, cobalt, manganese and aluminum is acetate; the second nitrogen-containing complexing agent is at least one of ammonia water, ammonium sulfite, ammonium bisulfate, ammonium sulfate, ammonium bisulfide, ammonium hydrosulfide, ammonium thiosulfate, ammonium chloride or ammonium carbonate.
In the above technical scheme, in S1, the first nitrogen-containing complexing agent is at least one of ammonia water, ammonium sulfite, ammonium bisulfide, ammonium sulfate, ammonium bisulfate, ammonium sulfide, ammonium bisulfide, ammonium thiosulfate, ammonium chloride or ammonium carbonate.
In the above technical solution, further, in S1, the hydroxide seed crystal is specifically obtained by the following method:
and respectively adding the quaternary B salt solution, the second alkali solution and the second nitrogen-containing complexing agent into a reaction kettle containing ammonia water base solution at a certain feeding speed, controlling the pH value of a reaction system to be 12.5-13.0 and the concentration of ammonia water in the reaction kettle to be 0.1-1.0 mol/L by adjusting the flow rate of added materials, and performing coprecipitation reaction to obtain hydroxide seed crystals with uniform particle sizes.
In the above technical scheme, further, the reaction kettle is 50L, and for the 50L reaction kettle, the feeding speeds of the quaternary B salt solution, the second liquid alkali solution and the second nitrogen-containing complexing agent are respectively 0.5-3L/h, 0.1-2L/h and 0.01-1.5L/h.
In the above technical scheme, further, the quaternary B salt solution is a mixed solution of inorganic salts or organic salts of nickel, cobalt, manganese and aluminum; the molar ratio of Ni to Co to Mn to Al in the quaternary B salt solution is (0.9-1.0):0.01-0.05:0.01-0.04:0.01-0.02.
In the above technical scheme, further, the inorganic salts of nickel, cobalt, manganese and aluminum are sulfate, nitrate or chloride; the organic salt of nickel, cobalt, manganese and aluminum is acetate; the first nitrogen-containing complexing agent is at least one of ammonia water, ammonium sulfite, ammonium bisulfate, ammonium sulfate, ammonium bisulfide, ammonium hydrosulfide, ammonium thiosulfate, ammonium chloride or ammonium carbonate.
In the technical scheme, the reaction temperature is 30-80 ℃; the reaction time is 0.1-5 h.
In the above technical scheme, further, the second nitrogen-containing complexing agent is at least one of ammonia water, ammonium sulfite, ammonium bisulfate, ammonium sulfate, ammonium bisulfate, ammonium sulfide, ammonium bisulfide, ammonium thiosulfate, ammonium chloride or ammonium carbonate.
In the above technical solution, further, the hydroxide seed crystal is in a spheroid shape.
The second technical scheme of the application is realized as follows: the preparation method is used for preparing the composite material.
In the above technical scheme, the precursor of the positive electrode material has an average particle diameter of 5-20 μm and a structural formula of Ni x Co y Mn z Al 1-x-y-z (OH) 2 Wherein x is more than or equal to 0.9 and less than or equal to 1.0, y is more than or equal to 0.01 and less than or equal to 0.05,0.01, and z is more than or equal to 0.04.
Compared with the prior art, the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology, which is obtained by the method, is compared with the prior conventional high nickel quaternary positive electrode material precursor with primary particles which are perpendicular to the circle center of the secondary particles and are in divergent distribution, and the ultra-high nickel quaternary positive electrode material precursor obtained by the method is characterized in that the primary particles are transversely stacked, and the primary particles are overlapped with each other, so that the occurrence of cracks of the large-particle-size high nickel quaternary positive electrode material precursor is effectively avoided; in addition, the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology, which is obtained by the method, effectively realizes the purpose of uniform particle size, and in addition, the reason for realizing uniform particle size is as follows: according to the application, the pH value is continuously reduced in the growth process, so that the excessive high nucleation supersaturation degree is avoided in the growth stage of precursor particles, new nucleation points are formed outside large particles, and a large number of new small particles are generated, so that the particles are uniform.
