CN114150378B - High-spherical ternary precursor and preparation method thereof - Google Patents
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Abstract
The invention discloses a high sphericity ternary medium-small particle precursor and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a mixed salt solution containing nickel cobalt manganese ions; under the protection of inert gas, continuously adding the mixed salt solution, caustic soda and ammonia water solution into a seed crystal kettle with base solution, ensuring the pH value of the reaction solution to be 10-13, and reacting to obtain seed crystal small particles; and the seed crystal kettle overflows and disperses the seed crystal small particles to a reaction kettle which is connected with the seed crystal small particles in series or in parallel in a step overflow mode for intermittent production, controls the fluctuation of the seed crystal small particles D50 in the seed crystal kettle, and processes the seed crystal small particles after the seed crystal particles reach the qualified granularity to obtain the high sphericity ternary medium-small particle precursor. The beneficial effects of the invention are as follows: according to the preparation method of the high sphericity precursor, the starting granularity of the seed crystal small particles is controlled to be reduced, the growth speed of the precursor in the early stage is controlled to increase the reaction time of the ternary precursor, and then the collision times among the seed crystal particles are increased, so that sphericity is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-spherical ternary precursor and a preparation method thereof.
Background
Lithium ion batteries have been increasingly used because of their high energy density, low cost, long life, and other advantages. In order to pursue higher capacity, a nickel cobalt lithium manganate ternary positive electrode material is a main development direction at present. The nickel cobalt lithium manganate anode material is mainly divided into two directions of a secondary sphere and a monocrystal. The secondary ball material can lead to the breakage of a crystal structure along with the deintercalation of lithium ions under the condition of higher charge-discharge voltage, so that the material is invalid; compared with a secondary ball, the single crystal material has higher charge and discharge voltage, large compaction density and long cycle life, and is widely applied to the fields of energy storage and the like.
The single crystal anode material is synthesized by mixing, sintering, crushing, sieving and other processes of metal lithium salt and ternary small particle precursor. The sphericity difference of the ternary small-sized particle precursors can affect the sintering uniformity of the single crystal positive electrode material, and further can affect the uniformity of a battery; meanwhile, the poor sphericity of the precursor can influence the processing performance of the monocrystalline anode material, so that the problems of difficult crushing, higher oversize products and the like are caused, and the processing cost is increased. It is therefore of particular importance to improve the sphericity of ternary small particle precursors.
The Chinese patent application No. CN110040790A discloses a high sphericity nickel-cobalt-manganese ternary precursor and a preparation method thereof, wherein hard microspheres are added into a coprecipitation reaction system to increase collision so as to improve sphericity.
The patent number CN111646521A utilizes bubbles to inhibit collision agglomeration of precursor particles, increases turbulent diffusion of a circulation dead zone, and improves dispersibility and sphericity of small-particle nickel-cobalt-manganese ternary precursors.
Patent number CN111196613a is a method for preparing high sphericity ternary precursor seed crystal and a method for preparing high sphericity ternary precursor by using the seed crystal. The solid particles insoluble in the base solution are added into the base solution for reaction synthesis, and are strongly stirred and dispersed to obtain seed crystals, slurry is pumped through a microporous filter tube of the small-particle seed crystals, and the small-particle seed crystals meeting the required granularity in a reaction kettle are separated for continuous production.
Disclosure of Invention
The main aim of the application is to provide a high sphericity ternary precursor capable of improving the uniformity and the processing performance of ternary monocrystal anode materials and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
a high sphericity ternary small and medium particle precursor, the general formula of the precursor is: ni (Ni) x Co y Mn z (OH) 2+a Wherein x+y+z=1, x is 0.5.ltoreq.0.95, y is 0.ltoreq. 0.6,0.ltoreq.z is 0.8, and a is 0.ltoreq.0.5;
the sphericity of the high sphericity ternary medium-small particle precursor is as follows: sphericity is more than 0 and less than 1;
the sphericity calculation formula is: 4 pi S/L 2 -1；
Wherein: s is the area of the particle and L is the perimeter. Note that the smaller the sphericity, the more round the particle.
