CN110061208B - Lithium battery positive active material precursor and preparation method thereof, lithium battery positive active material and preparation method thereof, and lithium battery - Google Patents
Lithium battery positive active material precursor and preparation method thereof, lithium battery positive active material and preparation method thereof, and lithium battery Download PDFInfo
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- CN110061208B CN110061208B CN201910265226.7A CN201910265226A CN110061208B CN 110061208 B CN110061208 B CN 110061208B CN 201910265226 A CN201910265226 A CN 201910265226A CN 110061208 B CN110061208 B CN 110061208B
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a lithium battery positive active material precursor and a preparation method thereof, a lithium battery positive active material and a preparation method thereof, and a lithium battery. The method for preparing the precursor of the positive active material of the lithium battery comprises the following steps: adding a nickel-cobalt salt solution, an aluminum salt solution, a precipitator and a complexing agent into the reaction base solution to carry out synthetic reaction to obtain mixed slurry; in the process of carrying out the synthesis reaction, obtaining a sample from the mixed slurry; detecting the concentration of free nickel and the concentration of free ammonia in the sample, and when the concentration of free nickel and the concentration of free ammonia reach a preset range, carrying out solid-liquid separation on the mixed slurry to obtain a solid-phase product; and carrying out post-treatment on the solid-phase product to obtain the lithium battery positive active material precursor. According to the method for preparing the lithium battery positive active material, the high-quality lithium battery positive active material precursor can be prepared by detecting and controlling the concentrations of free nickel and free ammonia in the reaction mixed slurry.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a lithium battery positive active material precursor and a preparation method thereof, a lithium battery positive active material and a preparation method thereof, and a lithium battery.
Background
Lithium ion batteries have received much attention from people because of their advantages of high energy density, good safety, long cycle life, and low self-discharge. Since the successful commercialization of lithium ion secondary batteries by the japan SONY energy technology corporation in 1990, the lithium ion secondary batteries have been widely used in many portable electronic devices such as mobile phones, notebook computers, instruments and meters, and have a promising application prospect in the fields of electric vehicles, electric tools, energy storage peak shaving power stations, and the like.
Currently, commercial lithium ion battery positive electrode materials mainly comprise lithium cobaltate, spinel lithium manganate, lithium iron phosphate and the like, and various problems are found in the using process of the lithium ion battery positive electrode materials, so that the research and development of ternary materials become a major key point in recent years, the nickel-cobalt-manganese ternary lithium ion positive electrode material in the lithium ion positive electrode material is developed rapidly, and the nickel-cobalt-manganese ternary lithium ion positive electrode material is just the synergistic effect of nickel-cobalt-manganese, and the nickel-cobalt-manganese ternary lithium ion battery positive electrode material integrates LiNiO2、LiCoO2、LiMn2O4The three layered structure materials have the advantages of high specific capacity, low cost, stable cycle performance, good safety performance and the like, and are considered to better replace LiCoO2The positive electrode material of (1). The current techniqueIn the operation, the nickel-cobalt-manganese ternary positive electrode material of the lithium ion secondary battery has the defects of high production cost, large particle size, wide particle size distribution, particle agglomeration phenomenon, large initial irreversible capacity and the like.
The performance of the ternary cathode material is mainly determined by the quality of the precursor of the ternary cathode material. At present, the content of impurities in a precursor of a ternary cathode material produced by domestic manufacturers is generally high, particularly the content of impurities such as Fe, Cr, Cu, Zn and the like which affect the safety performance of a battery is high, the impurity metals can be dissolved out in the charging and discharging processes of the battery, migrate to a cathode and precipitate to form dendritic crystals, the dendritic crystals of the impurity metals can pierce a diaphragm to cause micro short circuit of the battery, the temperature of a battery core is increased, the electrochemical performance of the battery is deteriorated, even the thermal runaway of the battery is caused, and finally the combustion and explosion of the battery are caused. However, the existing method for preparing the precursor of the positive active material for lithium batteries still needs to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to provide a lithium battery positive active material precursor and a method for preparing the same, a lithium battery positive active material and a method for preparing the same, and a lithium battery. The method for preparing the lithium battery positive active material can be used for preparing a high-quality lithium battery positive active material precursor by detecting and controlling the concentrations of free nickel and free ammonia in the reaction mixed slurry.
