CN115557541A - Preparation method of nickelic core-shell structure ternary precursor and precursor prepared by preparation method - Google Patents
Preparation method of nickelic core-shell structure ternary precursor and precursor prepared by preparation method Download PDFInfo
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Abstract
The invention discloses a method for preparing a nickelic core-shell structure ternary precursor, which comprises the steps of respectively preparing two parts of ternary mixed salt feed liquid, and introducing inert atmosphere into one part of ternary mixed salt feed liquid to mark as feed liquid A; the other part is added with an oxidant and marked as feed liquid B. Adding the feed liquid A, ammonia water and caustic soda liquid into a first reaction kettle by using a metering pump, introducing inert gas, overflowing slurry in the first reaction kettle into a second reaction kettle after the first reaction kettle reaches a certain discharge granularity, adding the feed liquid B into the second reaction kettle, introducing oxidizing gas or solution, and aging, filter-pressing, washing and drying the slurry to obtain the ternary precursor after the slurry reaches the required granularity. The method effectively solves the technical problems of the ball crack phenomenon caused by the fact that water cannot effectively overflow in the drying process of the high-nickel ternary precursor and the migration and mixed discharge of lithium ions in the subsequent calcining process.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a method for preparing a high-nickel core-shell structure ternary precursor and the ternary precursor prepared by the method.
Background
The ternary cathode material has a very wide market in the power battery market as a lithium ion battery material with a very promising development prospect. The ternary positive electrode material is obtained by mixing and calcining a ternary precursor and a lithium source by lithium carbonate.
At present, high-nickel ternary precursors prepared by most manufacturers have conventional particle sizes (9-15 micrometers), and although the method has high yield and stable batches, the high-nickel ternary precursors prepared by the method have excessively wide particle size distribution, and water cannot overflow in time in the drying process, so that particles crack, and excessive micro powder is generated. In the subsequent calcining process, lithium ions are not facilitated to enter the ternary precursor, so that the nickel and lithium mixed discharge of the prepared ternary cathode material is increased, the capacity of the cathode material is reduced, and the cycle performance is poor.
In view of this, the present invention is directed to the research of the present invention for the problems of the ball cracking phenomenon caused by the water not being able to overflow effectively during the drying process of the high-nickel ternary precursor, and the migration and mixing of lithium ions during the subsequent calcination process.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a method for preparing a ternary precursor with a high nickel core-shell structure.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a ternary precursor with a high nickel core-shell structure comprises the following steps:
s1, preparing raw materials: mixing soluble nickel salt, soluble cobalt salt and soluble manganese salt according to Ni x Co y Mn z (OH) 2 Preparing two parts of ternary mixed salt solution according to the molar ratio of the corresponding elements, wherein x, y and z are positive numbers and x + y + z =1, respectively marking as solution A and solution B, introducing inert gas such as nitrogen or helium into the solution A in the preparation process, and adding an oxidant into the solution B;
simultaneously, using purchased liquid caustic soda as a precipitator and preparing ammonia water as a complexing agent;
s2, internal nucleation at the early stage: adding pure water into a first reaction kettle, wherein the adding amount just submerges the stirring position, then adding the material liquid A, caustic soda liquid and ammonia water prepared in the step S1 into the first reaction kettle, wherein the ammonia water is added quantitatively, the adding amount of the caustic soda liquid is adjusted to enable the pH value in the first reaction kettle to be at a high level, the discharging granularity of the discharging port of the first reaction kettle is kept between 4 and 6 micrometers by controlling the feeding speed of the material liquid A and the pH value in the kettle in the period, and when the discharging granularity is reached, an overflow port of the first reaction kettle is opened to enable slurry in the first reaction kettle to automatically overflow into a second reaction kettle, wherein the discharging amount of the first reaction kettle is 20 to 40 percent of the capacity of the second reaction kettle;
s3, shell growth: when the discharge amount of the first reaction kettle reaches the stirring height of the second reaction kettle, starting stirring of the second reaction kettle, adding the feed liquid B, the liquid caustic soda and the ammonia water into the second reaction kettle in a high-speed feeding mode for reaction to generate ternary precursor slurry, starting an overflow port of the second reaction kettle, enabling the slurry in the second reaction kettle to overflow into a thickener continuously, separating the slurry into clear liquid and thick slurry by the thickener, returning the thick slurry into the second reaction kettle for continuous reaction, so as to increase the solid content of the slurry in the second reaction kettle, and keeping the solid content in the second reaction kettle to be 20-30%;
s4, aging: when the slurry in the second reaction kettle reaches the required granularity, opening a discharge hole of the second reaction kettle to enable the slurry to automatically overflow to an aging tank for aging; and keeping conventional feeding, observing the granularity condition of the slurry in the process, and injecting oxidizing gas or solution into the second reaction kettle at any time to maintain the oxidizing atmosphere in the reaction kettle, wherein the adding amount is finely adjusted according to the specific surface area of the granularity.