Drawings
FIG. 1 is an SEM image of the crystal nucleus prepared in example 1 of the present application and the crystal nucleus prepared in comparative example 1 (using the same crystal nucleus, different growth modes);
FIG. 2 is a high-power SEM image of the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology prepared in example 1 of the present application;
FIG. 3 is a low-magnification SEM image of the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology prepared in example 1 of the present application;
FIG. 4 is a high-power SEM image of the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology prepared in example 2 of the present application;
FIG. 5 is a low-magnification SEM image of the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology prepared in example 2 of the present application;
FIG. 6 is a high-magnification SEM image of the quaternary positive electrode material precursor prepared in comparative example 1 of the present application;
fig. 7 is a low-magnification SEM image of the quaternary positive electrode material precursor prepared in comparative example 1 of the present application.
Description of the embodiments
The present application will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The chemical reagents used in the examples of the present application, unless otherwise specified, were all obtained by conventional commercial means.
The preparation method of the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology provided by the embodiment of the application comprises the following steps:
s1, continuously adding a quaternary A salt solution, a first liquid alkali solution and a first nitrogen-containing complexing agent into a reaction kettle containing hydroxide seed crystals with uniform particle size, ammonia water with the concentration of 0.1-1.0 mol/L and a mixed solution with the pH value of 12.5-13.0 at a certain feeding speed, stopping feeding when the pH value of a reaction system is gradually reduced to 11.5-12 by adjusting the flow rate of the first liquid alkali solution to 0.1-2.0L/h, aging for 20-120 min, continuously adding the quaternary A salt solution, the first liquid alkali solution and the first nitrogen-containing complexing agent, and stopping the coprecipitation reaction when the pH value of the reaction system is gradually reduced to 10.0-10.5 by adjusting the flow rate of the first liquid alkali solution, wherein the temperature of the coprecipitation reaction is 50-80 ℃ to obtain hydroxide slurry;
wherein, the reaction kettle is 50L, and the feeding speed of the quaternary A salt solution and the first nitrogen-containing complexing agent is respectively 0.5-3L/h and 0.01-1.5L/h for the 50L reaction kettle; the concentration of each metal element in the quaternary A salt solution is 1.0-3.0 mol/L; the concentration of the first liquid alkali solution is 2.7-14.0 mol/L; the concentration of the first nitrogen-containing complexing agent is 5.0-15.0 mol/L; the quaternary A salt solution is a mixed solution of inorganic salts or organic salts of nickel, cobalt, manganese and aluminum; the inorganic salt of nickel, cobalt, manganese and aluminum is sulfate, nitrate or chloride; the organic salt of nickel, cobalt, manganese and aluminum is acetate; the second nitrogen-containing complexing agent is at least one of ammonia water, ammonium sulfite, ammonium bisulfate, ammonium sulfate, ammonium sulfide, ammonium hydrosulfide, ammonium thiosulfate, ammonium chloride or ammonium carbonate; the molar ratio of Ni to Co to Mn to Al in the quaternary A salt solution is (0.9-1.0):0.01-0.05:0.01-0.04:0.01-0.02); the first nitrogen-containing complexing agent is at least one of ammonia water, ammonium sulfite, ammonium bisulfate, ammonium sulfate, ammonium bisulfide, ammonium hydrosulfide, ammonium thiosulfate, ammonium chloride or ammonium carbonate;
in addition, the hydroxide seed crystal is specifically obtained by the following method:
respectively adding the quaternary B salt solution, the second alkali solution and the second nitrogen-containing complexing agent into a reaction kettle containing ammonia water base solution at a certain feeding speed, controlling the pH value of a reaction system to be 12.5-13.0 and the concentration of ammonia water in the reaction kettle to be 0.1-1.0 mol/L by adjusting the flow rate of the added materials, and performing coprecipitation reaction for 0.1-5 hours at the temperature of 30-80 ℃ to obtain hydroxide seed crystals which are spherical and uniform in particle size;
the reaction kettle is 50L, and the feeding speeds of the quaternary B salt solution, the second liquid alkali solution and the second nitrogen-containing complexing agent are respectively 0.5-3L/h, 0.1-2L/h and 0.01-1.5L/h for the 50L reaction kettle; the quaternary B salt solution is a mixed solution of inorganic salts or organic salts of nickel, cobalt, manganese and aluminum; the inorganic salt of nickel, cobalt, manganese and aluminum is sulfate, nitrate or chloride; the organic salt of nickel, cobalt, manganese and aluminum is acetate; the second nitrogen-containing complexing agent is at least one of ammonia water, ammonium sulfite, ammonium bisulfate, ammonium sulfate, ammonium sulfide, ammonium hydrosulfide, ammonium thiosulfate, ammonium chloride or ammonium carbonate; the molar ratio of Ni to Co to Mn to Al in the quaternary B salt solution is (0.9-1.0):0.01-0.05:0.01-0.04:0.01-0.02);
s2, washing and drying the hydroxide slurry obtained in the step S1 to obtain a super-high nickel quaternary positive electrode material precursor with a transverse lamination morphology and uniform particle size; the precursor of the positive electrode material has an average particle diameter of 5-20 μm and a structural formula of Ni x Co y Mn z Al 1-x-y-z (OH) 2 Wherein x is more than or equal to 0.9 and less than or equal to 1.0, y is more than or equal to 0.01 and less than or equal to 0.05,0.01, and z is more than or equal to 0.04.
