CN113880148A - Ternary precursor and preparation method and application thereof - Google Patents
Ternary precursor and preparation method and application thereof Download PDFInfo
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Abstract
The application relates to the technical field of lithium ion battery materials, in particular to a ternary precursor and a preparation method and application thereof, wherein the ternary precursor is of a core-shell structure, an inner core is loose and porous, a shell is of a compact orange petal type structure with a central epitaxial enlargement shape, and a fan-shaped central angle of the orange petal type structure is 10-30 degrees; the obtained ternary precursor particle inner core has a loose and porous structure, so that the internal stress is reduced in the lithium battery charging and discharging process, and microcracks are avoided; the shell is compact and has a orange-peel structure, lithium salt is easier to permeate into the core of the ternary precursor in the sintering process of preparing the anode material, the diffusion mass transfer resistance is smaller, the sintering temperature is lower, the dynamic performance is better, and the use is more facilitated; the material has the advantages of high tap density, good sphericity, uniform primary particle distribution and narrow particle size distribution, and provides good premise and basis for the subsequent preparation of high-quality cathode materials.
Description
Technical Field
The application belongs to the technical field of lithium ion battery materials, and particularly relates to a ternary precursor and a preparation method and application thereof.
Background
New energy automobiles have become a major direction for the development of global automobile industry transitions and are important engines to promote the continued growth of the world economy. As a power battery of the heart of a new energy automobile, the problem of endurance mileage and flat price pain points is urgently needed to be solved. In order to further improve the energy density of the nickel-cobalt-manganese ternary cathode material, high nickel is one of the most mature and highest acceptable technical progress directions in the identifiable path, the high nickel deepens the technical barrier, the high nickel ternary precursor becomes the impetus of enterprises, and the competitive intensity rate is further improved. The technology in the high-nickel ternary NCM material system is changed, nickel element is beneficial to improving specific capacity and energy density, cobalt is beneficial to improving conductivity and rate capability, and high-nickel low-cobalt enables the specific capacity of the battery to be improved, but capacity retention rate and stability are weakened. Therefore, the research on the structural design of the high-nickel material starts from the structure of the precursor, and has very important significance for improving the electrochemical performance of the high-nickel material and accelerating the industrialization process of the high-nickel material.
At present, the failure mechanism of the high-nickel ternary cathode material mainly comprises the generation of spherical microcracks of the ternary cathode material, the aggravation of nickel-lithium mixed discharge, the gradual transformation of a crystal cell layered structure to a spinel and rock phase structure and the gradual and serious disorder of a bulk phase structure, and the high-nickel ternary cathode material has the problems of surface lithium residue, gas generation, formation of rock salt phase, microcrack, metal ion dissolution, thermal runaway and the like, so that potential safety hazards are brought, and further large-scale application of the high-nickel ternary cathode material is limited.
Disclosure of Invention
The application aims to provide a ternary precursor and a preparation method and application thereof, and aims to solve the problems that in the prior art, the properties of a sphere of a ternary precursor material are unstable, such as low capacity, poor circulation and the like, due to easy generation of microcracks.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the application provides a ternary precursor which is of a core-shell structure, wherein an inner core of the ternary precursor is loose and porous, a shell of the ternary precursor is of a compact orange petal-shaped structure with an enlarged central extension, and a sector central angle of the orange petal-shaped structure is 10-30 degrees.
In a second aspect, the present application provides a method for preparing a ternary precursor, comprising the steps of:
providing a first mixed solution of a mixed solution of soluble salts of nickel ions, cobalt ions and manganese ions, a precipitator, a complexing agent and a base solution, introducing inert gas to create a micro-nano bubble aqueous solution condition to perform a first mixing reaction to obtain a first precipitate, stopping feeding when the median particle size of the first precipitate reaches a first target particle size, and performing aging treatment to obtain a ternary precursor crystal nucleus;
carrying out a second mixing reaction on the ternary precursor crystal nucleus, a nickel ion, cobalt ion and manganese ion soluble salt mixed solution, a precipitator and a complexing agent to obtain a second precipitate, and stopping feeding when the median particle size of the second precipitate reaches a second target particle size to obtain ternary precursor slurry;
and filtering, washing and drying the ternary precursor slurry to obtain the ternary precursor.
In a third aspect, the present application provides a cathode material, wherein the cathode material is prepared from a ternary precursor or a ternary precursor obtained by a preparation method of the ternary precursor.
In a fourth aspect, the present application provides a lithium ion battery comprising a positive electrode material.
