CN112694139A - Preparation method of single crystal NCM ternary positive electrode material precursor - Google Patents
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Abstract
The invention provides a preparation method of a single crystal NCM ternary cathode material precursor, which comprises the following steps: s1, mixing Ni with the total concentration of 1.0-2.2 mo1/Lx:Coy:MnzAdding a sulfate solution, a 4-10 mol/L caustic soda solution and 20% ammonia water into a reaction unit (10), and introducing inert gas to perform a first-stage reaction, wherein the reaction conditions are as follows: the stirring speed is 800-1100 r/min, the pH is 11.50-13.00, the temperature is 40-60 ℃, and the inert gas flow is 0.1-2 m3H, x + y + z is 1, and x is more than 1.0 and is more than or equal to 0.5; and S2, after the D50 of the particles is measured to be 1.5-1.8 mu m, increasing the ammonia value in the reaction kettle to carry out a second-stage reaction, wherein the reaction conditions are as follows: keeping stirring speed, temperature and gasThe flow speed is unchanged, the concentration of ammonia water is controlled to be 2-7g/L, the pH value is controlled to be 9.00-11.00, a solid content is improved by concentrating through a solid lifting unit (20), the clear-out speed of a solid lifting device is adjusted, and finally the reaction is stopped when the D50 particles are 3.8-4.5 mu m; and S3, washing, drying and screening the slurry to obtain the precursor of the single crystal NCM ternary cathode material.
Description
Technical Field
The invention relates to a preparation method of a single crystal NCM ternary cathode material precursor.
Background
With the rapid development of the lithium battery industry and the use of new energy automobiles in the traffic field, the high-nickel NCM ternary cathode material is always considered as the most mainstream development direction, however, in recent years, natural problems of domestic new energy automobiles frequently appear, and a high-nickel ternary material system is rather controversial in the market. Under the influence, the single crystal NCM anode material with better safety performance gradually becomes the key point of the public anode material enterprises in China and is concerned about. In order to meet the application of nickel cobalt lithium manganate ternary materials in small-sized high-energy-density lithium ion batteries for power batteries and electronic products in the future, the development direction of NCM nickel cobalt lithium manganate ternary materials tends to improve the charging voltage of the batteries and the compaction density of the materials, and the NCM ternary positive electrode materials of single crystal series with high voltage and high compaction density are high in competition in the later lithium battery positive electrode material industry.
The main method for preparing the nickel-cobalt-manganese precursor at the present stage comprises the following steps: firstly, preparing nickel-cobalt-manganese solid salt into a mixed solution with a certain concentration and a certain proportion, and carrying out coprecipitation crystallization on the mixed solution, a precipitator and a complexing agent; and secondly, aging, washing, drying, sieving, removing iron and other processes are carried out on the crystallization slurry to obtain the nickel-cobalt-manganese hydroxide precursor. Due to the characteristics of the precursor seed crystal stage, when a single-crystal small-particle NCM ternary precursor product is prepared, the conditions of multi-stage agglomeration, poor particle uniformity and the like are easily caused in the reaction stage, so that the subsequent anode material is difficult to sinter, the sintering time is greatly influenced, and the performance of the subsequent anode material is further influenced by the precursor stage.
Disclosure of Invention
The invention provides a preparation method for preparing a single crystal NCM ternary cathode material precursor which has the advantages of less agglomeration amount, fine crystal whiskers, orderly whisker arrangement and large specific surface area.