And S5, performing filter pressing, washing and drying on the aged slurry to obtain the core-shell structure ternary precursor.
In a further step S1, the soluble nickel salt is nickel sulfate, the soluble cobalt salt is cobalt sulfate, the soluble manganese salt is manganese sulfate, and the concentration of metal salts in the feed liquid A and the feed liquid B is 80-100 g/L.
In a further step S1, introducing inert gas into the feed liquid A through a peristaltic pump in the preparation process, wherein the oxygen content is lower than 1%; adding hydrogen peroxide or sodium chlorate solution into the feed liquid B as an oxidant, wherein the mass percentage of the oxidant in the feed liquid B is 0.1-3%. The function of the oxidant is to oxidize manganese ions into +3 valences, and to maintain sufficient oxidizing property of the feed liquid, so that the slurry in the reaction kettle is in an oxidizing atmosphere during the reaction process, thereby controlling the specific surface area and tap density of the product.
In a further step S1, the precipitant is liquid caustic soda (aqueous sodium hydroxide solution) with a mass concentration of 30%, so that the feed liquid in the reaction kettle can be rapidly precipitated with the liquid caustic soda. The complexing agent is ammonia water with the mass concentration of 12-14%.
In the further step S2, the feed rate of the feed liquid A is 40-60L/h. The feed liquid A adopts low feed speed because the nucleation of the material is excessive at the stage, and the tap density is too low when the low feed speed is adopted to prevent the granularity of the slurry from growing to be capable of discharging, so that a product with high tap density cannot be obtained.
In the further step S2, the pH value in the first reaction kettle in the nucleation stage is 11.3-12, the reaction temperature is 50-65 ℃, and the stirring speed is 500-600 r/min.
In a further step S2, an inert gas, such as nitrogen or argon, is introduced during the reaction to maintain the non-oxidizing atmosphere in the first reaction vessel.
In a further step S3, when the discharge amount of the first reaction vessel reaches 60% of the capacity of the second reaction vessel, the second reaction vessel is started to stir. At the moment, the slurry in the second reaction kettle reaches the stirring height, and the stirring effect is better.
In a further step S3, after the nucleation reaction, the feed liquid B is added into the second reaction kettle at a high feed speed of 200-300L/h, so that the tap density of the precursor can be improved to the maximum extent.
In a further step S3, during the shell growth process, an oxidizing gas, such as oxygen or air, is kept introduced throughout the shell growth process. The amount of the oxidizing gas is controlled by the amount of the oxidizing gasThe tap density and the specific surface area of the slurry in the reaction kettle are determined, and excessive oxidation of the surface of the precursor can be caused by excessive introduction, so that the tap density of the precursor is reduced, and the single crystal is easy to fall off; too small an amount of the feed or too fast a particle size growth of the precursor slurry, resulting in too small a specific surface area. The standard for the introduction of the oxidizing gas is: e.g. having a specific surface area of the slurry particles of less than 10m 2 The introduction amount of oxygen or air is increased; if the specific surface area is larger than 10m 2 And/g, reducing or stopping the introduction of oxygen or air. The oxidizing gas can be replaced by an oxidant, such as hydrogen peroxide or a sodium chlorate solution.