According to the ternary precursor provided by the first aspect of the application, the obtained ternary precursor particle inner core has a loose and porous structure, so that the internal stress is reduced in the lithium battery charging and discharging process, and microcracks are prevented from being generated in the particles; the shell is compact and has a orange-peel structure, lithium salt is easier to permeate into the core of the high-nickel ternary precursor in the sintering process of preparing the positive electrode material, the diffusion mass transfer resistance is smaller, the sintering temperature is lower, the crystal boundary is less during sintering, the dynamic performance is better, and therefore the DCR of the material is smaller and is more beneficial to use; the material has the advantages of high tap density, good sphericity, uniform primary particle distribution and narrow particle size distribution, and provides good premise and basis for the subsequent preparation of excellent high-nickel cathode materials.
In the preparation method of the ternary precursor provided by the second aspect of the present application, an inert gas is introduced into a first mixed solution of a mixed solution of soluble salts of nickel ions, cobalt ions and manganese ions, a precipitant, a complexing agent and a base solution to create an alkaline aqueous solution environment containing micro-nano bubbles, and a gas-liquid interface formed by the micro-nano bubbles in water has a characteristic of easily accepting H+And OH-The formed precursor core comprises a part of micro-nano bubbles to form a precursor core material with a loose porous structure, and the stable form and the good shaping effect of the ternary precursor core are ensured through long-time aging treatment; further adding a soluble salt mixed solution, a precipitator and a complexing agent to grow the shell, and inducing the shell to grow on the basis of the dominant crystal face of the loose and porous core material to finally form a compact shell structure, wherein the shell structure is an orange petal type structure which is enlarged from the center in an extending way; the preparation method can accurately regulate and control the crystal structure of the ternary precursor material, ensures that a high-capacity and long-circulation ternary precursor product is obtained, is simple and easy to operate, can be produced in a large scale, and is suitable for wide application.
The positive electrode material that this application third aspect provided, positive electrode material carry out the high temperature sintering by ternary precursor and lithium salt and prepare and obtain, because ternary precursor has inside loose porous, the shell is tight and orange petal type structure, and during preparation positive electrode material, the lithium salt permeates the nuclear inside of ternary precursor more easily and the lithium salt that combines is more even more, consequently, the positive electrode material that obtains can show the cyclicity performance and the capacity that improves lithium ion battery.
In the lithium ion battery provided by the fourth aspect of the present application, the lithium ion battery includes the anode material, and the anode material includes the ternary precursor with a special structure, so that the service life of the lithium ion battery is prolonged, and the electrochemical stability and the cycle performance of the lithium ion battery are improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a ternary precursor provided in an embodiment of the present application.
Fig. 2 is an electron microscope analysis diagram of the ternary precursor provided in example 1 provided in the present application.
Fig. 3 is a graph showing a particle size distribution analysis of the ternary precursor provided in example 1 provided in the examples of the present application.
Figure 4 is an XRD analysis of the ternary precursor provided in example 1 provided in the examples of the present application.
Fig. 5 is a performance analysis test chart of the lithium ion battery prepared in example 1 and comparative examples 1 and 2 provided in the examples of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiment of the application provides a ternary precursor, wherein the ternary precursor is of a core-shell structure, an inner core of the ternary precursor is loose and porous, a shell of the ternary precursor is of a compact orange petal-shaped structure with an enlarged central extension, and a fan-shaped central angle of the orange petal-shaped structure is 10-30 degrees.
According to the ternary precursor provided by the first aspect of the application, the obtained ternary precursor particle inner core has a loose and porous structure, so that the internal stress is reduced in the lithium battery charging and discharging process, and microcracks are prevented from being generated in the particles; the shell is compact and has a orange-peel structure, lithium salt is easier to permeate into the core of the high-nickel ternary precursor in the sintering process of preparing the positive electrode material, the diffusion mass transfer resistance is smaller, the sintering temperature is lower, the crystal boundary is less during sintering, the dynamic performance is better, and therefore the DCR of the material is smaller and is more beneficial to use; the material has the advantages of high tap density, good sphericity, uniform primary particle distribution and narrow particle size distribution, and provides good premise and basis for the subsequent preparation of high-quality high-nickel cathode materials.
In some embodiments, the proportion of the inner core in the ternary precursor is 0.2-0.4: 1, and the proportion of the inner core is controlled, so that the performance of the obtained product is better, lithium salt is more easily permeated into the inner core of the high-nickel ternary precursor in the sintering process of preparing the anode material, the diffusion mass transfer resistance is smaller, the sintering temperature is lower, the crystal boundary is less during sintering, the dynamic performance is better, and the DCR of the material is smaller and is more favorable for use; the material has the advantages of high tap density, good sphericity, uniform primary particle distribution and narrow particle size distribution, and provides good premise and basis for the subsequent preparation of excellent high-nickel cathode materials.
In some embodiments, the morphology of the ternary precursor is a sphere-like structure, forming a sphere, which is beneficial for mixing uniformly to perform the reaction.
