CN112174223A - Preparation process of high-nickel NCA precursor - Google Patents

Preparation process of high-nickel NCA precursor Download PDF

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CN112174223A
CN112174223A CN202010881562.7A CN202010881562A CN112174223A CN 112174223 A CN112174223 A CN 112174223A CN 202010881562 A CN202010881562 A CN 202010881562A CN 112174223 A CN112174223 A CN 112174223A
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nickel
solution
nca precursor
aluminum
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吴有志
吉同棕
吴海军
钱志挺
毛秦钟
王寅峰
周浩
余凡
许益伟
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Zhejiang Meidu Haichuang Lithium Electricity Technology Co ltd
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Abstract

The invention discloses a preparation process of a high-nickel NCA precursor, belonging to the technical field of lithium ion battery preparation. The invention relates to a preparation process of a high-nickel NCA precursor, which is characterized in that a prepared nickel-cobalt mixed salt solution, an alkali-aluminum solution, a complexing agent and a precipitator are subjected to coprecipitation reaction according to a proportion, and then solid-liquid separation, washing, drying, uniformly mixing, screening and demagnetizing are carried out to prepare the high-nickel NCA precursor. The high-nickel NCA precursor prepared by the method has the characteristics of simple process, good safety, low cost and high sphericity.

Description

Preparation process of high-nickel NCA precursor
Technical Field
The invention belongs to the technical field of lithium ion battery preparation, relates to the field of aluminum-containing precursors NCA, and particularly relates to a preparation process of a high-nickel NCA precursor.
Background
With the popularization of new energy automobiles all over the world, government departments support the great force of new energy materials, the popularization of the new energy automobiles and the competitive pressure of related enterprises. Therefore, the development of lithium batteries has certain value and significance.
The method for preparing the precursor is a plurality of methods, and at present, the most common method is mainly a coprecipitation synthesis method, wherein a raw material solution, a precipitator solution and a complexing agent solution are introduced into a reaction kettle in a parallel flow manner under the condition of protective gas to obtain binary, ternary and other multi-element precursors. The high-nickel aluminum-containing precursor NCA has the advantages of large capacity, high voltage plateau and the like, and thus becomes the development direction of lithium batteries.
The current precursors comprise conventional series such as NCM622 type and NCM523 type, high-nickel series such as NCM811 type, NCA, NCMA, lithium-rich manganese-based precursors and the like.
Disclosure of Invention
Based on the existing problems, the invention provides a preparation process of the high-nickel NCA precursor, which has the advantages of simple process, good safety, low cost and high sphericity of the obtained high-nickel NCA precursor.
The solution of the invention for solving the technical problem is as follows:
a process for preparing a high nickel NCA precursor, comprising the steps of:
s1, preparing a nickel-cobalt mixed salt solution by taking solid nickel sulfate hexahydrate and cobalt sulfate heptahydrate as raw materials;
s2, weighing aluminum salt, and adding the aluminum salt into a sodium hydroxide solution to obtain an alkali aluminum solution;
s3. in N2Under the protection of gas, adding the nickel-cobalt mixed salt solution S1, the alkali-aluminum solution S2, a precipitator and a complexing agent into a reaction kettle simultaneously for intermittent or continuous stirring reaction, wherein the stirring speed is 500-1100 r/min;
and S4, after the reaction is finished, performing solid-liquid separation, washing, drying, uniformly mixing, screening and demagnetizing on the materials obtained by the reaction to obtain a high-nickel NCA precursor finished product.
Further, in step S1, the total ion concentration of the nickel-cobalt mixed salt solution is 1.4-1.8mol/L, and the molar ratio of nickel to cobalt is X: y, wherein X is more than or equal to 0.875 and less than or equal to 0.885, Y is more than or equal to 0.085 and less than or equal to 0.095, and X + Y is 0.97.