The following are specific examples
Example 1
Ni of the lateral Stacking morphology obtained in example 1 of the present application 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 The precursor is obtained through the following steps:
s1, hydroxide seed crystal preparation: MSO of 1.5mol/L 4 (M= Ni, co, mn, al), wherein the molar ratio of Ni to Co to Mn to Al is 0.96 to 0.015 to 0.015:0.01), the mixed salt solution, the NaOH solution of 5.0mol/L and the aqueous ammonia complexing agent solution of 10.0mol/L are respectively added into a 50L reaction kettle containing 0.5mol/L aqueous ammonia as bottom water at a feeding rate of 1.5L/h, 0.9L/h and 0.06L/h, and the pH value of the coprecipitation reaction system is controlled to be 128, controlling the coprecipitation reaction temperature to be 60 ℃, controlling the concentration of ammonia water in the reaction kettle to be 0.5mol/L, continuously feeding, and reacting for 3.0h to obtain Ni 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 Seed crystal;
for Ni obtained above 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 The seed crystal is subjected to electron microscope scanning detection, the detection result is shown in fig. 1, and as can be seen from the observation of fig. 1, the seed crystal obtained in the embodiment 1 is in a sphere-like shape, the primary flaky particles are perpendicular to the circle center of the secondary particles, and the primary particles are in divergent distribution;
s2, a precursor growth stage: with Ni obtained in S1 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 The seed crystal is used as a base material, the concentration of ammonia water in the reaction kettle is regulated to be 0.5mol/L, the pH value of the mixed solution in the reaction kettle is regulated to be 12.8, and then the MSO of 1.5mol/L is regulated 4 (m= Ni, co, mn, al), wherein the molar ratio of ni:co:mn:al is 0.96:0.015:0.015:0.01) the mixed salt solution, 5.0mol/L NaOH solution, 10.0mol/L aqueous ammonia complexing agent solution are added into the reaction vessel, the feeding rate of the mixed salt solution is 1.5L/h, the feeding rate of the aqueous nitrogen complexing agent solution is 0.06L/h, the coprecipitation reaction temperature is controlled to be 60 ℃, the concentration of aqueous ammonia in the coprecipitation reaction vessel is controlled to be 0.5 mol/h, when the pH value of the reaction system is gradually reduced to 11.8 by adjusting the feeding rate of the NaOH solution, the feeding is stopped, and the mixture is aged for 60 min, and then 1.5mol/L of MSO is continuously added 4 10.0mol/L of ammonia water complexing agent solution, wherein in the feeding process, the feeding speed of the mixed solution is 1.5L/h, the feeding speed of the nitrogen water complexing agent solution is 0.06L/h, the temperature is controlled to be 60 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be 0.5mol/L, and the pH value of a reaction system is gradually reduced to 10.5 by adjusting the feeding speed of NaOH solution to be 0.1-1.0L/h, the coprecipitation reaction is stopped, and the Ni with the shape of transverse stacking of primary particles is obtained 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 A slurry;
s3, a precursor obtaining stage: washing and drying the slurry obtained in the step S2,ni for obtaining primary particle transverse stacking morphology 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 A precursor.