In some embodiments, in the ternary precursor, the peak intensity ratio of characteristic diffraction peak 001 appearing at 2 θ of 18.8 to 19.8 to characteristic diffraction peak 101 appearing at 2 θ of 38 to 39.5 in the xrd spectrum is 0.6 to 1.0, the crystallinity is high, the crystal lattice is perfect, and the crystal lattice is substantially defect-free.
In some embodiments, the tap density of the ternary precursor is 2.00-2.50 g/cm3The specific surface area is 5 to 7m2/g。
A second aspect of the embodiments of the present application provides a method for preparing a ternary precursor, including the following steps:
s01, providing a first mixed solution of a mixed solution of soluble salts of nickel ions, cobalt ions and manganese ions, a precipitator, a complexing agent and a base solution, introducing an inert gas to create a micro-nano bubble aqueous solution condition to perform a first mixing reaction to obtain a first precipitate, stopping feeding when the median particle size of the first precipitate reaches a first target particle size, and performing aging treatment to obtain a ternary precursor crystal nucleus;
s02, carrying out a second mixing reaction on the ternary precursor crystal nucleus, a nickel ion, cobalt ion and manganese ion soluble salt mixed solution, a precipitator and a complexing agent to obtain a second precipitate, and stopping feeding when the median particle size of the second precipitate reaches a second target particle size to obtain ternary precursor slurry;
and S03, filtering, washing and drying the ternary precursor slurry to obtain a ternary precursor.
In the preparation method, inert gas is introduced into a first mixed solution of a mixed solution of soluble salts of nickel ions, cobalt ions and manganese ions, a precipitator, a complexing agent and a base solution to create an alkaline aqueous solution environment containing micro-nano bubbles, and a gas-liquid interface formed by the micro-nano bubbles in water has a characteristic of easily accepting H+And OH-The formed precursor core comprises a part of micro-nano bubbles to form a precursor core material with a loose porous structure, and the stable form and the good shaping effect of the ternary precursor core are ensured through long-time aging treatment; further adding an ion soluble salt mixed solution, a precipitator and a complexing agent to grow the shell, and inducing the shell to grow on the basis of the dominant crystal face of the loose and porous core material to finally form a compact shell structure, wherein the shell structure is an orange petal type structure which is enlarged from the center in an extending way; the preparation method can accurately regulate and control the crystal structure of the ternary precursor material, ensures that a high-capacity and long-circulation ternary precursor product is obtained, is simple and easy to operate, can be produced in a large scale, and is suitable for wide application.
In step S01, a mixed solution of soluble salts of nickel ions, cobalt ions and manganese ions, a precipitant and a complexing agent are providedAnd introducing inert gas into the first mixed solution of the base solution to create a micro-nano bubble aqueous solution condition, carrying out a first mixing reaction to obtain a first precipitate, stopping feeding when the median particle size of the first precipitate reaches a first target particle size, and carrying out aging treatment to obtain a ternary precursor crystal nucleus. Inert gas is introduced into the first mixed solution to create an alkaline aqueous solution environment containing micro-nano bubbles, and gas-liquid interfaces formed by the micro-nano bubbles in water are easy to accept H+And OH-The formed precursor core comprises a part of micro-nano bubbles to form a precursor core material with a loose porous structure, and the stable form and the good shaping effect of the ternary precursor core are ensured through long-time aging treatment.
In some embodiments, in the mixed solution of soluble salts of nickel ions, cobalt ions and manganese ions, the molar ratio of nickel ions, cobalt ions and manganese ions is 70-98: 1-29: 1-29, wherein the proportion of nickel ions is controlled to be 70-98, the obtained ternary precursor material is ensured to be a high-nickel product, the nickel content in the obtained ternary precursor material is ensured to be higher, the battery capacity can be better improved, and the higher the nickel content is, the higher the battery capacity is, and further the electrochemical property of the battery is improved.
In some embodiments, the molar concentration of the mixed solution of soluble salts of nickel ions, cobalt ions and manganese ions is 1.0-2.0 mol/L; the molar concentration of the mixed ion soluble salt solution is controlled, so that the obtained ternary precursor material has good agglomeration effect, stable forming and high tap density, and is favorable for use. If the concentration of the soluble salt mixed solution is too high, the number of the obtained crystal seeds is large, and the obtained ternary precursor precipitate is serious in agglomeration, poor in sphericity and uneven in distribution of primary particle morphology, so that the ternary precursor precipitate is not beneficial to subsequent use; if the concentration of the soluble salt mixed solution is too low, the obtained crystal seeds are few, the growth speed is too fast, the sphericity is poor, and the tap density of the obtained ternary precursor is low, the use is also not facilitated.