In the further step S3, the temperature of the second reaction kettle is 50-65 ℃, the pH value of the slurry is 10.3-11.2, and the stirring speed is 300-450 r/min.
In a further step S4, when the granularity of the slurry in the second reaction kettle reaches 10-12 microns, a discharge hole of the second reaction kettle is opened to enable the slurry to automatically overflow to an aging tank for aging. The particle size of 10-12 microns is the conventional particle size of products in the industry at present, and other particle size ranges can be selected.
In the further step S4, the aging time is 2 to 3 hours.
In the further steps S2-S4, the adding amount of the liquid caustic soda is adjusted according to the pH value of the slurry required in the reaction stage, and the concentration of the ammonia water in the slurry is 0.4-0.45 mol/L.
The tap density of the ternary precursor prepared by the method is 2.0-2.4 g/cm 3 The surface area of the core is 2-6 m 2 The specific surface area of the finally obtained ternary precursor is 9-16 m 2 /g。
Compared with the prior art, the technical scheme of the invention has the following positive effects:
the invention provides a method for preparing a nickelic core-shell structure ternary precursor, which comprises the steps of respectively preparing two parts of ternary mixed salt solution before the reaction starts, introducing inert atmosphere into one part of ternary mixed salt solution, and marking the solution as solution A; the other part is added with an oxidant and marked as feed liquid B. And simultaneously adding the feed liquid A, the ammonia water and the liquid caustic soda into a first reaction kettle by using a metering pump, introducing inert gas, and maintaining the atmosphere in the reaction kettle to be a reducing atmosphere.
And after the first reaction kettle reaches a certain discharge granularity, overflowing the slurry in the first reaction kettle into a second reaction kettle, adding the feed liquid B into the second reaction kettle, introducing oxidizing gas or solution, and after the slurry reaches the required granularity, sequentially aging, press-filtering, washing and drying to obtain the ternary precursor.
By the method, the high-nickel core-shell structure ternary precursor with compact inside and loose outside is prepared, and the technical problems of the ball crack phenomenon caused by the fact that moisture cannot effectively overflow in the drying process of the high-nickel ternary precursor and the migration and mixed discharge of lithium ions in the subsequent calcining process are effectively solved.
Drawings
FIG. 1 is a scanning electron micrograph of the discharge from the first reaction vessel in step S2 of example 1.
FIG. 2 is a SEM photograph of the final product obtained in step S4 of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
Example 1
S1, preparing raw materials: mixing nickel sulfate, cobalt sulfate and manganese sulfate with Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 Preparing two parts of ternary mixed salt solution with the molar ratio of the corresponding elements, marking as solution A and solution B, and introducing nitrogen into the solution A through a peristaltic pump in the solution preparation process; and adding a trace amount of hydrogen peroxide solution into the feed liquid B, wherein the mass fraction of the hydrogen peroxide solution in the feed liquid B is 0.5%.
The purchased sodium hydroxide solution with the mass concentration of 30% is directly used as a precipitator, and ammonia water with the mass fraction of 14% is prepared to be used as a complexing agent.
S2, internal nucleation at the early stage: and (3) adding pure water into the first reaction kettle in the early stage, wherein the adding amount just submerges the stirring position, adding the feed liquid A prepared in the step (S1), liquid caustic soda and ammonia water into the first reaction kettle, wherein the feed speed of the feed liquid A is 60L/h, and introducing nitrogen to maintain the non-oxidizing atmosphere of the first reaction kettle. The adding amount of the liquid caustic soda is controlled to ensure that the pH value in the reaction kettle is between 11.3 and 11.45, and the concentration of the ammonia water in the first reaction kettle is kept between 0.35 and 0.4mol/L. When the discharge granularity of the discharge hole of the first reaction kettle reaches 4-4.5 microns, the overflow hole is opened, so that the slurry in the first reaction kettle automatically overflows into the second reaction kettle, and the discharge amount of the first reaction kettle is 25% of the feed liquid capacity of the second reaction kettle.