The second aspect of the application provides a preparation method of a high sphericity ternary medium-small particle precursor, which comprises the following steps:
(1) Preparing a mixed salt solution containing nickel cobalt manganese ions;
(2) Under the protection of inert gas, continuously adding the mixed salt solution, caustic soda and ammonia water solution into a seed crystal kettle added with base solution, ensuring the pH value of the reaction solution to be 10-13, and uniformly mixing and stirring under the heating condition to obtain seed crystal small particles;
(3) And the seed crystal kettle overflows and disperses the seed crystal small particles to a reaction kettle which is connected with the seed crystal small particles in series or in parallel in a step overflow mode for intermittent production, controls the fluctuation of the seed crystal particles D50 in the seed crystal kettle until the D50 of the seed crystal particles rises to 2-3um, and carries out washing, dehydration, drying and iron removal after the seed crystal particles reach the qualified granularity to obtain the high sphericity ternary medium-small particle precursor.
According to the method disclosed by the invention, the starting granularity of the small seed crystal particles is controlled to be reduced, the growth speed of the precursor in the early stage (if the expansion speed is too high, crystals preferentially grow and the morphology of the crystal particles is more irregular) is controlled, the reaction time of the ternary precursor is increased, and the collision times among the seed crystal particles are further increased, so that the sphericity is improved.
In addition, the preparation method disclosed by the invention adopts a step overflow mode to overflow and disperse small seed crystal particles into a reaction kettle connected with the seed crystal kettle in series or in parallel for batch production, so that the seed crystal with poor early sphericity can be diluted, the duty ratio of particles with poor early sphericity is reduced, and the sphericity of the precursor is further improved.
In the preparation method of the ternary medium-small particle precursor with high sphericity, as a preferred embodiment, in the step (1), the total concentration of metal ions contained in the nickel-cobalt-manganese ion mixed salt solution is 1-3mol/L.
In the above method for preparing a ternary medium-small particle precursor with high sphericity, in step (1), the mixed salt solution is at least one of sulfate, nitrate, oxalate or chloride.
In the preparation method of the ternary medium-small particle precursor with high sphericity, as a preferred embodiment, in the step (2), the inert gas is nitrogen.
In the preparation method of the ternary medium-small particle precursor with high sphericity, as a preferred embodiment, in the step (2), the concentration of caustic soda is 5-12mol/L, and the concentration of ammonia water is 0.5-2mol/L; the temperature of stirring and heating is 40-60 ℃.
In the above method for preparing a ternary medium-small particle precursor with high sphericity, as a preferred embodiment, in the step (2), the D50 of the obtained seed small particle is 0.5-2.0um.
In the preparation method of the high sphericity ternary medium-small particle precursor, as a preferred embodiment, in the step (3), the production mode of step overflow is realized by the following devices:
the device comprises: a seed crystal kettle and a plurality of reaction kettles;
the seed crystal kettles and the reaction kettles are sequentially connected in series;
or the seed crystal kettles are connected in parallel with the reaction kettles;
or the seed crystal kettle is communicated with a plurality of reaction kettles in a series connection and parallel connection mode.
In the above method for preparing a ternary medium-small particle precursor with high sphericity, as a preferred embodiment, in the step (3), the fluctuation of the seed particles D50 in the seed crystal kettle is controlled to be 0.05-0.2um/8h.
Preferably, in step (3), the acceptable finished product has a particle size of 2.5um to 7um.
In a third aspect of the invention, a positive electrode material is provided comprising the precursor according to any one of claims 1-10.
The beneficial effects of the invention are as follows: according to the preparation method of the high sphericity ternary medium-small particle precursor, the starting granularity of the seed crystal small particles is controlled to be reduced, the growth speed of the precursor in the early stage is controlled to increase the reaction time of the ternary precursor, and then the collision times among the seed crystal particles are increased, so that sphericity is improved.
In addition, the preparation method disclosed by the invention adopts a step overflow mode to overflow and disperse small seed crystal particles into a reaction kettle connected with the seed crystal kettle in series or in parallel for batch production, so that the seed crystal with poor early sphericity can be diluted, the duty ratio of particles with poor early sphericity is reduced, and the sphericity of the precursor is further improved.
Drawings
FIG. 1 is an SEM image of a ternary precursor of example 1 of the present invention;
FIG. 2 is an SEM image of a ternary precursor of example 2 of the present invention;
FIG. 3 is an SEM image of a ternary precursor of comparative example 1 of the present invention;
FIG. 4 is an SEM image of a ternary precursor of comparative example 2 of the present invention;
FIG. 5 is a schematic diagram of the structure of a seed crystal kettle (1A) and 3 reaction kettles connected in series in sequence;
FIG. 6 is a schematic diagram of the structure of a seed tank (1A) connected in parallel with 3 reaction tanks.