In some embodiments, the mixed solution of soluble salts of nickel ions, cobalt ions, and manganese ions is selected from at least one of a sulfate solution, a chloride solution, and a nitrate solution.
In some embodiments, the precipitating agent comprises a sodium hydroxide solution, which is provided to further promote precipitation of the ternary precursor nuclei during the reaction. In some embodiments, the sodium hydroxide solution is selected from a sodium hydroxide solution with a mass percentage concentration of 25-32%, and if the concentration of the provided sodium hydroxide solution is too low, the yield in the preparation process is low; if the concentration is too high, the production speed of the obtained product is too high, the product is precipitated too early, the morphology of the product is not controlled easily, and crystal nuclei with good sphericity and uniform particle morphology distribution cannot be obtained.
In some embodiments, the complexing agent comprises an aqueous ammonia solution, and is provided to facilitate mixing of the reactants. In some embodiments, the ammonia water solution is selected from 12-20% by mass, and if the concentration of the provided ammonia water solution is too low, the yield is low, the crystallinity is poor, and the wastewater treatment capacity is increased in the preparation process; if the concentration is too high, the production speed of the obtained product is too high, the product is precipitated too early, the morphology of the product is not controlled easily, and crystal nuclei with good sphericity and uniform particle morphology distribution cannot be obtained.
In some embodiments, the base solution is selected from an alkaline aqueous solution having a pH of 11.0 to 11.50, and the concentration of free ammonium groups in the base solution is 1.0 to 2.5 g/L. The base solution is added for better controlling reaction parameters, providing a buffering effect, being beneficial to creating an alkaline aqueous solution environment containing micro-nano bubbles and being convenient for obtaining a precursor inner core with a loose porous structure; if the base solution is not added, the dispersion of the reaction materials is not facilitated, and the uniform mixing of the materials is not facilitated. The concentration of free ammonium radicals in the provided base solution is low and is only 1.0-2.5g/L, and the reaction is carried out under the condition of low ammonia water complexation, so that the formation of a core material with a loose porous structure is facilitated, the reduction of internal stress is facilitated, and the generation of cracks is avoided. If the concentration of the ammonium radical is higher than 2.5g/L, the obtained product has a compact structure, is easy to suffer from cracks caused by the impact of internal stress in the using process, and is not favorable for stable properties.
Further, mixing a mixed solution of soluble salts of nickel ions, cobalt ions and manganese ions, a precipitator, a complexing agent and a base solution to obtain a first mixed solution, and introducing inert gas to create a micro-nano bubble aqueous solution to perform a first mixing reaction to obtain a first precipitate.
In some implementations, the inert gas is at least one selected from nitrogen, helium, argon and neon, and the inert gas is provided, so that on one hand, the conditions of the micro-nano bubble aqueous solution can be created, and the gas-liquid interface formed by the micro-nano bubbles in water has an acceptable H easily-And OH-The formed precursor core comprises a part of micro-nano bubbles to form a precursor core material with a loose porous structure; on the other hand, the introduction of the inert gas ensures that the reaction with the reactants is avoided, no impurity substance is introduced, and the purity of the material is ensured to be higher.
In some embodiments, the introduction amount of the inert gas is 0.1-0.5L/min, and the conditions for creating the micro-nano bubble aqueous solution can be ensured by controlling the introduction amount of the gas, so that the formed precursor core comprises a part of micro-nano bubbles, and the precursor core material with the loose porous structure is formed. If the flow rate of the introduced gas is too high, the loose porous structure of the core material is not uniform, which is not beneficial to the formation of the whole material.
In some embodiments, the inert gas is introduced at 0.1L/min, 0.15L/min, 0.2L/min, 0.25L/min, 0.3L/min, 0.35L/min, 0.4L/min, 0.45L/min, 0.5L/min.
In some embodiments, in the reaction process, the reaction kettle is matched with a micro-nano bubble machine, nitrogen gas of 0.1-0.5L/min is introduced in the reaction process to create an atmosphere of micro-nano bubble aqueous solution, and a first mixing reaction is performed to obtain a first precipitate.
In some embodiments, the first mixture is introduced with an inert gas to form a micro-nano bubble aqueous solution, and a first mixing reaction is performed to obtain a first precipitate. In the first mixing reaction step, the reaction temperature is 50-60 ℃, the reaction speed is 250-350 rpm, and the first precipitate is promoted to be generated by mixing reaction.
Further, when the median particle size of the first precipitate reaches a first target particle size, stopping feeding, and performing aging treatment to obtain a ternary precursor crystal nucleus.