In one aspect of the present invention, a method of preparing a precursor for a positive active material of a lithium battery is provided. According to an embodiment of the invention, the method comprises: (1) adding a nickel-cobalt salt solution, an aluminum salt solution, a precipitator and a complexing agent into the reaction base solution to carry out synthetic reaction to obtain mixed slurry; obtaining a sample from the mixed slurry in the process of the synthesis reaction; (2) detecting the concentration of free nickel and the concentration of free ammonia in the sample, and when the concentration of free nickel and the concentration of free ammonia reach a preset range, carrying out solid-liquid separation on the mixed slurry to obtain a solid-phase product; (3) and carrying out post-treatment on the solid-phase product to obtain the lithium battery positive active material precursor.
According to the method for preparing the precursor of the positive active material of the lithium battery, disclosed by the embodiment of the invention, through sampling and detecting the mixed slurry of the nickel-cobalt salt solution, the aluminum salt, the precipitator and the complexing agent, parameters such as the granularity and the tap density of the precursor product of the positive active material can be indirectly judged according to the content of free nickel and free ammonia in the reaction slurry. The inventors have found that, in the precursor synthesis reaction, the contents of free nickel and free ammonia in the reaction mixture slurry can be adjusted by adjusting the flow rates of the complexing agent and the precipitating agent supplied to the reaction system, and further, the grain size growth of the positive electrode active material precursor can be controlled. Therefore, in the synthesis reaction of the precursor of the positive electrode active material, the flow rates of the complexing agent and the precipitating agent are controlled so that the concentration of free nickel and the concentration of free ammonia in the mixed slurry sample reach the preset range, and the high-quality positive electrode active material can be obtained.
In addition, the method for preparing the lithium battery positive active material precursor according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the nickel cobalt salt solution is Ni2+Co at a concentration of 1.6 to 2.0mol/L2+The concentration is 0.3-0.375 mol/L.
In some embodiments of the invention, AlO in the aluminum salt solution2 -The concentration is 0.3-0.625 mol/L.
In some embodiments of the present invention, the reaction bottom liquid is a mixed liquid of ammonia water and water, the volume concentration of the ammonia water in the reaction bottom liquid is 1.0% to 3.0%, and NH in the ammonia water3The mass concentration of (A) is 25-28%.
In some embodiments of the present invention, the reaction base solution has a pH value of 11 to 12.
In some embodiments of the present invention, the temperature of the reaction base solution is 50 to 60 ℃.
In some embodiments of the invention, the precipitant is an aqueous solution of sodium hydroxide with a mass concentration of 25% to 40%.
In some embodiments of the present invention, the complexing agent is ammonia water with a mass concentration of 15% to 25%.
In some embodiments of the present invention, the predetermined range of the free nickel concentration is 0 to 0.1mol/L, and the predetermined range of the free ammonia concentration is 11.0 to 11.5 g/L.
In some embodiments of the present invention, during the process of adding the nickel cobalt salt solution, the aluminum salt solution, the precipitant, and the complexing agent to the reaction base solution, a flow rate of the nickel cobalt salt solution is 50 to 60mL/min, a flow rate of the aluminum salt solution is 5 to 15mL/min, a flow rate of the precipitant is 10 to 12mL/min, and a flow rate of the complexing agent is 4 to 5 mL/min.
In some embodiments of the invention, in step (2), the sample is allowed to stand for stratification, and then the free nickel content and the free ammonia content in the supernatant of the sample are detected.
In some embodiments of the invention, the post-processing comprises: and sequentially carrying out alkali soaking, water washing and drying on the solid-phase product.
In another aspect of the present invention, the present invention provides a precursor for a positive active material of a lithium battery. According to the embodiment of the present invention, the lithium battery positive active material precursor is prepared by the method for preparing the lithium battery positive active material precursor of the above embodiment. Therefore, the lithium battery positive active material precursor has the advantages of low impurity content, proper granularity, high tap density and excellent comprehensive performance.
In yet another aspect of the present invention, a method of forming a positive active material for a lithium battery is provided. According to an embodiment of the invention, the method comprises: (a) preparing a precursor of the positive active material of the lithium battery according to the method for preparing the precursor of the positive active material of the lithium battery in the embodiment; (b) and mixing the precursor of the positive active material with a lithium source and roasting to obtain the positive active material of the lithium battery. Therefore, the lithium battery positive active material prepared by the method has the advantages of low impurity content, proper granularity, high tap density and excellent comprehensive performance.