S3, shell growth: when the discharge amount of the first reaction kettle reaches 60% of the capacity of the second reaction kettle, starting stirring of the second reaction kettle, adding the feed liquid B, the liquid caustic soda and the ammonia water into the second reaction kettle in a high-speed feeding mode for reaction, wherein the feeding speed of the feed liquid B is 280L/h, adjusting the liquid caustic soda to enable the pH value in the second reaction kettle to be 10.6-10.7 and the concentration of the ammonia water to be kept at 0.5-0.53 mol/L to generate ternary precursor slurry, starting an overflow port of the second reaction kettle, continuously overflowing into a thickener, returning the thick slurry in the thickener into the second reaction kettle for continuous reaction, so as to improve the solid content of the slurry in the second reaction kettle and maintain the solid content at 20%.
S4, aging: and when the slurry in the second reaction kettle reaches the required granularity of 10-12 microns, opening a discharge hole of the second reaction kettle to enable the slurry to automatically overflow to an aging tank for aging, keeping the conventional feeding, observing the granularity condition of the slurry in the process, detecting the oxidability in the second reaction kettle, and injecting oxygen into the second reaction kettle at any time to maintain the oxidizing atmosphere in the reaction kettle.
And S5, performing filter pressing, washing and drying on the aged ternary precursor slurry to obtain the core-shell structure ternary precursor.
FIG. 1 is a scanning electron micrograph of the discharge from the first reaction vessel in step S2 of example 1. The structure of the ternary precursor core is compact, and the single crystal is in a lath shape and is precisely arranged. The particle size of the core is 4.58 microns, and the specific surface area detected by a comparator is 3.68m 2 /g。
FIG. 2 is a SEM photograph of the final product obtained in step S4 of example 1. The surface single crystal is loose in arrangement, long in strip shape and large in pore size. The granularity of the finally obtained ternary precursor is 10.5 microns, and the tap density is 2.21g/cm 3 The specific surface area detected by a comparator is 11.65m 2 /g。
Example 2
S1, preparing raw materials: mixing nickel sulfate, cobalt sulfate and manganese sulfate according to Ni 0.93 Co 0.05 Mn 0.02 (OH) 2 Preparing two parts of ternary mixed salt solution with the molar ratio of the corresponding elements, marking as solution A and solution B, and introducing nitrogen into the solution A through a peristaltic pump in the solution preparation process; and adding a trace amount of hydrogen peroxide solution into the feed liquid B, wherein the mass fraction of the hydrogen peroxide solution in the feed liquid B is 3.0%.
The purchased sodium hydroxide solution with the mass concentration of 30% is directly used as a precipitator, and ammonia water with the mass fraction of 14% is prepared to be used as a complexing agent.
S2, internal nucleation at the early stage: and (3) adding pure water into the first reaction kettle in the early stage, wherein the adding amount just submerges the stirring position, adding the material liquid A prepared in the step (S1), liquid caustic soda and ammonia water into the first reaction kettle, wherein the feeding speed of the material liquid A is 40L/h, and simultaneously introducing nitrogen to maintain the non-oxidizing atmosphere of the first reaction kettle. The adding amount of the liquid caustic soda is controlled to ensure that the pH value in the reaction kettle is between 11.3 and 11.40, and the concentration of the ammonia water in the first reaction kettle is kept between 0.35 and 0.4mol/L. When the discharge granularity of the discharge hole of the first reaction kettle reaches 5-6 microns, the overflow hole is opened to enable the slurry in the first reaction kettle to automatically overflow into the second reaction kettle, and the discharge amount of the first reaction kettle is 35% of the feed liquid capacity of the second reaction kettle.
S3, shell growth: when the discharge amount of the first reaction kettle reaches 60% of the capacity of the second reaction kettle, starting stirring of the second reaction kettle, adding the feed liquid B, the liquid caustic soda and the ammonia water into the second reaction kettle in a high-speed feeding mode for reaction, wherein the feeding speed of the feed liquid B is 220L/h, adjusting the liquid caustic soda to enable the pH value in the second reaction kettle to be 10.8-10.9, keeping the concentration of the ammonia water at 0.6-0.65 mol/L, generating ternary precursor slurry, starting an overflow port of the second reaction kettle, continuously overflowing into a thickener, returning the thick slurry in the thickener into the second reaction kettle for continuous reaction, so as to improve the solid content of the slurry in the second reaction kettle and maintain the solid content at 25%.