The invention is realized by the following steps:
a method for preparing a precursor of a single crystal NCM ternary cathode material based on a reactor with controllable particle size, wherein the reactor with controllable particle size comprises the following steps: a reaction unit and a solid lifting unit;
the preparation method comprises the following steps:
s1, mixing Ni with the total concentration of 1.0-2.2 mo1/Lx:Coy:MnzAdding a sulfate solution, a 4-10 mol/L caustic soda solution and 20% ammonia water into a reaction unit, and introducing inert gas to perform a first-stage reaction, wherein the reaction conditions are as follows: the stirring speed is 800-1100 r/min, the pH is 11.50-13.00, the temperature is 40-60 ℃, and the inert gas flow is 0.1-2 m3H, x + y + z is 1, and x is more than 1.0 and is more than or equal to 0.5;
and S2, after the D50 of the particles is measured to be 1.5-1.8 mu m, increasing the ammonia value in the reaction kettle to carry out a second-stage reaction, wherein the reaction conditions are as follows: keeping the stirring speed, the temperature and the air flow velocity unchanged, controlling the concentration of ammonia water at 2-7g/L, controlling the pH to be 9.00-11.00, concentrating by using a solid-extracting unit to improve the solid content and adjust the clear-out speed of a solid-extracting device, and finally, stopping the reaction when the D50 of the particles is 3.8-4.5 mu m;
and S3, washing, drying and screening the slurry to obtain the precursor of the single crystal NCM ternary cathode material.
The invention has the beneficial effects that: the invention divides the coprecipitation reaction into two stages: in the first stage, high pH nucleation is carried out, and a certain amount of precursor crystal seeds are contained in reaction base liquid with long nitrogen flow; and in the second stage, low pH solid-lifting growth is carried out, a connecting reaction is opened to obtain a solid-lifting groove, so that the mass percentage of the precursor seed crystal of the reaction bottom liquid with the nitrogen gas long-pass is improved, and the granularity required by the target is achieved under the growth condition of uniform and slow growth. And finally, washing, drying and screening the obtained product to obtain the precursor of the single crystal NCM ternary cathode material. In addition, the preparation method can be used for preparing the single crystal NCM ternary cathode material precursor which has less agglomeration amount, fine crystal whiskers, orderly whisker arrangement and large specific surface area.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a schematic structural diagram of a reactor with controllable particle size according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a solids-lifting unit in a reactor with a controllable particle size according to an embodiment of the present invention.
FIG. 3 is a top view of a grid plate in a lifting unit of a reactor with controllable particle size according to an embodiment of the present invention.
Fig. 4 is a flowchart of a method for preparing a precursor of a single crystal NCM ternary positive electrode material based on a reactor with a controllable particle size according to an embodiment of the present invention.
FIG. 5 shows Ni prepared in example 1 of the present invention0.60Co0.20Mn0.20(OH)2Scanning electron micrographs of (A) and (B).
FIG. 6 shows Ni prepared in example 1 of the present invention0.65Co0.15Mn0.20(OH)2Scanning electron micrographs of (A) and (B).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Referring to FIG. 1, the present invention provides a reactor with controllable particle size. The reactor with the controllable particle size is suitable for preparing a ternary precursor.
The reactor with controllable particle size comprises:
the reaction unit 10 comprises a reaction vessel 12, a feeding pipe 11 arranged in the reaction vessel 12, a stirring assembly arranged in the reaction vessel 12, a temperature control assembly 15 sleeved outside the bottom of the reaction vessel 12, an overflow pipeline 18 arranged on the upper part of the reaction vessel 12 and an overflow valve 17 arranged on the overflow pipeline 18;
the lifting and fixing unit 20 includes: the device comprises a lifting and fixing device 23 for accumulating and rapidly precipitating the ternary precursor, a lifting and fixing pipeline 21 respectively connected to the upper part of the lifting and fixing device 23 and the upper part of the reaction container 12, a lifting and fixing valve 22 arranged on the lifting and fixing pipeline 21, a drain pipeline 24 connected to the upper part of the lifting and fixing device 23, an observation port 28 connected to the top of the lifting and fixing device 23, a drain valve 25 and an observation window 28 arranged on the drain pipeline 24, a return pipeline 26 respectively connected to the bottom of the lifting and fixing device 23 and the bottom of the reaction container 12, and a return valve 27 arranged on the return pipeline 26. The supernatant valve 25 is used for discharging the supernatant liquid containing sulfur. The purge pipe 24 further includes a connection elbow 241 disposed in the extractor 23 and a filter screen 242 disposed in the connection elbow 241, and an inlet of the connection elbow 241 faces the bottom of the extractor 23.