In yet another aspect of the present invention, a positive active material for a lithium battery is provided. According to the embodiment of the present invention, the positive active material for a lithium battery is prepared by the method for preparing the positive active material for a lithium battery of the above embodiment. Therefore, the lithium battery positive active material is low in impurity content, appropriate in granularity, high in tap density and excellent in comprehensive performance.
In yet another aspect of the present invention, a lithium battery is provided. According to an embodiment of the present invention, the lithium battery includes: the battery comprises a positive pole piece, a diaphragm, a negative pole piece and electrolyte; the positive pole piece comprises a positive pole current collector and a positive pole material formed on the surface of the positive pole current collector, and the positive pole material comprises the positive pole active material of the lithium battery in the embodiment. The lithium battery has excellent cycle stability and reliability by using the positive active material of the above embodiment.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow chart of a method for preparing a precursor of a positive active material for a lithium battery according to an embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the present invention, a method of preparing a precursor for a positive active material of a lithium battery is provided. According to an embodiment of the invention, the method comprises: (1) adding a nickel-cobalt salt solution, an aluminum salt solution, a precipitator and a complexing agent into the reaction base solution to carry out synthetic reaction to obtain mixed slurry; in the process of carrying out the synthesis reaction, obtaining a sample from the mixed slurry; (2) detecting the concentration of free nickel and the concentration of free ammonia in the sample, and when the concentration of free nickel and the concentration of free ammonia reach a preset range, carrying out solid-liquid separation on the mixed slurry to obtain a solid-phase product; (3) and carrying out post-treatment on the solid-phase product to obtain the lithium battery positive active material precursor.
According to the method for preparing the precursor of the positive active material of the lithium battery, disclosed by the embodiment of the invention, through sampling and detecting the mixed slurry of the nickel-cobalt salt solution, the aluminum salt solution, the precipitator and the complexing agent, parameters such as the granularity and the tap density of the precursor product of the positive active material can be indirectly judged according to the content of free nickel and free ammonia in the reaction slurry. The inventors have found that, in the precursor synthesis reaction, the contents of free nickel and free ammonia in the reaction mixture slurry can be adjusted by adjusting the flow rates of the complexing agent and the precipitating agent supplied to the reaction system, and further, the grain size growth of the positive electrode active material precursor can be controlled. Therefore, in the synthesis reaction of the precursor of the positive electrode active material, the flow rates of the complexing agent and the precipitating agent are controlled so that the concentration of free nickel and the concentration of free ammonia in the mixed slurry sample reach the preset range, and the high-quality positive electrode active material can be obtained.
A method for preparing a precursor for a positive active material for a lithium battery according to an embodiment of the present invention is further described in detail with reference to fig. 1. According to an embodiment of the invention, the method comprises:
s100: synthesis reaction and sampling
In the step, a nickel-cobalt salt solution, an aluminum salt solution, a precipitator and a complexing agent are added into a reaction base solution for synthetic reaction to obtain mixed slurry; during the synthesis reaction, samples were taken from the mixed slurry. According to a specific example of the present invention, the synthesis reaction may be performed by a synthesis reaction kettle commonly used in the art, wherein a reaction bottom solution is added into the reaction kettle in advance, and then a nickel-cobalt salt solution, an aluminum salt solution, a precipitant and a complexing agent are respectively supplied into the reaction kettle through different feed inlets to perform the synthesis reaction.
According to some embodiments of the present invention, the nickel cobalt salt solution may be prepared from conventional nickel cobalt salt solutionsAnd mixing the nickel salt and the cobalt salt with water (preferably deionized water). According to a specific example of the present invention, the nickel salt may be at least one selected from nickel sulfate, nickel nitrate, and nickel chloride; the cobalt salt may be at least one selected from the group consisting of cobalt sulfate, cobalt nitrate, and cobalt chloride. In the above nickel cobalt salt solution, Ni2+Co at a concentration of 1.6 to 2.0mol/L2+The concentration is 0.3-0.375 mol/L. Thus, Ni in the nickel cobalt salt2+、Co2+The concentration is proper, and the concentration of the precursor in the reaction kettle can be easily adjusted by adjusting the flow of the precursor, so that the high-quality precursor of the positive active material can be obtained.