Ni of the primary particle transverse stacking morphology prepared in example 1 of the application 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 The precursor is scanned and detected by a low-power electron microscope and a high-power electron microscope respectively, the detection results are shown in fig. 2 and 3, and by observing fig. 2 and 3, it can be known that the primary particles prepared in the embodiment 1 of the application have Ni in a transverse stacking morphology 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 The precursor is crack-free and free of small particles.
Example 2
Ni of the lateral Stacking morphology obtained in example 2 of the present application 0.90 Co 0.05 Mn 0.04 Al 0.01 (OH) 2 The precursor is obtained through the following steps:
s1, hydroxide seed crystal preparation: MSO of 2.0mol/L 4 (M= Ni, co, mn, al), wherein the molar ratio of Ni to Co to Mn to Al is 0.90 to 0.05 to 0.04 to 0.01), the mixed salt solution, the 6.0mol/L NaOH solution and the 12.0mol/L ammonia complexing agent solution are respectively added into a reaction kettle with 0.8mol/L ammonia water as bottom water at the feeding rate of 1.2L/h, 0.8L/h and 0.05L/h, the pH value of the coprecipitation reaction system is controlled to be 12.5, the coprecipitation reaction temperature is controlled to be 55 ℃, the concentration of the ammonia water in the reaction kettle is controlled to be 0.8mol/L, the continuous feeding is carried out, and the Ni is obtained after the reaction for 1.0h 0.90 Co 0.05 Mn 0.04 Al 0.01 (OH) 2 And (5) seed crystal.
S2, a precursor growth stage: with Ni obtained in S1 0.90 Co 0.05 Mn 0.04 Al 0.01 (OH) 2 The seed crystal is used as a base material, the concentration of ammonia water in the reaction kettle is regulated to be 0.8mol/L, the pH value of the mixed solution in the reaction kettle is regulated to be 12.5, and then the MSO of 2.0mol/L is regulated 4 (M= Ni, co, mn, al), wherein the molar ratio of Ni to Co to Mn to Al is 0.90 to 0.05 to 0.04 to 0.01), the mixed salt solution, 6.0mol/L NaOH solution and 12.0mol/L ammonia complexing agent solution are added into a reaction kettle, and during the adding process, the mixture is mixedThe feeding speed of the salt-synthesizing solution is 1.2L/h, the feeding speed of the nitrogen water complexing agent solution is 0.05L/h, the coprecipitation reaction temperature is controlled to be 65 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be 0.6mol/L, when the pH value of a reaction system is gradually reduced to 11.5 by adjusting the feeding speed of the NaOH solution to be 0.1-2.0L/h, the feeding is stopped, the mixture is aged for 20min, and then 2.0mol/L of MSO is continuously added 4 6.0mol/L NaOH solution and 12.0mol/L ammonia water complexing agent solution, wherein in the feeding process, the feeding speed of the mixed solution is 1.2L/h, the feeding speed of the nitrogen water complexing agent solution is 0.05L/h, the coprecipitation reaction temperature is controlled to be 65 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be 0.6mol/L, and the pH value of a reaction system is gradually reduced to 10.0 by adjusting the feeding speed of the NaOH solution to be 0.1-1.0L/h, the coprecipitation reaction is stopped, and the Ni with the transverse stacking morphology of primary particles is obtained 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 A slurry;
s3, a precursor obtaining stage: washing and drying the slurry obtained in the step S2 to obtain Ni with the transverse stacking morphology of primary particles 0.90 Co 0.05 Mn 0.04 Al 0.01 (OH) 2 A precursor.
Ni of the primary particle transverse stacking morphology prepared in example 2 of the present application 0.90 Co 0.05 Mn 0.04 Al 0.01 (OH) 2 The precursor is scanned and detected by a low-power electron microscope and a high-power electron microscope respectively, the detection results are shown in fig. 4 and 5, and by observing fig. 4 and 5, it can be known that the primary particles prepared in the embodiment 2 of the application have Ni in a transverse stacking morphology 0.90 Co 0.05 Mn 0.04 Al 0.01 (OH) 2 The precursor is crack-free and free of small particles.