S4, aging: and when the size in the second reaction kettle reaches the required granularity of 10-12 microns, opening a discharge port of the second reaction kettle to enable the size to automatically overflow to an aging tank for aging, keeping the conventional feeding, observing the size condition of the size in the process, detecting the oxidability in the second reaction kettle, and injecting oxygen into the second reaction kettle at any time to maintain the oxidizing atmosphere in the reaction kettle.
And S5, performing filter pressing, washing and drying on the aged ternary precursor slurry to obtain the ternary precursor with the core-shell structure.
The discharge from the first reaction vessel in step S2 of example 2 was examined to determine a nuclear particle size of 2.36 μm and a specific surface area of 5.89m 2 /g。
The final product obtained in the step S4 of the embodiment 2 is detected, and the finally obtained ternary precursor has the granularity of 10.15 microns and the tap density of 2.0g/cm 3 The specific surface area detected by a comparator is 15.85m 2 /g。
Comparative example 1
1. Preparing feed liquid: mixing nickel sulfate, cobalt sulfate and manganese sulfate with Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 Preparing soluble ternary mixed salt feed liquid according to the molar ratio of the corresponding elements, wherein the concentration of the ternary mixed salt in the feed liquid is 100g/L; in the preparation process, a small amount of hydrogen peroxide solution (with the mass concentration of 27.5%) is added into the feed liquid through a peristaltic pump.
The purchased liquid caustic soda with the mass concentration of 30 percent is directly used as a precipitation solvent, and ammonia water with the mass concentration of 12 percent is prepared to be used as a complexing agent.
2. Nucleation: adding pure water into a reaction kettle, wherein the adding amount just submerges the stirring position, uniformly adding the feed liquid prepared in S1 into the reaction kettle at the flow rate of 120L/h, controlling the temperature of the reaction kettle to be 58 ℃, adding ammonia water into the reaction kettle at a certain flow rate, detecting the concentration of the ammonia water in the reaction kettle to be 0.4-0.43 mol/L, keeping the concentration unchanged, adjusting the flow rate of liquid alkali by using a metering pump, keeping the pH in the reaction kettle to be 12-12.3, opening a discharge port and starting increasing the flow of the feed liquid when the granularity D50 in the reaction kettle is 1.5-2.5 microns, namely, stopping nucleation and entering the next stage. Tong (Chinese character of 'tong')The reaction time of the normal nucleation stage is about 24 hours, and the tap density of the granularity can be controlled to reach 1.2g/m 3 As described above. The slurry at the overflow port flows into the thickener at this stage and then flows back to enter the reaction kettle.
3. After the nucleation is finished, the feeding speed of the ternary mixed salt solution is increased to 250-300L/h, and the pH value of the slurry in the reaction kettle is reduced to maintain the pH value in the slurry at 11.3-11.8. And the speed of the slurry in the reaction kettle flowing into the concentration machine is adjusted according to the solid content in the reaction kettle, so that the solid content in the reaction kettle is maintained to be more than 20 percent.
Introducing oxygen at any time during the reaction process, and maintaining the atmosphere in the reaction kettle as oxidizing gas; when the slurry in the reaction kettle reaches 3.5-4 microns, a discharge hole of the reaction kettle is opened to enable the slurry to automatically overflow to an ageing tank for ageing.
4. And carrying out filter pressing, washing and drying on the aged ternary precursor slurry to obtain the large-ratio single crystal ternary precursor.
The core particle size D50 of the ternary precursor is 3.6 microns, and the specific surface area is 4.56m 2 (iv)/g, final particle size of 10.3 microns, tap density of 1.95g/cm 3 The specific surface area is 15.28m 2 /g。
Different from the ternary precursor obtained in the embodiment, the ternary precursor obtained in the comparative example 1 has a loose integral structure, and is easy to break in the application process when used as an electrode material.