According to some embodiments of the invention, AlO in the aluminum salt solution2 -The concentration is 0.3-0.625 mol/L. According to some embodiments of the present invention, the aluminum salt solution used in the method of the present invention may be formulated as follows: common aluminum salts (e.g., aluminum sulfate, aluminum chloride, aluminum nitrate, etc.) are mixed with an appropriate amount of sodium hydroxide and water to satisfy the above concentration requirements, and then the resulting mixed solution is filtered to remove flocculent precipitates to obtain an aluminum salt solution. In addition, yellowing of the solution should be avoided during the preparation of the aluminum salt solution.
According to some embodiments of the present invention, the reaction bottom liquid is a mixed liquid of ammonia water and water, in the reaction bottom liquid, the volume concentration of the ammonia water is 1.0% to 3.0%, and NH in the ammonia water3The mass concentration of (A) is 25-28%. Therefore, in the reaction base solution, the impurity content of the precursor of the positive electrode active material generated by the reaction of the nickel cobalt salt and the aluminum salt is lower, and the performances such as granularity, tap density and the like are better.
According to some embodiments of the present invention, the pH of the reaction base solution is 11 to 12, preferably 11.30 to 11.50, and specifically, the pH of the reaction base solution may be adjusted to the above range by using sodium hydroxide in the preparation stage of the reaction base solution. Therefore, in the reaction base solution, the impurity content of the precursor of the positive electrode active material generated by the reaction of the nickel cobalt salt and the aluminum salt is lower, and the performances such as granularity, tap density and the like are better.
According to some embodiments of the present invention, the temperature of the reaction bottom liquid is 55 to 70 ℃, and preferably, the temperature of the reaction bottom liquid is 60 ℃. Therefore, in the reaction base solution, the impurity content of the precursor of the positive electrode active material generated by the reaction of the nickel cobalt salt and the aluminum salt is lower, and the performances such as granularity, tap density and the like are better.
According to some embodiments of the invention, the precipitant is an aqueous solution of sodium hydroxide with a mass concentration of 25% to 40%. Therefore, the precipitant can not introduce impurity ions which are difficult to remove into the reaction system, has proper concentration, and is easy to adjust parameters such as pH value, reaction progress and the like of the reaction system through the flow rate of the precipitant in the synthesis reaction, thereby further reducing the impurity content of the product and further improving the properties such as granularity, tap density and the like of the product.
According to some embodiments of the invention, the complexing agent is ammonia water with a mass concentration of 15% to 25%. Therefore, the complexing agent can not introduce impurity ions which are difficult to remove into the reaction system, has proper concentration, and is easy to adjust parameters such as pH value, reaction progress and the like of the reaction system through the flow rate of the conditional complexing agent in the synthesis reaction, thereby further reducing the impurity content of the product and further improving the properties such as granularity, tap density and the like of the product.
Further, according to some embodiments of the present invention, when the reaction bottom liquid satisfies the conditions as described above, the nickel cobalt salt solution, the aluminum salt solution, the precipitant, and the complexing agent are simultaneously added to the reaction bottom liquid to start the synthesis reaction. According to some embodiments of the present invention, the synthesis reaction is performed at a stirring speed of 600-1200 rpm (preferably 800rpm) to further ensure that the raw materials are well mixed. In addition, high-purity raw materials are used in the synthesis reaction, so that the phenomenon that the impurity content of the product is too high due to the purity of the raw materials is avoided.
S200: detecting sample, separating solid phase product
In the step, the concentration of free nickel and the concentration of free ammonia in a sample are detected, and when the concentration of free nickel and the concentration of free ammonia reach a preset range, solid-liquid separation is carried out on the mixed slurry to obtain a solid-phase product. The inventor finds that the concentrations of free nickel and free ammonia in the reaction system can change along with the change of the reaction progress, and the concentrations of the free nickel and the free ammonia in the reaction system can represent performance parameters such as impurity content, granularity, tap density and the like of the prepared precursor of the positive electrode active material. When the concentration of the free nickel and the concentration of the free ammonia reach the preset range, the product performance is indicated to reach the requirement. Further, the inventors have found, through intensive studies, that the concentrations of free nickel and free ammonia in the reaction system can be controlled by controlling the flow rates of the nickel-cobalt salt solution, the aluminum salt solution, the precipitant and the complexing agent to be fed into the reaction bottom liquid. Therefore, the method for preparing the precursor of the positive active material can adjust the concentration of free nickel and free ammonia in a reaction system by controlling the flow rate of inputting the nickel-cobalt salt solution, the aluminum salt solution, the precipitator and the complexing agent into the reaction bottom liquid, and can obtain a high-quality precursor product of the positive active material. Further, when the concentration of free nickel and the concentration of free ammonia in the reaction system reach a predetermined range, the mixed slurry is subjected to solid-liquid separation to separate the positive electrode active material precursor from the reaction system.