Example 3
Ni of the lateral Stacking morphology obtained in example 3 of the present application 0.95 Co 0.02 Mn 0.02 Al 0.01 (OH) 2 The precursor is obtained through the following steps:
s1, hydroxide seed crystal preparation: MSO of 2mol/L 4 (m= Ni, co, mn, al, wherein the molar ratio of Ni to Co to Mn to Al is 0.95 to0.02:0.02:0.01) mixed salt solution, 4.0mol/L NaOH solution and 10.0mol/L ammonia water complexing agent solution are respectively added into a 50L reaction kettle with 0.3mol/L ammonia water as bottom water at the feeding speed of 1.2L/h, 1.0L/h and 0.06L/h, the pH value of a coprecipitation reaction system is controlled to be 12.6, the coprecipitation reaction temperature is controlled to be 55 ℃, the concentration of the ammonia water in the reaction kettle is controlled to be 0.3mol/L, continuous feeding is carried out, and the reaction is carried out for 2.0h, thus obtaining Ni 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 Seed crystal;
s2, a precursor growth stage: with Ni obtained in S1 0.95 Co 0.02 Mn 0.02 Al 0.01 (OH) 2 The seed crystal is used as a base material, the concentration of ammonia water in the reaction kettle is regulated to be 0.3mol/L, the pH value of the mixed solution in the reaction kettle is regulated to be 12.6, and then 2mol/L of MSO is added 4 (m= Ni, co, mn, al), wherein the molar ratio of ni:co:mn:al is 0.95:0.02:0.02:0.02:0.01), a mixed salt solution, a NaOH solution of 4.0mol/L and an ammonia complexing agent solution of 10.0mol/L are added into a reaction kettle, the feeding rate of the mixed salt solution is 1.2L/h, the feeding rate of the ammonia complexing agent solution is 0.06L/h, the coprecipitation reaction temperature is controlled to be 70 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be 0.3 mol/h, when the pH value of the reaction system is gradually reduced to 11.6 by adjusting the feeding rate of the NaOH solution, the feeding is stopped, the mixture is aged for 120min, and then 2.0mol/L of MSO is continuously added 4 10.0mol/L of ammonia water complexing agent solution, wherein in the feeding process, the feeding speed of the mixed solution is 1.2L/h, the feeding speed of the ammonia water complexing agent solution is 0.06L/h, the coprecipitation reaction temperature is controlled to be 70 ℃, the concentration of ammonia water in a coprecipitation reaction kettle is controlled to be 0.3mol/L, and the pH value of a reaction system is gradually reduced to 10.2 by adjusting the feeding speed of NaOH solution to be 0.1-1.0L/h, the coprecipitation reaction is stopped, and the Ni with the shape of transverse stacking of primary particles is obtained 0.95 Co 0.02 Mn 0.02 Al 0.01 (OH) 2 A slurry;
s3, a precursor obtaining stage: washing and drying the slurry obtained in the step S2 to obtain Ni with the transverse stacking morphology of primary particles 0.95 Co 0.02 Mn 0.02 Al 0.01 (OH) 2 A precursor.