Detailed Description
In order that those skilled in the art will better understand the present application, a technical solution in the embodiments of the present application will be clearly and completely described in the following in connection with examples, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, shall fall within the scope of the present application.
The invention provides a ternary medium-small with high sphericityA particulate precursor, the precursor having the formula: ni (Ni) x Co y Mn z (OH) 2+a Wherein x+y+z=1, x is 0.5.ltoreq.0.95, y is 0.ltoreq. 0.6,0.ltoreq.z is 0.8, and a is 0.ltoreq.0.5;
the sphericity of the high sphericity ternary medium-small particle precursor is as follows: sphericity is more than 0 and less than 1;
the sphericity calculation formula is: 4 pi S/L 2 -1；
Wherein: s is the area of the particle and L is the perimeter.
Example 1
The high sphericity ternary small particle precursor described in example 1 had a sphericity of 0.104.
The preparation method of the high sphericity ternary medium-small particle precursor in the embodiment 1 comprises the following steps:
step 1, preparing sulfate solution containing nickel cobalt manganese ions with the total concentration of 1.8 mol/L; wherein the molar ratio of nickel ions, cobalt ions and manganese ions is 50:20:30;
step 2, stirring in a seed crystal kettle, introducing nitrogen for protection, adding caustic soda with the concentration of 5mol/L and ammonia water with the concentration of 1mol/L into the seed crystal kettle as base solution, continuously adding the sulfate salt solution, the caustic soda and the ammonia water solution, ensuring the pH value of the reaction solution to be 12.3, and reacting at the heating temperature of 40 ℃ to obtain seed crystal small particles with the D50 of 1.0 um;
step 3, preparing a step overflow device, wherein 3 reaction kettles are sequentially connected in series at the position of a discharge hole of a seed crystal kettle (1A), and are respectively named as 2A, 3A and 4A in sequence;
the seed crystal kettle 1A overflows and disperses seed crystals to other reaction kettles 2A, 3A and 4A for 4 hours in sequence through cascade serial overflow, and a thickener batch process is started for production; after the reaction kettle 1A overflows for 12 hours, stopping overflowing and starting total reflux to be used as a growth kettle. After the reaction kettles 2A, 3A and 4A receive seed crystals overflowed by 1A for 4 hours, the seed crystals are independently fed and opened for total reflux to be used as a growth kettle; (schematic structure of the seed tank (1A) and 3 reaction tanks in series in order, as shown in FIG. 5).
And 4, controlling the rising speed of the D50 at about 0.05um by adjusting the pH of the seed crystal kettle in the early stage, (controlling the rising speed of the D50 by controlling the pH of the reaction liquid, reducing the adding amount of caustic soda if rising too slowly, and increasing the adding amount of caustic soda if rising too quickly), and not controlling the rising speed after the D50 rises to 2.3 um. And (3) shutting down after the granularity reaches 4.2um, and performing treatments such as centrifugation, washing, drying, removing magnetic foreign matters and the like to obtain a nickel-cobalt-manganese ternary precursor finished product with good sphericity.
The SEM image of the ternary precursor obtained in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the sphericity of the ternary precursor obtained in example 1 is relatively uniform and the uniformity is good.
Example 2
The high sphericity ternary small particle precursor described in example 2 had a sphericity of 0.107.