According to some embodiments of the present invention, the concentration of free nickel is in the range of 0 to 0.1g/L and the concentration of free ammonia is in the range of 11.0 to 11.5g/L, wherein the pH of the reaction system is about 11.60 to 11.80. When the concentration of free nickel and free ammonia in the reaction system reaches the range, the granularity of the precursor product of the prepared positive active material can reach D508-10 mu m, and the tap density is not less than 1.8g/cm3The design standard of (2), the impurity content is extremely low, and the comprehensive performance of the product is excellent.
According to some embodiments of the invention, in the process of adding the nickel cobalt salt solution, the aluminum salt solution, the precipitant and the complexing agent to the reaction base solution, the flow rate of the nickel cobalt salt solution is 50-60 mL/min, the flow rate of the aluminum salt solution is 5-15 mL/min, the flow rate of the precipitant is 10-12 mL/min and the flow rate of the complexing agent is 4-5 mL/min. By controlling the flow rate of each raw material within the above range, the concentration of free nickel and free ammonia in the reaction system can be easily controlled to reach a predetermined range, thereby preparing a high-quality precursor product of the positive electrode active material. According to a specific example of the present invention, the above-mentioned respective raw materials may be fed into the reaction system by a peristaltic pump and an electromagnetic metering pump.
According to some embodiments of the present invention, in S200, the sample is allowed to stand for stratification, and then the free nickel concentration and the free ammonia concentration in the supernatant of the sample are measured. The inventors found that the reaction system was in a suspension state during the synthesis reaction, and that the operation was simplified by allowing a sample taken out from the reaction system to stand for separation to obtain a supernatant, sealing was necessary to prevent overflow of NH3 during standing, and then measuring the concentration of free nickel and the concentration of free ammonia in the supernatant. In addition, the concentration of free nickel and the concentration of free ammonia in the supernatant obtained by allowing the sample to stand and stratify were the same as those in the reaction system.
S300: post-treatment
In the step, the solid-phase product is subjected to post-treatment to obtain the precursor of the lithium battery positive active material. As described above, the solid-phase product contains a positive electrode active material precursor that meets design criteria. And carrying out post-treatment on the solid-phase product so as to obtain a precursor product of the positive active material of the lithium battery.
According to some embodiments of the invention, the post-processing comprises: and (4) sequentially carrying out alkali soaking, water washing and drying on the solid-phase product. Specifically, the solid-phase product can be subjected to alkaline alkali soaking and water washing until the pH value of a water phase is 8-9, and then solid-liquid separation is carried out to obtain a precipitate. And drying the precipitate at 80-120 ℃ for 20-24 h to obtain a precursor product of the lithium battery positive active material.
In another aspect of the present invention, the present invention provides a precursor for a positive active material of a lithium battery. According to the embodiment of the present invention, the lithium battery positive active material precursor is prepared by the method for preparing the lithium battery positive active material precursor of the above embodiment. Therefore, the lithium battery positive active material precursor has the advantages of low impurity content, proper granularity, high tap density and excellent comprehensive performance. In addition, it should be noted that all the features and advantages described above for the "method for preparing a precursor of a positive active material of a lithium battery" are also applicable to the precursor of the positive active material of the lithium battery, and are not described in detail herein.
In yet another aspect of the present invention, a method of forming a positive active material for a lithium battery is provided. According to an embodiment of the invention, the method comprises: (a) preparing a precursor of the positive active material of the lithium battery according to the method for preparing the precursor of the positive active material of the lithium battery in the embodiment; (b) and mixing the precursor of the positive active material with a lithium source and roasting to obtain the positive active material of the lithium battery. Therefore, the lithium battery positive active material prepared by the method has the advantages of low impurity content, proper granularity, high tap density and excellent comprehensive performance.
It should be noted that, in the step (b), the positive electrode active material precursor may be mixed with a lithium source and calcined by a method conventional in the art, for example, according to a specific example of the present invention, the lithium source may be selected from inorganic salts of lithium, such as lithium nitrate, lithium carbonate, lithium hydroxide monohydrate, and the like. The mixing ratio of the positive electrode active material precursor and the lithium source is also not particularly limited, and may be determined according to the chemical composition of the lithium oxide; the roasting treatment can be carried out at a roasting temperature of 600-800 ℃. In addition, it should be noted that the method for preparing the positive active material of the lithium battery has all the features and advantages described in the foregoing for the "method for preparing a precursor of a positive active material of a lithium battery", and thus, detailed description is omitted.