Comparative example 2
The difference between the preparation method of the nickelic core-shell structure ternary precursor and the preparation method in the embodiment 1 is that no nitrogen is introduced into the feed liquid A, and the rest reaction processes are the same as the embodiment 1.
The final ternary precursor has a core particle size of 5.98 microns and a specific surface area of 6.59m 2 (iv) g, final ternary precursor particle size of 10.25 microns, tap density of 2.35g/cm 3 Specific surface area of 11.85m 2 (ii) in terms of/g. The nuclear structure is not dense enough, and the single crystal on the surface of the shell has slight oxidation reaction.
Comparative example 3
The difference between the preparation method of the nickelic core-shell structure ternary precursor and the embodiment 1 is that hydrogen peroxide is not added into the feed liquid B, and the rest reaction process is the same as the embodiment 1.
The final ternary precursor has a core particle size of 5.98 μm and a specific surface area of 4.89m 2 (ii) a final ternary precursor particle size of 11.8 microns and tap density of 2.35g/cm 3 Specific surface area of 6.85m 2 (ii) in terms of/g. The surface of the obtained final precursor is compact in monocrystal without adding hydrogen peroxide, the surface porosity is not large enough, the specific surface area is too small, or the precursor is subjected to spherical cracking in the drying process.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing a ternary precursor with a high nickel core-shell structure is characterized by comprising the following steps:
s1, preparing raw materials: mixing soluble nickel salt, soluble cobalt salt and soluble manganese salt according to Ni x Co y Mn z (OH) 2 Preparing two parts of ternary mixed salt solution according to the molar ratio of the corresponding elements, wherein x, y and z are positive numbers and x + y + z =1, respectively marking as solution A and solution B, introducing inert gas such as nitrogen or helium into the solution A in the preparation process, and adding an oxidant into the solution B;
simultaneously, using purchased liquid caustic soda as a precipitator and preparing ammonia water as a complexing agent;
s2, internal nucleation at the early stage: adding pure water into a first reaction kettle, wherein the adding amount just submerges the stirring position, then adding the material liquid A, caustic soda liquid and ammonia water prepared in the step S1 into the first reaction kettle, wherein the ammonia water is added quantitatively, the adding amount of the caustic soda liquid is adjusted to enable the pH value in the first reaction kettle to be at a high level, the discharging granularity of the discharging port of the first reaction kettle is kept between 4 and 6 micrometers by controlling the feeding speed of the material liquid A and the pH value in the kettle in the period, and when the discharging granularity is reached, an overflow port of the first reaction kettle is opened to enable slurry in the first reaction kettle to automatically overflow into a second reaction kettle, wherein the discharging amount of the first reaction kettle is 20 to 40 percent of the capacity of the second reaction kettle;
s3, shell growth: when the discharge amount of the first reaction kettle reaches the stirring height of the second reaction kettle, starting stirring of the second reaction kettle, adding feed liquid B, liquid caustic soda and ammonia water into the second reaction kettle in a high-speed feeding mode for reaction to generate ternary precursor slurry, starting an overflow port of the second reaction kettle, continuously overflowing the slurry in the second reaction kettle into a concentration machine, separating the slurry into clear liquid and thick slurry by the concentration machine, returning the thick slurry into the second reaction kettle for continuous reaction, so that the solid content of the slurry in the second reaction kettle is increased, and the solid content in the second reaction kettle is kept to be 20-30%;
s4, aging: when the size in the second reaction kettle reaches the required granularity, opening a discharge hole of the second reaction kettle to enable the size to automatically overflow to an aging tank for aging;
and S5, performing filter pressing, washing and drying on the aged slurry to obtain the ternary precursor with the core-shell structure.
2. The method for preparing the nickelic core-shell structure ternary precursor according to claim 1, wherein in step S1, the soluble nickel salt is nickel sulfate, the soluble cobalt salt is cobalt sulfate, the soluble manganese salt is manganese sulfate, and the concentration of metal salts in the feed liquid A and the feed liquid B is 80-100 g/L.