Example 4
Ni of the lateral Stacking morphology obtained in example 4 of the present application 0.92 Co 0.05 Mn 0.02 Al 0.01 (OH) 2 The precursor is obtained through the following steps:
s1, hydroxide seed crystal preparation: MSO of 2.0mol/L 4 (M= Ni, co, mn, al), wherein the molar ratio of Ni to Co to Mn to Al is 0.92 to 0.05 to 0.02 to 0.01), the mixed salt solution, the NaOH solution with concentration of 5.0mol/L and the ammonia complexing agent solution with concentration of 12.0mol/L are respectively added into a reaction kettle with ammonia water with concentration of 0.4mol/L as bottom water at feeding rates of 1.2 mol/h, 0.9L/h and 0.05L/h, the pH value of the coprecipitation reaction system is controlled to 12.8, the coprecipitation reaction temperature is controlled to 60 ℃, the concentration of ammonia water in the reaction kettle is controlled to 0.4mol/L, continuous feeding is carried out, and the Ni is obtained 0.92 Co 0.05 Mn 0.02 Al 0.01 (OH) 2 Seed crystal;
s2, a precursor growth stage: with Ni obtained in S1 0.92 Co 0.05 Mn 0.02 Al 0.01 (OH) 2 The seed crystal is used as a base material, the concentration of ammonia water in the reaction kettle is regulated to be 0.4mol/L, the pH value of the mixed solution in the reaction kettle is regulated to be 12.8, and then the MSO of 2.0mol/L is regulated 4 (m= Ni, co, mn, al), wherein the molar ratio of ni:co:mn:al is 0.90:0.05:0.04:0.01), the mixed salt solution and the aqueous ammonia complexing agent solution of 12.0mol/L are added into the reaction kettle, the feeding speed of the mixed salt solution is 1.2L/h, the feeding speed of the aqueous ammonia complexing agent solution is 0.05L/h, the coprecipitation reaction temperature is controlled to 65 ℃, the concentration of aqueous ammonia in the coprecipitation reaction kettle is controlled to be 0.6mol/L, when the pH value of the reaction system is gradually reduced to 11.8 by adjusting the feeding speed of the NaOH solution to be 0.1-1.0L/h, the feeding is stopped, and the mixture is aged for 80min, and then 2.0mol/L of MSO is continuously added 4 12.0mol/L of ammonia water complexing agent solution, wherein in the feeding process, the feeding speed of the mixed solution is 1.2L/h, the feeding speed of the ammonia water complexing agent solution is 0.05L/h, the coprecipitation reaction temperature is controlled to be 65 ℃, the concentration of ammonia water in the coprecipitation reaction kettle is controlled to be 0.6mol/L, and the feeding speed of the NaOH solution is adjusted to be 0.1-0.11.0L/h, stopping coprecipitation reaction when the pH value of the reaction system is gradually reduced to 10.5, and obtaining Ni with the transverse stacking morphology of primary particles 0.92 Co 0.05 Mn 0.02 Al 0.01 (OH) 2 A slurry;
s3, a precursor obtaining stage: washing and drying the slurry obtained in the step S2 to obtain Ni with the transverse stacking morphology of primary particles 0.90 Co 0.05 Mn 0.04 Al 0.01 (OH) 2 A precursor.
Comparative example 1
Quaternary Ni obtained in comparative example 1 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 The precursor is obtained through the following steps:
s1, hydroxide seed crystal preparation: MSO of 1.5mol/L 4 (M= Ni, co, mn, al), wherein the molar ratio of Ni to Co to Mn to Al is 0.96 to 0.015 to 0.015:0.01), the mixed salt solution, the NaOH solution of 5.0mol/L and the ammonia complexing agent solution of 10.0mol/L are respectively added into a reaction kettle with 0.5mol/L ammonia water as bottom water at the feed rate of 1.5L/h, 0.9L/h and 0.06L/h, the pH value of the coprecipitation reaction system is controlled to be 12.8, the coprecipitation reaction temperature is controlled to be 60 ℃, the concentration of the ammonia water in the coprecipitation reaction kettle is controlled to be 0.5mol/L, the continuous feeding is carried out, and the reaction is carried out for 3.0h, thus obtaining Ni 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 Seed crystal;
for Ni obtained above 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 The seed crystal is subjected to electron microscope scanning detection, the detection result is shown in fig. 1, and as can be seen from the observation of fig. 1, the seed crystal obtained in the comparative example is in a sphere-like shape, the primary flaky particles are perpendicular to the circle center of the secondary particles, and the primary particles are in divergent distribution.
S2, a precursor growth stage: ni prepared in S1 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 Seed crystal is used as a base material, MSO with the concentration of 1.5mol/L is added 4 (M=Ni, co, mn, wherein the molar ratio of Ni to Co to Mn to Al is 0.96 to 0.015 to 0.015:0.01), naOH solution of 5.0mol/LAdding 10.0mol/L ammonia water complexing agent solution into a reaction kettle containing 0.5mol/L ammonia water as bottom water at a feeding rate of 1.5L/h, 0.9L/h and 0.06L/h respectively, controlling the coprecipitation reaction temperature to be 60 ℃, controlling the concentration of the ammonia water in the coprecipitation reaction kettle to be 0.5mol/L, at this time, keeping the pH value of a coprecipitation reaction system at 11.2, continuously feeding, reacting for 80h, and obtaining Ni with primary flaky particles perpendicular to the circle centers of the secondary particles and the primary particles in divergent distribution 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 A slurry;
s3, a precursor obtaining stage: washing and drying the slurry obtained in the step S2 to obtain primary flaky particles which are perpendicular to the circle centers of the secondary particles and the primary particles show divergent distribution Ni 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 A precursor.