The feed pipe 11 is used for introducing nickel-cobalt-manganese salt solution prepared according to a proportion. The reaction vessel 12, the stirring member and the temperature control member 15 may be of any conventional structure, and will not be described in detail herein. Further, the overflow pipe 18 is flush with the lifting and fixing pipe 21. The reaction unit 10 may further include an exit conduit 16.
Referring to fig. 2-3, the lifting device 23 is a top bucket, the bottom is an inverted cone, and the space volume is 1/3-1/2 of the effective volume of the reaction vessel 12. The material of the lifting and fixing device 23 is not limited, and can be any one of 316L steel and PP. Further, a plurality of layers of grid plates 234 which are arranged in a stacked manner and used for accumulating and rapidly precipitating the ternary precursor are transversely arranged in the lifting and fixing device 23; each grid plate 234 includes a plurality of grids 2342 arranged in an inclined manner, and the grids 2342 between two adjacent grid plates 234 are communicated with each other and the inclined directions of the grids 2342 are crossed. It can be understood that by arranging the grids 2342 obliquely and crossing the oblique directions, the solid can be accumulated and rapidly precipitated through continuous collision, and finally the overall morphology of the ternary precursor is improved. Preferably, the number of the grid plates 234 is 2-5 layers. It can be understood that when the number of grating plates 234 is small, the number of collisions is low and accumulation is difficult, and rapid sedimentation and morphology lifting are achieved; when the number is large, the particle size tends to be excessively large. Further, the angle formed by the axis of each grid 2342 and the lifter 23 is controlled to allow solids to accumulate and rapidly settle through continuous collision. Too small an angle results in too small a collision area, and too large an angle tends to accumulate in grating plate 234. Therefore, preferably, the axis of each grid 2342 forms an angle of 15 ° to 80 ° with the anchor 23. More preferably, the axis of each grid 2342 forms an angle of 25 ° to 35 ° with the anchor 23. In one embodiment, the axis of each grid 2342 forms an angle of about 30 ° with the lifting device 23.
Each grid plate 234 is 10-30 cm in height, and the distance from the top grid plate 234 to the top of the lifter 23 is 30-50 cm. The shape of each grid 2342 is not limited and can be selected according to actual needs; the shape of each grid 2342 may be a regular or irregular structure. In one embodiment, each grid 2342 is a regular hexagonal structure with sides of 5-20 centimeters.
As a further improvement, the backflow pipeline 26 includes two first bending discharging sections, a second bending discharging section connected to the first bending discharging section, a first extending section extending along the extending direction of the first bending discharging section, and a second extending section extending along the second bending discharging section in the opposite direction, and the first extending section and the second extending section are respectively provided with a first spiral push rod 262 and a second spiral push rod 264. The screw ejector pin can play a role in dredging when the backflow pipeline 26 is blocked.
The aperture of the filter screen 242 is 0.5um-15um, and in one embodiment, the aperture of the filter screen 242 is 9 um. The connecting bend 241 is directed towards the bottom of the carrier 23 so as to avoid clogging of the screen with particles.
Referring to fig. 4, a method for preparing a precursor of a single crystal NCM ternary positive electrode material based on a reactor with controllable particle size includes: a reaction unit (10) and a lifting unit (20); the preparation method comprises the following steps:
s1, mixing Ni with the total concentration of 1.0-2.2 mo1/Lx:Coy:MnzAdding a sulfate solution, a 4-10 mol/L caustic soda solution and 20% ammonia water into a reaction unit (10), and introducing inert gas to perform a first-stage reaction, wherein the reaction conditions are as follows: the stirring speed is 800-1100 r/min, the pH is 11.50-13.00, the temperature is 40-60 ℃, and the inert gas flow is 0.1-2 m3H, x + y + z is 1, and x is more than 1.0 and is more than or equal to 0.5;
and S2, after the D50 of the particles is measured to be 1.5-1.8 mu m, increasing the ammonia value in the reaction kettle to carry out a second-stage reaction, wherein the reaction conditions are as follows: keeping the stirring speed, the temperature and the air flow velocity unchanged, controlling the concentration of ammonia water at 2-7g/L and the pH at 9.00-11.00, concentrating by using a solid-lifting unit (20) to improve the solid content and adjust the clear-out speed of a solid-lifting device, and finally, stopping the reaction when the D50 is measured to be 3.8-4.5 mu m;
and S3, washing, drying and screening the slurry to obtain the precursor of the single crystal NCM ternary cathode material. 2. The method for preparing a single-crystal NCM ternary positive electrode material precursor according to claim 1, wherein Ni is added to a total concentration of 1.6mo1/L in a ratio in step S1x:Coy:MnzThe sulfate solution, 8mol/L caustic soda solution and 20% ammonia water are added into the reaction unit (10) and inert gas is introduced at the same time to carry out the first stage reaction.