Further, in step S2, the aluminum salt is industrial aluminum sulfate; al in the alkali aluminum solution3+The concentration is 0.1 mol/L; the molar concentration of the sodium hydroxide solution is 4.0-5.0 mol/L.
Further, in step S3, the concentration of the complexing agent is 10-14mol/L, and the complexing agent is at least one of EDTA, ammonia water, citric acid, ammonium carbonate and ammonium bicarbonate; the precipitant is 4.0-5.0mol/L sodium hydroxide solution; said N is2The flow rate is 0.6-1m3/h。
Further, in step S3, the flow rate of the nickel-cobalt mixed salt solution is 2.31-3.00L/h, the flow rate of the alkali-aluminum solution is 1.05-1.50L/h, the flow rate of the complexing agent is 0.10-0.80L/h, the flow rate of the precipitant is controlled by the pH automatic control system, and the pH is controlled at 11.25-11.65.
Further, in step S3, the batch reaction conditions are: the reaction temperature is 50-60 ℃, the ammonia value is 5-10g/L, the pH value in the kettle is gradually and slowly reduced to 11.25 from 11.65 according to the growth rate of the particles, and the discharge is stopped when the particle size D50 is 3.5-13.5 mu m.
Further, in step S3, the continuous reaction conditions are: pH of 11.25-11.65, reaction temperature of 50-60 deg.C, ammonia value of 5-6g/L, and particle size D50When the pH value is 6.0-10.0 μm, the pH value is increased to generate a large amount of small particles in the reaction kettle, and then the reaction kettle is loweredThe inner pH value is used for stopping the flow when the particles further grow to 13.0 mu m, and then the machine is stopped for discharging.
Further, in step S4, the washing specifically includes: washing the material obtained by the reaction with alkali liquor, and then washing with deionized water at 70-80 ℃, wherein the resistivity of the washing water after washing is less than 0.030 cm/mu s; the alkali liquor is at least one of sodium carbonate solution and sodium hydroxide solution, and the molar concentration of the alkali liquor is 4.0-5.0 mol/L.
Further, in step S4, the drying temperature is 100 ℃ and 130 ℃, and the moisture is controlled below 0.5 wt%; the content of the magnetic foreign matter in the NCA precursor is controlled to be 100ppb or less.
The invention has the beneficial effects that: the invention provides a preparation process of a high-nickel NCA precursor, which comprises the steps of carrying out coprecipitation reaction on a prepared nickel-cobalt mixed salt solution, an alkali-aluminum solution, a complexing agent and a precipitator in proportion, and then carrying out solid-liquid separation, washing, drying, uniformly mixing, screening and demagnetizing to prepare the high-nickel NCA precursor. The high-nickel NCA precursor prepared by the method has the characteristics of simple process, good safety, low cost and high sphericity.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a high-nickel NCA precursor according to the present invention;
FIG. 2 is a 5000-fold scanning electron micrograph of a high-nickel NCA precursor prepared in example 1 of the present invention;
FIG. 3 is a particle size distribution plot of a high nickel NCA precursor prepared in example 1 of the present invention;
FIG. 4 is a 5000-fold scanning electron micrograph of a high-nickel NCA precursor prepared in example 2 of the present invention;
FIG. 5 is a particle size distribution plot of a high nickel NCA precursor prepared in example 2 of the present invention;
FIG. 6 is a 5000-fold scanning electron micrograph of a high-nickel NCA precursor prepared in example 3 of the present invention;
FIG. 7 is a particle size distribution plot of a high nickel NCA precursor prepared in example 3 of the present invention;
FIG. 8 is a graph of the particle size distribution of the high nickel NCA precursor prepared in example 4 of the present invention.