Comparative example Ni 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 The precursor was subjected to electron microscope scanning detection at low magnification and high magnification, respectively, and the detection results are shown in FIG. 6 and FIG. 7, and as can be seen from the examination of FIG. 6 and FIG. 7, ni was obtained in this comparative example 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 The precursor develops cracks and a large number of small particles.
In summary, compared with the existing conventional high-nickel quaternary positive electrode material precursor with primary flaky particles perpendicular to the center of the secondary particles and primary particles in a divergent distribution, the precursor of the ultra-high-nickel quaternary positive electrode material with uniform particle size and transverse lamination morphology, which is obtained by the method, is found: the primary particles of the ultra-high nickel precursor obtained by the method are transversely stacked, and the primary particles which are transversely stacked are mutually overlapped, so that the occurrence of cracks of the precursor of the large-particle-size high nickel quaternary positive electrode material is effectively avoided; in addition, the equipment adopted by the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology is used for preparing the conventional quaternary positive electrode material precursor, and the process is simple, high in yield and low in process cost; in addition, the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology, which is obtained by the method, effectively realizes the purpose of uniform particle size, and in addition, the reason for realizing uniform particle size is as follows: according to the application, the pH value is continuously reduced in the growth process, so that the excessive high nucleation supersaturation degree is avoided in the growth stage of precursor particles, new nucleation points are formed outside large particles, and a large number of new small particles are generated, so that the particles are uniform. .
In addition, 5Kg of Ni of the transverse stacking morphology obtained in example 1 of the present application 0.96 Co 0.015 Mn 0.015 Al 0.01 (OH) 2 Precursor and 4.5Kg of LiOH H 2 O is evenly mixed in a high-speed mixer, the mixed materials are placed in a resistance furnace for presintering for 10 hours at 400 ℃, then are calcined for 15 hours at 700 ℃ in oxygen atmosphere, and the calcined materials are crushed and screened to finally obtain the ultra-high nickel quaternary positive electrode material with the transverse lamination morphology.
The cathode materials are assembled into a CR2025 rechargeable battery, and electrochemical performance detection is carried out on the rechargeable battery, so that the result shows that: the discharge capacity of the battery was 225.0mA/g and the capacity retention rate at 50 cycles of 1C was 98.8% in the current density of 0.1C (17 mA/g) and the voltage range of 2.5 to 4.3V.
Therefore, when the precursor obtained by the method is used for preparing the positive electrode material and the prepared positive electrode material is assembled into the battery, the discharge capacity and the capacity retention rate of the battery are effectively improved, and a solid foundation is further laid for the development of the new energy battery.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims (7)

1. The preparation method of the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology is characterized by comprising the following steps:
s1, continuously adding a quaternary A salt solution, a first liquid alkali solution and a first nitrogen-containing complexing agent into a reaction kettle containing hydroxide seed crystals with uniform particle size, ammonia water with the concentration of 0.1-1.0 mol/L and a mixed solution with the pH value of 12.5-13.0, stopping feeding when the pH value of a reaction system is gradually reduced to 11.5-12 by adjusting the flow rate of the first liquid alkali solution to 0.1-2.0L/h, aging for 20-120 min, continuously adding the quaternary A salt solution, the first liquid alkali solution and the first nitrogen-containing complexing agent, and stopping coprecipitation reaction when the pH value of the reaction system is gradually reduced to 10.0-10.5 by adjusting the flow rate of the first liquid alkali solution to 0.1-1.0L/h, thereby obtaining hydroxide slurry;
s2, washing and drying the hydroxide slurry obtained in the step S1 to obtain a super-high nickel quaternary positive electrode material precursor with a transverse lamination morphology and uniform particle size;
the quaternary A salt solution is a mixed solution of inorganic salts or organic salts of nickel, cobalt, manganese and aluminum, and the molar ratio of Ni to Co to Mn to Al in the quaternary A salt solution is (0.9-1.0):0.01-0.05:0.01-0.04:0.01-0.02;
the hydroxide seed crystal is specifically obtained by the following method:
respectively adding the quaternary B salt solution, the second alkali solution and the second nitrogen-containing complexing agent into a reaction kettle containing ammonia water base solution at a certain feeding speed, controlling the pH value of a reaction system to be 12.5-13.0 and the concentration of ammonia water in the reaction kettle to be 0.1-1.0 mol/L by adjusting the flow rate of the added materials, and performing coprecipitation reaction to obtain hydroxide seed crystals with uniform particle sizes;
the quaternary B salt solution is a mixed solution of inorganic salts or organic salts of nickel, cobalt, manganese and aluminum, and the molar ratio of Ni to Co to Mn to Al in the quaternary B salt solution is (0.9-1.0):0.01-0.05:0.01-0.04:0.01-0.02.