In some embodiments, the first target particle size is 2-5 micrometers, and the size of the first target particle size is controlled to be moderate, that is, the size of the obtained ternary precursor crystal nucleus is controlled to be moderate, which is beneficial to subsequent reactions. If the first target granularity is too large or too small, the structural design of the product is influenced, if the first target granularity is too small, the structural design effect is not obvious, the loose structure of the inner core is not obvious, the battery capacity is low, and the cycle difference is influenced; if the first target particle size is too large, the obtained product has too many voids and low tap density, resulting in low volume density and more side reactions of the battery.
Further, stopping feeding the first precipitate when the median particle size reaches a first target particle size, and performing aging treatment to shape the loose and porous crystal nucleus; in the aging process, fine particles are continuously dissolved, normal particles are modified, and impurities adsorbed or occluded in the particles enter the solution, so that the obtained precipitate is purer, incomplete crystal grains become more complete, the morphological characteristics of crystal nuclei are improved, and the preparation of the particles is facilitated.
In some embodiments, in the aging step, the rotation speed of the aging is 120-160 rpm, the temperature of the aging is 50-60 ℃, and the time of the aging is 10-15 h. The long-time aging treatment is carried out under the condition of low rotating speed, so that the morphology of the ternary precursor crystal nucleus can be further improved, the obtained crystal nucleus is round, and meanwhile, the property of the ternary precursor crystal nucleus is improved, and the loose and porous structure of the ternary precursor crystal nucleus is more stable.
In step S02, performing a second mixing reaction on the ternary precursor crystal nucleus, the nickel ion, the cobalt ion, the manganese ion, the mixed solution of soluble salts, the precipitant, and the complexing agent to obtain a second precipitate, and stopping feeding when the median particle size of the second precipitate reaches a second target particle size to obtain a ternary precursor slurry. In the step, the obtained ternary precursor crystal nucleus and the raw material are subjected to secondary feeding, and the orange petal-shaped shell grows on the basis of the basic kernel.
In some embodiments, the soluble salt mixed solution of nickel ions, cobalt ions, manganese ions, the precipitant, and the complexing agent are selected as in step S01, and the specific addition species is consistent with that added in step S01.
In some embodiments, a ternary precursor crystal nucleus, a nickel ion, a cobalt ion, a manganese ion soluble salt mixed solution, a precipitator and a complexing agent are subjected to a second mixing reaction to obtain a second precipitate, in the second mixing reaction step, the reaction temperature is 50-60 ℃, the reaction rotating speed is 200-300 rpm, the pH of a reaction system is 11.0-11.80, and the concentration of free ammonium radicals in the reaction system is 8.0-10.0 g/L. In the process of controlling the growth of the shell, the mixed solution is a high-ammonia and high-pH system, so that nickel, cobalt, manganese and other ions in the system are easily complexed by ammonium ions, compact shell particles can be grown on the surface of a ternary precursor crystal nucleus, and the formed ternary precursor crystal nucleus is of a loose porous structure, so that the shell epitaxially grown from the center of the crystal nucleus is of a orange-petal-shaped structure, the lithium salt can be more easily permeated into the core of the high-nickel ternary precursor in the process of preparing the anode material, the diffusion mass transfer resistance is smaller, and the performance of the material is improved.
And further, stopping feeding when the median particle size of the second precipitate reaches a second target particle size, so as to obtain the ternary precursor slurry. In some embodiments, the second target particle size is 5-25 micrometers, and the size of the second target particle size is controlled to be moderate, that is, the size of the obtained ternary precursor is controlled to be moderate, which is beneficial to subsequent reaction. If the second target granularity is too large or too small, the structural design of the product is influenced, if the second target granularity is too small, the structural design effect is not obvious, the loose structure of the inner core is not obvious, the battery capacity is low, and the cycle difference is influenced; if the second target particle size is too large, the obtained product has too many voids and low tap density, resulting in low volume density and more side reactions of the battery.
In some embodiments, the ratio of the first target particle size to the second target particle size is 0.2-0.4, and the ratio of the first target particle size to the second target particle size is controlled to be moderate, so that the performance of the obtained product is ensured to be excellent.
And in the step S03, filtering, washing and drying the ternary precursor slurry to obtain a ternary precursor.
In some embodiments, the purpose of filtration is to separate the ternary precursor precipitate from the reaction solution, using conventional filtration methods.
In some embodiments, the purpose of washing is to remove impurities remaining on the surface of the ternary precursor precipitate, and washing is performed for multiple times by using distilled water.
In some embodiments, the drying is performed to remove the solvent from the ternary precursor precipitate, thereby ensuring that ternary precursor particles are obtained. Wherein, the drying is carried out by adopting a conventional method to ensure that a dried product is obtained.
The second aspect of the embodiment of the application provides a ternary precursor prepared by a preparation method of the ternary precursor, wherein the ternary precursor is of a core-shell structure, as shown in fig. 1, the core is loose and porous, the shell is of a compact orange petal-shaped structure with an enlarged central extension, and a sector central angle of the orange petal-shaped structure is 10-30 °.