Detailed Description
The conception, specific structure, and technical effects of the present application will be described clearly and completely with reference to the following embodiments, so that the purpose, features, and effects of the present application can be fully understood. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
Example 1
A preparation process of a high-nickel NCA precursor comprises the following steps:
s1, nickel sulfate hexahydrate and cobalt sulfate heptahydrate are mixed according to the mol ratio of Ni: mixing Co 0.88:0.09 to prepare a nickel-cobalt mixed salt solution with the total concentration of 1.5 mol/L;
s2, weighing 1.65Kg of aluminum sulfate octadecahydrate, adding the aluminum sulfate octadecahydrate into 49.20L of sodium hydroxide with the molar concentration of 4.8mol/L, and preparing Al3+An alkali aluminum solution with the concentration of 0.1 mol/L;
s3, preparing 4.8mol/L NaOH solution as a precipitator; preparing 12mol/L ammonia water solution as a complexing agent; will N2At 0.6m3Introducing air into the reaction kettle for completely discharging the air in the reaction kettle, enabling the nickel-cobalt mixed salt solution, the alkali-aluminum solution and the ammonia water solution to flow into the reaction kettle with the volume of 50L in parallel by using a cultured pump at the flow rates of 2.89L/h, 1.30L/h and 0.23-0.52L/h respectively, and regulating the flow rate of the ammonia water solution to enable the ammonia value to be 5-6 g/L; the flow of the precipitator NaOH solution is controlled by a pH automatic control system, and the pH in the kettle is between 11.25 and 11.65; controlling the temperature in the reaction kettle to be 55 ℃, the stirring speed to be 1100r/min, carrying out continuous reaction in the reaction kettle, gradually and slowly reducing the pH value in the reaction kettle according to the particle growth speed in the early stage, wherein the lowest pH value in the reaction kettle is 11.25 in the later stage, and rising the particle size in the reaction kettle when D is50The rotating speed is reduced to 1000r/min at 4.0 mu m, the rotating speed is reduced by 100r/min when the rotating speed is increased by 1.0 mu m at the later stage, and the rotating speed is reduced to 600r/min at the lowest stage when the particle size D is reached50When the particle grows to 9.5 mu m, the pH value is increased to generate a large amount of small particles in the kettle, then the pH value in the reaction kettle is reduced to further grow the particles to 13.0 mu m for interception, the interception time reaches 20h, and the reactor is stopped to discharge the materials. Putting the cut-off material and the slurry in the reaction kettle to be agedDissolving in a bucket, and precipitating for several hours until complete precipitation.
S4, after complete precipitation, discharging supernatant, adding 5L of NaOH solution with the concentration of 4.8mol/L and 50L of deionized water at 70 ℃, stirring for half an hour by using a stirring device, discharging the supernatant, then sending the precipitation slurry to a washing tank for washing, and washing by using the deionized water at 70 ℃ until the resistivity measured by a conductivity meter is less than 0.030cm/us during washing. Then drying at 130 ℃, controlling the water content to be 0.5 wt%, uniformly mixing, screening, and removing the magnetic foreign matters in the precursor to be less than 100ppb by using an iron remover to prepare the NCA precursor. The molar ratio of nickel, cobalt and aluminum prepared by the method is Ni: co: al 0.88: 0.09: 0.03, D5013.0 μm, loose packed density 1.43g/cm3Tap density of 1.67g/cm3Specific surface area of 26.01m2/g。
Example 2
A preparation process of a high-nickel NCA precursor comprises the following steps:
s1, nickel sulfate hexahydrate and cobalt sulfate heptahydrate are mixed according to the mol ratio of Ni: mixing Co 0.88:0.09 to prepare a nickel-cobalt mixed salt solution with the total concentration of 1.5 mol/L;
s2, weighing 1.65Kg of aluminum sulfate octadecahydrate, adding the aluminum sulfate octadecahydrate into 49.20L of sodium hydroxide solution with the molar concentration of 4.8mol/L, and preparing Al3+An alkali aluminum solution with the concentration of 0.1 mol/L;