2. The method for preparing the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology according to claim 1, wherein in the step S1, the temperature of the coprecipitation reaction is 50-80 ℃.
3. The method for preparing the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology according to claim 2, wherein in the step S1, the concentration of each metal element in the quaternary A salt solution is 1.0-3.0 mol/L; the concentration of the first liquid alkali solution is 2.7-14.0 mol/L; the concentration of the first nitrogen-containing complexing agent is 5.0-15.0 mol/L.
4. The method for preparing the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology according to claim 3, wherein in the step S1, a 50L reaction kettle is used, and for the 50L reaction kettle, the feeding speeds of the quaternary A salt solution and the first nitrogen-containing complexing agent are respectively 0.5-3L/h and 0.01-1.5L/h.
5. The preparation method of the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology according to claim 1 is characterized in that the reaction kettle is 50L, and the feeding speeds of the quaternary B salt solution, the second liquid alkali solution and the second nitrogen-containing complexing agent are respectively 0.5-3L/h, 0.1-2L/h and 0.01-1.5L/h for the 50L reaction kettle.
6. The method for preparing the ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology according to claim 1, wherein the reaction temperature is 30-80 ℃; the reaction time is 0.1-5 h.
7. An ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology, which is characterized by being prepared by the preparation method of any one of claims 1-6; the precursor of the positive electrode material has an average particle diameter of 5-20 μm and a structural formula of Ni x Co y Mn z Al 1-x-y-z (OH) 2 Wherein x is more than or equal to 0.9 and less than or equal to 1.0, y is more than or equal to 0.01 and less than or equal to 0.05,0.01, and z is more than or equal to 0.04.
CN202310869776.6A 2023-07-17 2023-07-17 Ultra-high nickel quaternary positive electrode material precursor with uniform particle size and transverse lamination morphology and preparation method thereof Pending CN116835669A (en)

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CN106784800A (en) * 2017-01-12 2017-05-31 江苏凯力克钴业股份有限公司 A kind of power lithium-ion battery activity spherical cobaltosic oxide and preparation method thereof
CN112537807A (en) * 2020-12-30 2021-03-23 浙江帕瓦新能源股份有限公司 High-performance nano rod-shaped nickel-manganese binary precursor and preparation method thereof
CN113651369A (en) * 2021-08-18 2021-11-16 宁波容百新能源科技股份有限公司 Spherical high-nickel ternary precursor material, preparation method thereof and high-nickel ternary cathode material
CN113651374A (en) * 2021-10-20 2021-11-16 浙江帕瓦新能源股份有限公司 Preparation method of ferrozirconium-doped nickel-cobalt-manganese ternary precursor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784800A (en) * 2017-01-12 2017-05-31 江苏凯力克钴业股份有限公司 A kind of power lithium-ion battery activity spherical cobaltosic oxide and preparation method thereof
CN112537807A (en) * 2020-12-30 2021-03-23 浙江帕瓦新能源股份有限公司 High-performance nano rod-shaped nickel-manganese binary precursor and preparation method thereof
CN113651369A (en) * 2021-08-18 2021-11-16 宁波容百新能源科技股份有限公司 Spherical high-nickel ternary precursor material, preparation method thereof and high-nickel ternary cathode material
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