In a third aspect of the embodiments of the present application, a positive electrode material is provided, where the positive electrode material is prepared from a ternary precursor.
The positive electrode material that this application third aspect provided, positive electrode material carry out the high temperature sintering by ternary precursor and lithium salt and prepare and obtain, because ternary precursor has inside loose porous, the shell is tight and orange petal type structure, and during preparation positive electrode material, the lithium salt permeates the nuclear inside of ternary precursor more easily and the lithium salt that combines is more even more, consequently, the positive electrode material that obtains can show the cyclicity performance and the capacity that improves lithium ion battery.
In some embodiments, the cathode material is prepared by mixing a ternary precursor and a lithium source and calcining, and the obtained cathode material can significantly improve the cycle performance and capacity of the lithium ion battery.
A fourth aspect of the embodiments of the present application provides a lithium ion battery, where the lithium ion battery includes a positive electrode material.
In the lithium ion battery provided by the fourth aspect of the present application, the lithium ion battery includes the anode material, and the anode material includes the ternary precursor with a special structure, so that the service life of the lithium ion battery is prolonged, and the electrochemical stability and the cycle performance of the lithium ion battery are improved.
The following description will be given with reference to specific examples.
Example 1
A preparation method of a ternary cathode material precursor comprises the following steps:
(1) feeding three materials, namely nickel, cobalt and manganese three-element with the total molar weight of 1.5mol/L and the molar ratio of nickel, cobalt and manganese of 80:10:10, a sulfate mixed solution, a 32 wt% NaOH solution, a 13.5 wt% ammonia water solution and the like, simultaneously and uniformly through a metering pump into reaction kettles containing base solution, respectively, controlling the temperature of a reaction system at 50 ℃, protecting the reaction kettle in a nitrogen atmosphere, controlling the nitrogen flow of a micro-nano bubble machine at 0.3L/h, controlling the pH in the reaction process at 11.0-11.50, controlling the ammonium concentration at 1.0-2.0g/L, stirring at a rotating speed of 200rpm, and stopping feeding when the material in the reaction kettles reaches 80% of the effective volume of the reaction kettles. Wherein the base solution has ammonium concentration of 2.0-3.0g/L, pH of 10.90-11.40, and temperature of 50 deg.C; aging for 14h after the reaction is finished, wherein the particle size D50 of the precursor is 3.0 um;
(2) simultaneously feeding three materials, namely a sulfate mixed solution with the total molar weight of nickel, cobalt and manganese being 1.5mol/L, a 32 wt% NaOH solution, a 13.5 wt% ammonia water solution and the like, into an aged reaction kettle at a constant speed through a metering pump, controlling the temperature of a reaction system to be 55 ℃, the pH value to be 10.50-11.00, the concentration of free ammonia in the solution to be 6.0-8.0g/L, the stirring speed to be 240rpm, and stopping feeding when the particle size D50 of precursor particles in the reaction kettle reaches 10.0 um.
(3) Conveying the qualified precursor slurry in the reaction kettle to a centrifugal machine for filtering, washing, drying, mixing, sieving, demagnetizing and packaging to obtain the nickel-cobalt-manganese ternary precursor Ni0.80Co0.10Mn0.10(OH)2And (3) precursor.
Wherein, the obtained ternary precursor particle size D5010.0um, tap density 2.20g/cm3Specific surface area of 5.98m2Per g, spheroidal particles, dark brown powder.
Example 2
A preparation method of a ternary cathode material precursor comprises the following steps:
(1) simultaneously feeding three materials, namely a sulfate mixed solution with the total molar weight of nickel, cobalt and manganese being 2.0mol/L and an ammonia water solution with the molar ratio of nickel, cobalt and manganese being 90:0.5:0.5 at a constant speed through a metering pump, into a reaction kettle containing a base solution respectively, controlling the temperature of a reaction system to be 60 ℃, protecting the nitrogen atmosphere, controlling the nitrogen flow of a micro-nano bubble machine to be 0.5L/h, controlling the pH value in the reaction process to be 11.0-11.50, controlling the ammonium concentration to be 1.5-2.5g/L, stirring the rotation speed to be 200rpm, and stopping feeding when the material in the reaction kettle reaches 80% of the effective volume of the reaction kettle. Wherein the base solution has ammonium concentration of 3.0-4.0g/L, pH of 10.90-11.20, and temperature of 60 deg.C; aging for 15h after the reaction is finished, wherein the particle size D50 of the precursor is 4.0 um;
(2) simultaneously feeding three materials, namely a sulfate mixed solution with the total molar weight of nickel, cobalt and manganese being 2.0mol/L, a 32 wt% NaOH solution, a 13.5 wt% ammonia water solution and the like, into an aged reaction kettle at a constant speed through a metering pump, controlling the temperature of a reaction system at 60 ℃, the pH value at 10.50-11.00, the concentration of free ammonia in the solution at 6.0-8.0g/L, stirring at the rotating speed of 220rpm, and stopping feeding when the particle size D50 of precursor particles in the reaction kettle reaches 10.0 um.