s3, preparing 4.8mol/L NaOH solution as a precipitator; preparing 12mol/L ammonia water solution as a complexing agent; will N2At 0.6m3Introducing air into the reaction kettle for completely discharging the air in the reaction kettle, enabling the nickel-cobalt mixed salt solution, the alkali-aluminum solution and the ammonia water solution to flow into the reaction kettle with the volume of 50L in parallel by using a cultured pump at the flow rates of 2.89L/h, 1.30L/h and 0.23-0.52L/h respectively, and regulating the flow rate of the ammonia water solution to enable the ammonia value to be 8-10 g/L; the flow of the precipitator NaOH solution is controlled by a pH automatic control system, and the pH in the kettle is gradually reduced to 11.25 from 11.65 according to the growth rate of the particles; controlling the temperature in the reaction kettle to be 55 ℃, the stirring speed to be 1100r/min, carrying out intermittent reaction in the reaction kettle, leading the granularity in the reaction kettle to rise to reach 4.0 mu m, reducing the rotating speed to 1000r/min, reducing the rotation speed to 100r/min every 1.0 mu m rise in the later period, and at least reducing the rotation speed to 600r/minAnd (4) stopping. When the particle size D is50Stopping the machine to discharge when the particle size reaches 13.0 mu m. And (4) putting the slurry in the reaction kettle into an aging barrel, and precipitating for several hours until complete precipitation.
S4, after complete precipitation, discharging supernatant, adding 5L of NaOH solution with the concentration of 4.8mol/L and 50L of deionized water at 70 ℃, stirring for half an hour by using a stirring device, discharging the supernatant, then sending the precipitation slurry to a washing tank for washing, and washing by using the deionized water at 70 ℃ until the resistivity measured by a conductivity meter is less than 0.030cm/us during washing. Then drying at 130 ℃, controlling the water content to be 0.5 wt%, uniformly mixing, screening, and removing the magnetic foreign matters in the precursor to be less than 100ppb by using an iron remover to prepare the NCA precursor. The molar ratio of nickel, cobalt and aluminum prepared by the method is Ni: co: al 0.88: 0.09: 0.03, D5013.0 μm, loose packed density 1.69g/cm3Tap density of 1.85g/cm3The specific surface area is 14.87m2/g。
Example 3
A preparation process of a high-nickel NCA precursor comprises the following steps:
s1, nickel sulfate hexahydrate and cobalt sulfate heptahydrate are mixed according to the mol ratio of Ni: mixing Co 0.88:0.09 to prepare a nickel-cobalt mixed salt solution with the total concentration of 1.5 mol/L;
s2, weighing 1.65Kg of aluminum sulfate octadecahydrate, adding the aluminum sulfate octadecahydrate into 49.20L of sodium hydroxide solution with the molar concentration of 4.8mol/L, and preparing Al3+An alkali aluminum solution with the concentration of 0.1 mol/L;
s3, preparing 4.8mol/L NaOH solution as a precipitator; preparing 12mol/L ammonia water solution as a complexing agent; will N2At 0.6m3Introducing air into the reaction kettle for completely discharging the air in the reaction kettle, enabling the nickel-cobalt mixed salt solution, the alkali-aluminum solution and the ammonia water solution to flow into the reaction kettle with the volume of 50L in parallel by using a cultured pump at the flow rates of 2.89L/h, 1.30L/h and 0.23-0.52L/h respectively, and regulating the flow rate of the ammonia water solution to enable the ammonia value to be 5-6 g/L; the flow of the precipitator NaOH solution is controlled by a pH automatic control system, and the pH in the kettle is gradually reduced to 11.40 from 11.65 according to the growth rate of the particles; controlling the temperature in the reaction kettle to be 55 ℃, the stirring speed to be 1100r/min, and carrying out batch reaction in the reaction kettle to ensure that the granularity in the reaction kettle is increased to reach 4.0 muStopping the machine when m is reached, discharging, placing the slurry in the reaction kettle into an aging barrel, and precipitating for several hours until complete precipitation.