In step S1, Ni with a total concentration of 1.6mo1/L is preferably addedx:Coy:MnzThe sulfate solution, 8mol/L caustic soda solution and 20% ammonia water are added into the reaction unit (10) and inert gas is introduced at the same time to carry out the first stage reaction. And the reaction conditions are as follows: the stirring speed is 1030-1050 r/min, the pH is 12.00-12.50, the temperature is 50-55 ℃, and the inert gas flow is 0.1-E0.5m3/h。
In step S2, after the particle D50 was measured to be 1.5 μm, the second-stage reaction was carried out by increasing the ammonia value in the reaction vessel. And the reaction conditions are as follows: keeping the stirring speed, the temperature and the air flow velocity unchanged, controlling the concentration of ammonia water at 3-4g/L and the pH at 10.50-10.80, concentrating by using a solid-extracting unit (20) to increase the solid content and adjust the clear-out speed of the solid-extracting device, and finally, stopping the reaction when the D50 is 4.0 mu m.
In step S3, the drying temperature is 110-. The washing medium may be deionized water and passed through a 200-450 mesh 316L stainless steel screen.
Example 1:
preparing NiSO with the concentration of 1.6mol/L according to the molar ratio of nickel ions to cobalt ions to manganese ions of 60:20:204、CoSO4、MnSO4Adding the mixed solution, 8mol/L caustic soda solution and 20% industrial ammonia water filtered by 200 mesh filter cloth into a reaction vessel 12 by using a precision metering pump, carrying out a first-stage reaction, wherein the stirring speed of the reaction vessel is 1050r/min, the pH value is 12.30, the temperature is 55 ℃, and the nitrogen gas is kept at 0.2m3H, long-pass reaction, and reaction for 1.5 h; and in the second stage, after the D50 is measured to be 1.5 mu m by a Dandong Baite model 2600 particle size analyzer, controlling the ammonia value in the reaction vessel 12 to be 3-4g/L, controlling the pH to be 10.60, fully opening the overflow valve 17, the solid lifting valve 22 and the backflow valve 27, opening the drain valve 24 by 15%, filtering the mother liquor by a solid lifter to improve the solid content and adjust the clear rate of the solid lifter, and stopping the reaction when the D50 is measured to be 4.0 mu m by the Dandong Baite model 2600 particle size analyzer. Washing, drying and screening the slurry to obtain a precursor material Ni0.60Co0.20Mn0.20(OH)2。
Example 2:
preparing NiSO with the concentration of 1.6mol/L according to the molar ratio of nickel ions to cobalt ions to manganese ions of 65:15:204、CoSO4、MnSO4Adding the mixed solution, 8mol/L caustic soda solution, and industrial ammonia water filtered by 20% 200 mesh filter cloth into the reaction container 12 with a precision metering pump, and performing a first stageReacting, wherein the stirring speed of the reaction kettle is 1030r/min, the pH is 12.22, the temperature is 55 ℃, and the nitrogen is kept at 0.3m3H, long-pass reaction, and reaction for 1.5 h; and in the second stage, after the D50 is measured to be 1.5 mu m by a Dandong Baite model 2600 particle size analyzer, controlling the ammonia value in the reaction vessel 12 to be 3-4g/L, controlling the pH to be 10.50, fully opening the overflow valve 17, the solid lifting valve 22 and the backflow valve 27, opening the drain valve 24 by 15%, filtering the mother liquor by a solid lifter to improve the solid content and adjust the clear rate of the solid lifter, and stopping the reaction when the D50 is measured to be 4.0 mu m by the Dandong Baite model 2600 particle size analyzer. Washing, drying and screening the slurry to obtain a precursor material Ni0.65Co0.15Mn0.20(OH)2。
The electron microscopy tests and other performance tests performed on examples 1 and 2 are shown in FIGS. 5-6 and Table 1. The figure shows that the preparation method can prepare the single crystal NCM ternary cathode material precursor with less aggregation, fine crystal whiskers, orderly whisker arrangement and large specific surface area. In addition, the sulfur content of the precursor of the single crystal NCM ternary cathode material can be remarkably reduced through the solid lifting device.