(3) Conveying the qualified precursor slurry in the reaction kettle to a centrifugal machine for filtering, washing, drying, mixing, sieving, demagnetizing and packaging to obtain the nickel-cobalt-manganese ternary precursor Ni0.90Co0.05Mn0.05(OH)2And (3) precursor.
Wherein the obtained ternary precursor D50 is 10.0um, and the tap density is 2.10g/cm3The specific surface area is 6.56m2Per g, spheroidal particles, dark brown powder.
Comparative example 1
Comparative example 1 the procedure for the preparation of the ternary precursor was essentially the same as in example 1, except that in step (1): in the reaction process, nitrogen is introduced without using a micro-nano bubble machine, and only the upper part of the reaction kettle is introduced with nitrogen, so that the reaction kettle forms a nitrogen protection atmosphere.
Comparative example 2
Comparative example 2 the procedure for preparing the ternary precursor was substantially the same as in example 1, except that in step (1): the aging time after the reaction is finished is 1 h.
Positive electrode material of lithium ion battery
Providing the ternary precursors obtained in the embodiments 1-2 and the comparative examples 1-2, and preparing the lithium ion battery anode material, wherein the preparation method of the lithium ion battery anode material specifically comprises the following steps:
(1) mixing with lithium: adding alumina and cerium dioxide into the ternary precursor obtained in the embodiments 1-2 and the comparative examples 1-2 according to a metered molar ratio of 1:1.05-1:1.10, and uniformly mixing the ternary precursor and the lithium hydroxide by using a high-speed mixer to obtain mixed powder;
(2) and (3) calcining: and (3) demagnetizing the mixed powder, filling the mixed powder into a pot, cutting the mixed powder into blocks, stacking the blocks, conveying the blocks into a roller kiln for sintering and cooling, unloading, roughly crushing, sieving and demagnetizing the blocks to obtain the nickel-cobalt-manganese ternary positive electrode material corresponding to the embodiments 1-2 and the comparative examples 1-2, wherein the doping amount of aluminum is 2000ppm of the mass of the matrix, and the doping amount of cerium is 1000ppm of the mass of the matrix.
Lithium ion battery
According to the lithium ion battery, the lithium ion battery anode materials corresponding to the preparation examples 1-2 and the comparative examples 1-2 are used as the lithium ion battery anode;
the positive electrode material of the lithium ion battery is assembled into the button battery according to the following method: mixing a positive electrode material, conductive carbon, polyvinylidene fluoride (PVDF) and Carbon Nano Tubes (CNT) according to a mass ratio of 96: 1.8: adding the mixture into N-methyl-2-pyrrolidone (NMP) at a ratio of 1.4:0.8, uniformly mixing to prepare positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, drying in vacuum to form a positive electrode, and assembling 2025 button cells corresponding to examples 1-2 and comparative examples 1-2 in a glove box by taking a lithium sheet as a negative electrode.
Performance testing
Taking the ternary precursor provided in example 1 as an example, electron microscope analysis, particle size distribution analysis, and XRD analysis were performed on the ternary precursor, respectively.
(II) the lithium ion batteries prepared in the embodiment 1 and the comparative examples 1 and 2 of the invention are subjected to electrochemical performance test by adopting a CT2001A battery detection system of blue-electron Limited company in Wuhan City, and are subjected to performance analysis at the voltage range of 2.8-4.3V and the charging and discharging temperature of 0.5C/0.5C.
Analysis of results
Taking the ternary precursor provided in example 1 as an example, the results of electron microscope analysis, particle size distribution analysis, and XRD analysis were performed on the ternary precursor, respectively, as follows:
as can be seen from fig. 2A, a 1000-fold electron micrograph, the obtained precursor has good sphericity and uniform size; from fig. 2B, an electron microscope image of 10000 times of the product section shows that the primary particles have an inner structure of loose and porous inside and compact shell, and a central extended and enlarged shape, and are orange segments, and in the orange segments, the fan-shaped central angle displayed by the orange segments is 10-30 °.
As can be seen from FIG. 3, the obtained precursor had good uniformity, narrow particle size distribution, a diameter distance of 0.658, and a minimum particle size, D504.5um without micropowder.
As can be seen from fig. 4, the ternary precursor obtained in example 1: the crystal degree is high, the crystal lattice is perfect, and the crystal lattice is basically free of defects, wherein the ratio of the 101 peak intensity to the 001 peak intensity is 0.73.