S4, after complete precipitation, discharging supernatant, adding 5L of NaOH solution with the concentration of 4.8mol/L and 50L of deionized water at 70 ℃, stirring for half an hour by using a stirring device, discharging the supernatant, then sending the precipitation slurry to a washing tank for washing, and washing by using the deionized water at 70 ℃ until the resistivity measured by a conductivity meter is less than 0.030cm/us during washing. Then drying at 130 ℃, controlling the water content to be 0.5 wt%, uniformly mixing, screening, and removing the magnetic foreign matters in the precursor to be less than 100ppb by using an iron remover to prepare the NCA precursor. The molar ratio of nickel, cobalt and aluminum prepared by the method is Ni: co: al 0.88: 0.09: 0.03, D50Has a bulk density of 1.21g/cm and a particle size of 4.0 μm3Tap density of 1.70g/cm3The specific surface area is 15.42m2/g。
Example 4
A preparation process of a high-nickel NCA precursor comprises the following steps:
s1, nickel sulfate hexahydrate and cobalt sulfate heptahydrate are mixed according to the mol ratio of Ni: mixing Co 0.88:0.09 to prepare a nickel-cobalt mixed salt solution with the total concentration of 1.5 mol/L;
s2, weighing 1.65Kg of aluminum sulfate octadecahydrate, adding the aluminum sulfate octadecahydrate into 49.20L of sodium hydroxide solution with the molar concentration of 4.8mol/L, and preparing Al3+An alkali aluminum solution with the concentration of 0.1 mol/L;
s3, preparing 4.8mol/L NaOH solution as a precipitator; preparing 12mol/L ammonia water solution as a complexing agent; will N2At 0.6m3Introducing air into the reaction kettle for completely discharging the air in the reaction kettle, enabling the nickel-cobalt mixed salt solution, the alkali-aluminum solution and the ammonia water solution to flow into the reaction kettle with the volume of 50L in parallel by using a cultured pump at the flow rates of 2.89L/h, 1.30L/h and 0.23-0.52L/h respectively, and regulating the flow rate of the ammonia water solution to enable the ammonia value to be 5-6 g/L; the flow of the precipitator NaOH solution is controlled by a pH automatic control system, and the pH in the kettle is gradually reduced to 11.25 from 11.65 according to the growth rate of the particles; controlling the temperature in the reaction kettle to be 55 ℃, the stirring speed to be 1100r/min, carrying out intermittent reaction in the reaction kettle to ensure that the granularity in the reaction kettle is increased to 1000r/min when the granularity reaches 4.0 mu m, and reducing the rotating speed to 1000r/min at the later stageThe decrease of 100r/min for every 1.0 mu m increase is as low as 600 r/min. When the particle size D is50Stopping the machine when the grain grows to 13.0 mu m, discharging, putting the slurry in the reaction kettle into an aging barrel, and precipitating for several hours until the grain is completely precipitated.
S4, discharging supernatant after complete precipitation, adding 5L of NaOH solution with the concentration of 4.8mol/L and 50L of deionized water at 70 ℃, stirring for half an hour by using a stirring device, discharging the supernatant, then sending the precipitate slurry to a washing tank for washing, and washing by using the deionized water at 70 ℃ until the resistivity measured by a conductivity meter is less than 0.030cm/us during washing. Then drying at 130 ℃, controlling the water content to be 0.5 wt%, uniformly mixing, screening, and removing the magnetic foreign matters in the precursor to be less than 100ppb by using an iron remover to prepare the NCA precursor. The molar ratio of nickel, cobalt and aluminum prepared by the method is Ni: co: al 0.88: 0.09: 0.03, D5013.0 μm, loose packed density 1.32g/cm3Tap density of 1.70g/cm3The specific surface area is 16.50m2/g。
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited to the details of the embodiments, but is capable of various modifications and substitutions without departing from the spirit of the invention.