The preparation method of the high sphericity ternary medium-small particle precursor in the embodiment 2 comprises the following steps:
step 1, preparing sulfate solution containing nickel cobalt manganese ions with the total concentration of 1.8mol/L, wherein the ratio of nickel ions to cobalt ions to manganese ions is 50:20:30;
step 2, stirring the seed crystal kettle, introducing nitrogen for protection, adding caustic soda with the concentration of 5mol/L and ammonia water with the concentration of 1mol/L into the seed crystal kettle as base solution, continuously adding the prepared sulfate solution, caustic soda and ammonia water solution, ensuring the pH value of the reaction solution to be 11.8, and reacting at the heating temperature of 40 ℃ to obtain seed crystal small particles with the D50 of 1.0 um;
step 3, preparing a step overflow device, wherein 3 reaction kettles are connected in parallel at the position of a discharge hole of a seed crystal kettle (1A) and are named as 2A, 3A and 4A respectively;
the seed crystal kettle 1A overflows in parallel through a thickener to disperse seed crystals to other reaction kettles 2A, 3A and 4A for 4 hours, and the thickener is started for batch production; after the reaction kettle 1A overflows for 12 hours, stopping overflowing and starting total reflux to be used as a growth kettle. After the reaction kettles 2A, 3A and 4A receive seed crystals overflowed by 1A for 4 hours, the seed crystals are independently fed and opened for total reflux to be used as a growth kettle; (schematic structure of the seed crystal kettle (1A) and 3 reaction kettles in parallel, as shown in FIG. 6);
and 4, controlling the rising speed of the D50 at about 0.1um in the early stage by adjusting the PH of the seed crystal kettle, after the D50 rises to 1.8um, not controlling the rising speed of the D50, and after the granularity reaches 4.2um, shutting down, and performing treatments such as centrifugation, washing, drying, removing magnetic foreign matters and the like to obtain a nickel-cobalt-manganese ternary precursor finished product with good sphericity.
The SEM image of the ternary precursor obtained in example 2 is shown in fig. 2, and it can be seen from fig. 2 that the sphericity of the ternary precursor obtained in example 2 is relatively uniform and the uniformity is good.
Example 3
The high sphericity ternary small particle precursor described in example 3 had a sphericity of 0.104.
The preparation method of the high sphericity ternary medium-small particle precursor in the embodiment 3 comprises the following steps:
step 1, preparing sulfate solution containing nickel cobalt manganese ions with the total concentration of 2.5/L; wherein the molar ratio of nickel ions, cobalt ions and manganese ions is 50:20:30;
step 2, stirring in a seed crystal kettle, introducing nitrogen for protection, adding caustic soda with the concentration of 8mol/L and ammonia water with the concentration of 0.5mol/L into the seed crystal kettle as base solution, continuously adding the sulfate salt solution, the caustic soda and the ammonia water solution, ensuring the pH value of the reaction solution to be 12.5, and reacting at the heating temperature of 50 ℃ to obtain seed crystal small particles with the D50 of 1.5 mu m;
step 3, preparing a step overflow device, wherein 3 reaction kettles are sequentially connected in series at the position of a discharge hole of a seed crystal kettle (1A), and are respectively named as 2A, 3A and 4A in sequence;
the seed crystal kettle 1A overflows and disperses seed crystals to other reaction kettles 2A, 3A and 4A for 4 hours in sequence through cascade serial overflow, and a thickener batch process is started for production; after the reaction kettle 1A overflows for 12 hours, stopping overflowing and starting total reflux to be used as a growth kettle. After the reaction kettles 2A, 3A and 4A receive seed crystals overflowed by 1A for 4 hours, the seed crystals are independently fed and opened for total reflux to be used as a growth kettle; (schematic structure of the seed tank (1A) and 3 reaction tanks in series in order, as shown in FIG. 5).
And 4, controlling the rising speed of the D50 at about 0.1um in the early stage by adjusting the pH of the seed crystal kettle, (controlling the rising speed of the D50 by controlling the pH of the reaction liquid, reducing the adding amount of caustic soda if rising too slowly, and increasing the adding amount of caustic soda if rising too quickly), and not controlling the rising speed after the D50 rises to 2.3 um. And shutting down after the granularity reaches 5.0um, and performing treatments such as centrifugation, washing, drying, removing magnetic foreign matters and the like to obtain a nickel-cobalt-manganese ternary precursor finished product with good sphericity.
Comparative example 1
The preparation method of the high sphericity ternary small particle precursor described in comparative example 1 is different from the preparation method described in example 1 in that: in the step (4): the fluctuation of the seed particles in the seed tank is not controlled.
The SEM image of the ternary precursor obtained in comparative example 1 is shown in fig. 3, and it can be seen from fig. 3 that the ternary precursor obtained in comparative example 1 has poor sphericity consistency and has an irregular oval morphology.
Comparative example 2
The preparation method of the high sphericity ternary small particle precursor described in comparative example 2 is different from the preparation method described in example 2 in that: in the step (3), the seed crystal kettle production mode is directly adopted to replace the step overflow mode to overflow and disperse the seed crystal small particles to a reaction kettle connected in series or in parallel to carry out batch method production mode.