In yet another aspect of the present invention, a positive active material for a lithium battery is provided. According to the embodiment of the present invention, the positive active material for a lithium battery is prepared by the method for preparing the positive active material for a lithium battery of the above embodiment. Therefore, the lithium battery positive active material is low in impurity content, appropriate in granularity, high in tap density and excellent in comprehensive performance. In addition, it should be noted that all the features and advantages described above for the "method for preparing a positive active material for a lithium battery" are also applicable to the positive active material for a lithium battery, and are not described in detail herein.
In yet another aspect of the present invention, a lithium battery is provided. According to an embodiment of the present invention, the lithium battery includes: the battery comprises a positive pole piece, a diaphragm, a negative pole piece and electrolyte; the positive pole piece comprises a positive pole current collector and a positive pole material formed on the surface of the positive pole current collector, and the positive pole material comprises the positive pole active material of the lithium battery in the embodiment. The lithium battery has excellent cycle stability and reliability by using the positive active material of the above embodiment. In addition, it should be noted that the lithium battery has all the features and advantages described in the foregoing for the "positive active material of lithium battery", and thus the description thereof is omitted.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1) Raw material preparation
Reaction base solution: mixing ammonia water and deionized water according to the volume concentration of 1.0 percent of the ammonia water, and adding NH in the ammonia water3The mass concentration of (2) is 25%;
nickel cobalt salt solution: adding nickel sulfate and cobalt sulfate into a proper amount of deionized water according to a molar ratio of 0.8:0.15, and uniformly stirring to obtain a nickel-cobalt salt solution containing Ni2+Concentration of 1.6mol/L, Co2+The concentration is 0.3 mol/L;
aluminum salt solution: adding aluminum sulfate and sodium hydroxide into a proper amount of deionized water according to the mass ratio of 0.125:0.252, uniformly stirring, filtering to remove flocculent precipitate, and adding AlO in the obtained aluminum salt solution2 -The concentration is 0.5 mol/L;
a precipitant: a 25% sodium hydroxide aqueous solution;
complexing agent: 15% ammonia water.
(2) Synthesis reaction
Adding deionized water into a 20L synthesis reaction kettle, stopping adding the deionized water until the deionized water is about to overflow out of the reaction kettle, heating the deionized water to 60 ℃, adding ammonia water at the rotating speed of 800rpm to obtain a reaction base solution, and adjusting the reaction base solution by using a sodium hydroxide solution until free ammonia is 11.8-12.0 g/L and the pH value is 11.80-12.00; respectively and simultaneously adding a nickel-cobalt salt solution, an aluminum salt solution, a precipitator and a complexing agent into the reaction base solution by using a peristaltic pump, and maintaining the pH value of the reaction base solution to be 11.60-11.80; wherein the flow rate of the nickel-cobalt salt solution is 50mL/min, the flow rate of the aluminum salt solution is 10mL/min, the flow rate of the precipitator is 10mL/min, and the flow rate of the complexing agent is 4 mL/min.
(3) Sampling detection
After the synthesis reaction is carried out for a stable period, 20mL of slurry is sampled from the reaction slurry, standing and layering are carried out, and the content of free nickel in the supernatant of the sample is detected to be 0-0.1 g/L and the concentration of free ammonia is detected to be 11.0-11.5 g/L by an acid-base titration method, so that the preset concentration range is reached.
(4) Solid-liquid separation
Discharging the reaction slurry (suspension) out of the reaction kettle, carrying out solid-liquid separation on the slurry, and collecting a solid-phase product.