Claims (9)

1. A process for preparing a high-nickel NCA precursor, comprising the steps of:
s1, preparing a nickel-cobalt mixed salt solution by taking solid nickel sulfate hexahydrate and cobalt sulfate heptahydrate as raw materials;
s2, weighing aluminum salt, and adding the aluminum salt into a sodium hydroxide solution to obtain an alkali aluminum solution;
s3. in N2Under the protection of gas, adding the nickel-cobalt mixed salt solution S1, the alkali-aluminum solution S2, a precipitator and a complexing agent into a reaction kettle simultaneously for intermittent or continuous stirring reaction, wherein the stirring speed is 500-1100 r/min;
and S4, after the reaction is finished, performing solid-liquid separation, washing, drying, uniformly mixing, screening and demagnetizing on the materials obtained by the reaction to obtain a high-nickel NCA precursor finished product.
2. The process of claim 1, wherein in step S1, the nickel-cobalt mixed salt solution has a total ion concentration of 1.4-1.8mol/L, a molar ratio of nickel to cobalt of X: y, wherein X is more than or equal to 0.875 and less than or equal to 0.885, Y is more than or equal to 0.085 and less than or equal to 0.095, and X + Y is 0.97.
3. The process for preparing a high-nickel NCA precursor according to claim 1, wherein in step S2, the aluminum salt is industrial aluminum sulfate; al in the alkali aluminum solution3+The concentration is 0.1 mol/L; the molar concentration of the sodium hydroxide solution is 4.0-5.0 mol/L.
4. The process according to claim 1, wherein in step S3, the concentration of the complexing agent is 10-14mol/L, and the complexing agent is at least one of EDTA, ammonia water, citric acid, ammonium carbonate and ammonium bicarbonate; the precipitant is 4.0-5.0mol/L sodium hydroxide solution; said N is2The flow rate is 0.6-1m3/h。
5. The process of claim 1, wherein in step S3, the flow rate of the nickel-cobalt mixed salt solution is 2.31-3.00L/h, the flow rate of the alkali-aluminum solution is 1.05-1.50L/h, the flow rate of the complexing agent is 0.10-0.80L/h, the flow rate of the precipitant is controlled by an automatic pH control system, and the pH is controlled at 11.25-11.65.
6. The process for preparing a high-nickel NCA precursor according to claim 1, wherein in step S3, the batch reaction conditions are: the reaction temperature is 50-60 ℃, the ammonia value is 5-10g/L, the pH value in the kettle is gradually and slowly reduced to 11.25 from 11.65 according to the growth rate of the particles, and the discharge is stopped when the particle size D50 is 3.5-13.5 mu m.
7. The method of claim 1A process for preparing a high-nickel NCA precursor, characterized in that in step S3, the continuous reaction conditions are: pH of 11.25-11.65, reaction temperature of 50-60 deg.C, ammonia value of 5-6g/L, and particle size D50When the particle size is 6.0-10.0 μm, the pH value is raised to generate a large amount of small particles in the kettle, the pH value in the reaction kettle is lowered to further grow the particles to 13.0 μm, the flow is stopped, and then the reactor is stopped to discharge the materials.
8. The process for preparing a high-nickel NCA precursor according to claim 1, wherein in step S4, the washing is specifically: washing the material obtained by the reaction with alkali liquor, and then washing with deionized water at 70-80 ℃, wherein the resistivity of the washing water after washing is less than 0.030 cm/mu s; the alkali liquor is at least one of sodium carbonate solution and sodium hydroxide solution, and the molar concentration of the alkali liquor is 4.0-5.0 mol/L.
9. The process for preparing a high-nickel NCA precursor as claimed in claim 1, wherein in step S4, the drying temperature is 100 ℃ and 130 ℃, and the moisture content is controlled to be less than 0.5 wt%; the content of the magnetic foreign matter in the NCA precursor is controlled to be 100ppb or less.
CN202010881562.7A 2020-08-27 2020-08-27 Preparation process of high-nickel NCA precursor Pending CN112174223A (en)

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