The SEM image of the ternary precursor obtained in comparative example 2 is shown in fig. 4, and it can be seen from fig. 4 that the ternary precursor obtained in comparative example 2 has poor sphericity consistency and has an irregular oval morphology.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (8)
1. A preparation method of a ternary medium-small particle precursor with high sphericity is characterized in that,
the method comprises the following steps:
(1) Preparing a mixed salt solution containing nickel cobalt manganese ions;
(2) Under the protection of inert gas, continuously adding the mixed salt solution, caustic soda and ammonia water solution into a seed crystal kettle added with base solution, ensuring the pH value of the reaction solution to be 10-13, and uniformly mixing and stirring under the heating condition to obtain seed crystal small particles with D50 of 0.5-2.0 um;
(3) Dispersing small seed particles in a step overflow manner in a reaction kettle connected in series or in parallel to the small seed particles for intermittent production, controlling the fluctuation of D50 of the seed particles in the seed crystal kettle to be 0.05-0.2um/8h by adjusting the pH value of the seed crystal kettle until the D50 of the seed particles rises to 2-3um, centrifuging, washing, drying and removing iron after the seed particles reach qualified granularity to obtain the ternary small and medium particle precursor with high sphericity;
the production mode of step overflow is realized by the following devices:
the device comprises: a seed crystal kettle and a plurality of reaction kettles;
the seed crystal kettles and the reaction kettles are sequentially connected in series;
or the seed crystal kettles are connected in parallel with the reaction kettles;
or the seed crystal kettles are communicated with a plurality of reaction kettles in a serial connection and parallel connection mode;
the general formula of the precursor is as follows: ni (Ni) x Co y Mn z (OH) 2+a Wherein x+y+z=1, x is 0.5.ltoreq.0.95, y is 0.ltoreq. 0.6,0.ltoreq.z is 0.8, and a is 0.ltoreq.0.5.
2. The method for preparing the high sphericity ternary medium-small particle precursor according to claim 1, wherein,
the sphericity of the high sphericity ternary medium-small particle precursor is as follows: sphericity is more than 0 and less than 1;
the sphericity calculation formula is: 4 pi S/L 2 -1；
Wherein: s is the area of the particle and L is the perimeter.
3. The method for preparing the high sphericity ternary medium-small particle precursor according to claim 1, wherein,
in the step (1), the total concentration of metal ions contained in the nickel-cobalt-manganese ion mixed salt solution is 1-3mol/L.
4. The method for preparing the high sphericity ternary medium-small particle precursor according to claim 1, wherein,
in the step (1), the mixed salt solution is at least one of sulfate, nitrate, oxalate or chloride.
5. The method for preparing the high sphericity ternary medium-small particle precursor according to claim 1, wherein,
in the step (2), the inert gas is nitrogen.
6. The method for preparing the high sphericity ternary medium-small particle precursor according to claim 1, wherein,
in the step (2), the concentration of caustic soda is 5-12mol/L, and the concentration of ammonia water is 0.5-2mol/L; the temperature of stirring and heating is 40-60 ℃.
7. The method for preparing the high sphericity ternary medium-small particle precursor according to claim 6, wherein,
in the step (3), the granularity of the qualified finished product is 2.5um-7um.
8. A positive electrode material is characterized in that,
comprising a precursor according to any one of claims 1-7.
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| JP5626382B2 (en) * | 2013-01-30 | 2014-11-19 | 住友金属鉱山株式会社 | Nickel-cobalt composite hydroxide and method for producing the same |
| CN108598441B (en) * | 2018-05-29 | 2021-02-26 | 东莞理工学院 | Different-granularity narrow-distribution ternary precursor and preparation method thereof |
| CN110550667A (en) * | 2019-07-23 | 2019-12-10 | 河南科隆新能源股份有限公司 | Preparation method of lithium ion positive electrode material precursor |
| CN111939859B (en) * | 2020-07-17 | 2021-12-14 | 广东芳源环保股份有限公司 | Ternary precursor reaction device with narrow particle size distribution |
| CN113321245B (en) * | 2021-05-25 | 2023-05-05 | 华友新能源科技（衢州）有限公司 | Nickel-cobalt-manganese hydroxide and preparation method thereof |
| CN113426398B (en) * | 2021-08-26 | 2021-12-14 | 广东芳源环保股份有限公司 | Production device and method of wide-distribution micro-powder-free ternary precursor |
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