(5) Post-treatment
Carrying out alkali soaking and water washing on the solid-phase product obtained in the step (4) until the pH value of a water phase is 8, and carrying out solid-liquid separation to collect precipitates; drying the precipitate at 100 deg.C for 24h to obtain NCA ternary material precursor with particle size D509.0 +/-1 mu m, and tap density of 1.80g/cm3。
Example 2
(1) Raw material preparation
Reaction base solution: mixing ammonia water and deionized water according to the volume concentration of the ammonia water of 2.0 percent, and adding NH in the ammonia water3The mass concentration of (A) is 26.5%;
nickel cobalt salt solution: adding nickel sulfate and cobalt sulfate into a proper amount of deionized water according to a molar ratio of 0.8:0.15, and uniformly stirring to obtain a nickel-cobalt salt solution containing Ni2+Concentration of 2.0mol/L, Co2+The concentration is 0.375 mol/L;
aluminum salt solution: adding aluminum sulfate and sodium hydroxide into a proper amount of deionized water according to the mass ratio of 0.125:0.252, uniformly stirring, filtering to remove flocculent precipitate, and adding AlO in the obtained aluminum salt solution2 -The concentration is 0.625 mol/L;
a precipitant: a 32% sodium hydroxide aqueous solution;
complexing agent: ammonia water with mass concentration of 18 percent.
(2) Synthesis reaction
Adding deionized water into a 20L synthesis reaction kettle, stopping adding the deionized water until the deionized water is about to overflow out of the reaction kettle, heating the deionized water to 60 ℃, adding ammonia water at the rotating speed of 800rpm to obtain a reaction base solution, and adjusting the reaction base solution by using a sodium hydroxide solution until free ammonia is 11.8-12.0 g/L and the pH value is 11.80-12.00; respectively and simultaneously adding a nickel-cobalt salt solution, an aluminum salt solution, a precipitator and a complexing agent into the reaction base solution by using an electromagnetic metering pump, and maintaining the pH value of the reaction base solution to be 11.60-11.80; wherein the flow rate of the nickel-cobalt salt solution is 50mL/min, the flow rate of the aluminum salt solution is 10mL/min, the flow rate of the precipitator is 10mL/min, and the flow rate of the complexing agent is 6 mL/min.
(3) Sampling detection
After the synthesis reaction is carried out for a stable period, 20mL of slurry is sampled from the reaction slurry, standing and layering are carried out, and the content of free nickel in the supernatant of the sample is detected to be 0-0.1 g/L and the concentration of free ammonia is detected to be 11.0-11.5 g/L by an automatic titrator and an acid-base titration method, so that the preset concentration range is reached.
(4) Solid-liquid separation
Discharging the reaction slurry (suspension) out of the reaction kettle, carrying out solid-liquid separation on the slurry, and collecting a solid-phase product.
(5) Post-treatment
Carrying out alkali soaking and water washing on the solid-phase product obtained in the step (4) until the pH value of a water phase is 8.5, and carrying out solid-liquid separation to collect precipitates; drying the precipitate at 120 deg.C for 20h to obtain NCM ternary material precursor with particle size D509.0 +/-1 mu m, and tap density of 1.82g/cm3。
Example 3
And (2) taking the NCA ternary material precursor prepared in the embodiment 1, mixing the precursor with lithium carbonate according to the mass ratio of 1:1.05, presintering at 700 ℃ for 5h, and roasting at 780 ℃ for 15h to obtain the NCA ternary material.
Example 4
And (3) taking the NCA ternary material precursor prepared in the embodiment 2, mixing the precursor with lithium hydroxide monohydrate according to the mass ratio of 1:1.06, and calcining at 500 ℃ for 5h and 760 ℃ for 20h to obtain the NCA ternary material.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (6)
1. A method for preparing a precursor of a positive active material for a lithium battery, comprising:
(1) raw material preparation
Reaction base solution: mixing ammonia water and deionized water according to the volume concentration of 1.0 percent of the ammonia water, and adding NH in the ammonia water3The mass concentration of (2) is 25%;
nickel cobalt salt solution: adding nickel sulfate and cobalt sulfate into deionized water according to the molar ratio of 0.8:0.15, and adding Ni into the nickel-cobalt salt solution2+Concentration of 1.6mol/L, Co2+The concentration is 0.3 mol/L;
aluminum salt solution: adding aluminum sulfate and sodium hydroxide into deionized water according to the mass ratio of 0.125:0.252, filtering to remove flocculent precipitate, and adding AlO into the obtained aluminum salt solution2 -The concentration is 0.5 mol/L;
a precipitant: a 25% sodium hydroxide aqueous solution;
complexing agent: ammonia water with the mass concentration of 15%;
(2) synthesis reaction
Adding deionized water into a 20L synthesis reaction kettle until the deionized water is about to overflow the reaction kettle, stopping adding the deionized water, heating the deionized water to 60 ℃, adding ammonia water at the rotating speed of 800rpm to obtain a reaction base solution, and adjusting the reaction base solution by using a sodium hydroxide solution until the concentration of free ammonia is 11.8-12.0 g/L and the pH value is 11.80-12.00; respectively and simultaneously adding a nickel-cobalt salt solution, an aluminum salt solution, a precipitator and a complexing agent into the reaction base solution, and maintaining the pH value of the reaction base solution to be 11.60-11.80; wherein the flow rate of the nickel-cobalt salt solution is 50mL/min, the flow rate of the aluminum salt solution is 10mL/min, the flow rate of the precipitator is 10mL/min, and the flow rate of the complexing agent is 4 mL/min;
(3) sampling detection
After the synthesis reaction enters a stable period, sampling from the reaction slurry, standing for layering, and detecting that the content of free nickel in a sample supernatant is 0-0.1 g/L and the concentration of free ammonia is 11.0-11.5 g/L by an acid-base titration method, wherein the content reaches a preset concentration range;
(4) solid-liquid separation
Discharging the reaction slurry out of the reaction kettle, carrying out solid-liquid separation on the slurry, and collecting a solid-phase product;
(5) post-treatment
And carrying out post-treatment on the solid-phase product to obtain the lithium battery positive active material precursor.