Secondly, the performance analysis of the lithium ion batteries prepared in the embodiment 1 and the comparative examples 1 and 2 of the invention is performed, and the test result is shown in the following fig. 5.
As can be seen from fig. 5, the button cell prepared in example 1 has a capacity retention rate of 97.2% and a discharge capacity of 182.2mAh/g after 100 cycles of charging and discharging at 30 ℃ and 0.5C/0.5C within a voltage range of 2.8-4.3V; the discharge capacity and capacity retention rate are superior to those of products prepared by conventional reactions in the market. In contrast, comparative examples 1 and 2, the capacity retention rate distribution of 100 cycles was 89.9% and 94.3%, and the discharge capacity was 167.6mAh/g and 175.8mAh/g, respectively. Therefore, the lithium ion battery obtained by the application comprises the anode material, and the anode material comprises the ternary precursor with the special structure, so that the service life of the lithium ion battery is prolonged, and the electrochemical stability and the cycle performance of the lithium ion battery are improved.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The ternary precursor is characterized in that the ternary precursor is of a core-shell structure, wherein the core of the ternary precursor is loose and porous, the shell of the ternary precursor is of a compact orange petal-shaped structure with an enlarged central extension, and the fan-shaped central angle of the orange petal-shaped structure is 10-30 degrees.
2. A method of preparing the ternary precursor of claim 1, comprising the steps of:
providing a first mixed solution of a mixed solution of soluble salts of nickel ions, cobalt ions and manganese ions, a precipitator, a complexing agent and a base solution, introducing inert gas to create a micro-nano bubble aqueous solution condition to perform a first mixing reaction to obtain a first precipitate, stopping feeding when the median particle size of the first precipitate reaches a first target particle size, and performing aging treatment to obtain a ternary precursor crystal nucleus;
carrying out a second mixing reaction on the ternary precursor crystal nucleus, the nickel ion, cobalt ion and manganese ion soluble salt mixed solution, the precipitator and the complexing agent to obtain a second precipitate, and stopping feeding when the median particle size of the second precipitate reaches a second target particle size to obtain ternary precursor slurry;
and filtering, washing and drying the ternary precursor slurry to obtain the ternary precursor.
3. The method of preparing a ternary precursor according to claim 2, wherein the inert gas is at least one selected from the group consisting of nitrogen, helium, argon, neon; and/or the presence of a gas in the gas,
the introduction amount of the inert gas is 0.1-0.5L/min.
4. The method of preparing a ternary precursor according to claim 2, wherein the first target particle size is 2 to 5 microns; the second target particle size is 5-25 microns; and the ratio of the first target granularity to the second target granularity is 0.2-0.4.
5. The method for preparing a ternary precursor according to claim 2, wherein in the aging step, the rotation speed of the aging is 120-160 rpm, the temperature of the aging is 50-60 ℃, and the time of the aging is 10-15 h.
6. The preparation method of the ternary precursor according to claim 2, wherein in the first mixing reaction step, the reaction temperature is 50-60 ℃, and the reaction speed is 250-350 rpm; and/or the presence of a gas in the gas,
in the second mixing reaction step, the reaction temperature is 50-60 ℃, the reaction rotating speed is 200-300 rpm, the pH of the reaction system is 11.0-11.80, and the concentration of free ammonium radicals in the reaction system is 8.0-10.0 g/L.
7. The preparation method of the ternary precursor according to any one of claims 2 to 6, wherein in the mixed solution of soluble salts of nickel ions, cobalt ions and manganese ions, the molar ratio of nickel ions, cobalt ions and manganese ions is 70-98: 1-29: 1-29; and/or the presence of a gas in the gas,
the molar concentration of the mixed solution of soluble salts of nickel ions, cobalt ions and manganese ions is 1.0-2.0 mol/L; and/or the presence of a gas in the gas,
the precipitant comprises a sodium hydroxide solution; and/or the presence of a gas in the gas,
the complexing agent comprises an ammonia solution; and/or the presence of a gas in the gas,
the base solution is selected from an alkaline aqueous solution with the pH value of 11.0-11.50, and the concentration of free ammonium radicals in the base solution is 1.0-2.5 g/L.
8. The preparation method of the ternary precursor according to claim 7, wherein the sodium hydroxide solution is selected from the group consisting of a sodium hydroxide solution with a mass percentage concentration of 25-32%; and/or the presence of a gas in the gas,
the ammonia water solution is selected from 12-20% by mass.
9. A positive electrode material, characterized in that the positive electrode material is prepared from the ternary precursor according to claim 1 or the ternary precursor obtained by the method for preparing the ternary precursor according to any one of claims 2 to 7.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the positive electrode material according to claim 9.
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