3. The method for preparing the nickelic core-shell structure ternary precursor according to claim 1, wherein in step S1, an inert gas is introduced into the feed liquid a through a peristaltic pump during the preparation process, with the oxygen content of the inert gas being lower than 1%; adding hydrogen peroxide or sodium chlorate solution into the feed liquid B as an oxidant, wherein the mass percentage of the oxidant in the feed liquid B is 0.1-3%.
4. The method for preparing the ternary precursor with the high nickel core-shell structure according to claim 1, wherein in the step S2, the feed rate of the feed liquid a is 40 to 60L/h, the pH value in the first reaction kettle in the nucleation stage is preferably 11.3 to 12, the reaction temperature is 50 to 65 ℃, and the stirring speed is 500 to 600r/min.
5. The method for preparing the nickelic core-shell structure ternary precursor according to claim 1, wherein in step S2, inert gas is introduced during the reaction.
6. The method for preparing the nickelic core-shell structure ternary precursor according to claim 1, wherein in step S3, when the discharge amount of the first reaction vessel reaches 60% of the capacity of the second reaction vessel, the stirring of the second reaction vessel is started, and preferably after the nucleation reaction, the feeding rate of the feed liquid B into the second reaction vessel is 200 to 300L/h.
7. The method for preparing the ternary precursor with the high nickel core-shell structure according to claim 1, wherein in the step S3, the oxidizing gas is kept to be introduced in the whole shell growth process stage, preferably, the temperature of the second reaction kettle is 50-65 ℃, the pH value of the slurry is 10.3-11.2, and the stirring speed is 300-450 r/min.
8. The method for preparing the ternary precursor with the high nickel core-shell structure according to claim 1, wherein in step S4, when the particle size of the slurry in the second reaction kettle reaches 10 to 12 microns, a discharge port of the second reaction kettle is opened to allow the slurry to automatically overflow to an aging tank for aging.
9. The method for preparing the nickelic core-shell structure ternary precursor according to claim 1, wherein in steps S2 to S4, the addition amount of the liquid alkali is adjusted according to the pH value of the slurry required in the reaction stage, and the concentration of the ammonia water in the slurry is 0.4 to 0.45mol/L.
10. The ternary precursor prepared according to any one of claims 1 to 9, having a tap density of 2.0 to 2.4g/cm 3 The specific surface area is 11 to 16m 2 /g。
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| CN111732132A (en) * | 2020-07-06 | 2020-10-02 | 金驰能源材料有限公司 | Nickel-cobalt-manganese core-shell structure precursor, preparation method thereof and positive electrode material |
| CN112723426A (en) * | 2020-12-31 | 2021-04-30 | 格林美（无锡）能源材料有限公司 | Porous positive electrode material precursor, preparation method thereof and ternary positive electrode material |
| CN112909260A (en) * | 2021-02-05 | 2021-06-04 | 东莞东阳光科研发有限公司 | Ternary cathode material and preparation method thereof |
| CN113716627A (en) * | 2021-09-28 | 2021-11-30 | 南通金通储能动力新材料有限公司 | High-performance ternary precursor and preparation method thereof |
| CN114804229A (en) * | 2022-04-24 | 2022-07-29 | 南通金通储能动力新材料有限公司 | High-nickel ternary precursor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111732132A (en) * | 2020-07-06 | 2020-10-02 | 金驰能源材料有限公司 | Nickel-cobalt-manganese core-shell structure precursor, preparation method thereof and positive electrode material |
| CN112723426A (en) * | 2020-12-31 | 2021-04-30 | 格林美（无锡）能源材料有限公司 | Porous positive electrode material precursor, preparation method thereof and ternary positive electrode material |
| CN112909260A (en) * | 2021-02-05 | 2021-06-04 | 东莞东阳光科研发有限公司 | Ternary cathode material and preparation method thereof |
| CN113716627A (en) * | 2021-09-28 | 2021-11-30 | 南通金通储能动力新材料有限公司 | High-performance ternary precursor and preparation method thereof |
| CN114804229A (en) * | 2022-04-24 | 2022-07-29 | 南通金通储能动力新材料有限公司 | High-nickel ternary precursor and preparation method thereof |
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