Table 1 shows the characterization data of the precursors of the single crystal NCM ternary positive electrode materials of examples 1 and 2
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of a single crystal NCM ternary cathode material precursor based on a reactor with controllable particle size is characterized in that the reactor with controllable particle size comprises the following steps: a reaction unit (10) and a lifting unit (20); the preparation method comprises the following steps:
s1, mixing Ni with the total concentration of 1.0-2.2 mo1/Lx:Coy:MnzAdding a sulfate solution, a 4-10 mol/L caustic soda solution and 20% ammonia water into a reaction unit (10), and introducing inert gas to perform a first-stage reaction, wherein the reaction conditions are as follows: the stirring speed is 800-1100 r/min, the pH is 11.50-13.00, the temperature is 40-60 ℃, and the inert gas flow is 0.1-2 m3H, x + y + z is 1, and x is more than 1.0 and is more than or equal to 0.5;
and S2, after the D50 of the particles is measured to be 1.5-1.8 mu m, increasing the ammonia value in the reaction kettle to carry out a second-stage reaction, wherein the reaction conditions are as follows: keeping the stirring speed, the temperature and the air flow velocity unchanged, controlling the concentration of ammonia water at 2-7g/L and the pH at 9.00-11.00, concentrating by using a solid-lifting unit (20) to improve the solid content and adjust the clear-out speed of a solid-lifting device, and finally, stopping the reaction when the D50 is measured to be 3.8-4.5 mu m;
and S3, washing, drying and screening the slurry to obtain the precursor of the single crystal NCM ternary cathode material.
2. The method for preparing a single-crystal NCM ternary positive electrode material precursor according to claim 1, wherein Ni is added to a total concentration of 1.6mo1/L in a ratio in step S1x:Coy:MnzThe sulfate solution, 8mol/L caustic soda solution and 20% ammonia water are added into the reaction unit (10) and inert gas is introduced at the same time to carry out the first stage reaction.
3. The method for producing a single-crystal NCM ternary positive electrode material precursor according to claim 1, wherein in step S1, the reaction conditions are: the stirring speed is 1030-1050 r/min, the pH is 12.00-12.50, the temperature is 50-55 ℃, and the inert gas flow is 0.1-0.5 m3/h。
4. The method for producing a single-crystal NCM ternary positive electrode material precursor according to claim 3, wherein in step S2, after the D50 is measured to be 1.5 μm, the ammonia value in the reaction vessel is increased to perform the second-stage reaction.
5. The method for producing a single-crystal NCM ternary positive electrode material precursor according to claim 4, wherein in step S2, the reaction conditions are: keeping the stirring speed, the temperature and the air flow velocity unchanged, controlling the concentration of ammonia water at 3-4g/L and the pH at 10.50-10.80, concentrating by using a solid-extracting unit (20) to increase the solid content and adjust the clear-out speed of the solid-extracting device, and finally, stopping the reaction when the D50 is 4.0 mu m.
6. The method for preparing a single crystal NCM ternary positive electrode material precursor as claimed in claim 1, wherein in step S3, the drying temperature is 110-120 ℃.
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| CN113415830A (en) * | 2021-08-24 | 2021-09-21 | 金驰能源材料有限公司 | Preparation method of lithium ion battery anode material precursor |
| CN113451565A (en) * | 2021-05-06 | 2021-09-28 | 福建常青新能源科技有限公司 | Production process of high-tap-density high-sphericity internal radial ternary precursor |
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