2. A method for preparing a precursor of a positive active material for a lithium battery, comprising:
(1) raw material preparation
Reaction base solution: mixing ammonia water and deionized water according to the volume concentration of the ammonia water of 2.0 percent, and adding NH in the ammonia water3The mass concentration of (A) is 26.5%;
nickel cobalt salt solution: adding nickel sulfate and cobalt sulfate into deionized water according to the molar ratio of 0.8:0.15, and adding Ni into the nickel-cobalt salt solution2+Concentration of 2.0mol/L, Co2+The concentration is 0.375 mol/L;
aluminum salt solution: adding aluminum sulfate and sodium hydroxide into deionized water according to the mass ratio of 0.125:0.252, filtering to remove flocculent precipitate, and adding AlO into the obtained aluminum salt solution2 -The concentration is 0.625 mol/L;
a precipitant: a 32% sodium hydroxide aqueous solution;
complexing agent: ammonia water with the mass concentration of 18%;
(2) synthesis reaction
Adding deionized water into a 20L synthesis reaction kettle until the deionized water is about to overflow the reaction kettle, stopping adding the deionized water, heating the deionized water to 60 ℃, adding ammonia water at the rotating speed of 800rpm to obtain a reaction base solution, and adjusting the reaction base solution by using a sodium hydroxide solution until the concentration of free ammonia is 11.8-12.0 g/L and the pH value is 11.80-12.00; respectively and simultaneously adding a nickel-cobalt salt solution, an aluminum salt solution, a precipitator and a complexing agent into the reaction base solution, and maintaining the pH value of the reaction base solution to be 11.60-11.80; wherein the flow rate of the nickel-cobalt salt solution is 50mL/min, the flow rate of the aluminum salt solution is 10mL/min, the flow rate of the precipitator is 10mL/min, and the flow rate of the complexing agent is 6 mL/min;
(3) sampling detection
After the synthesis reaction enters a stable period, sampling from the reaction slurry, standing for layering, and detecting that the content of free nickel in a sample supernatant is 0-0.1 g/L and the concentration of free ammonia is 11.0-11.5 g/L by an acid-base titration method, wherein the content reaches a preset concentration range;
(4) solid-liquid separation
Discharging the reaction slurry out of the reaction kettle, carrying out solid-liquid separation on the slurry, and collecting a solid-phase product;
(5) post-treatment
And carrying out post-treatment on the solid-phase product to obtain the lithium battery positive active material precursor.
3. A precursor of a positive active material for a lithium battery, characterized in that it is prepared by the method of claim 1 or 2.
4. A method of preparing a positive active material for a lithium battery, comprising:
(a) preparing a precursor of the positive electrode active material according to the method of claim 1 or 2;
(b) and mixing the precursor of the positive active material with a lithium source and roasting to obtain the positive active material of the lithium battery.
5. A positive active material for a lithium battery, characterized in that it is prepared by the method of claim 4.
6. A lithium battery, comprising: the battery comprises a positive pole piece, a diaphragm, a negative pole piece and electrolyte; wherein the positive pole piece comprises a positive pole current collector and a positive pole material formed on the surface of the positive pole current collector, and the positive pole material comprises the positive pole active material of the lithium battery in claim 5.
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