CN114084914A - Ternary precursor and preparation method and application thereof - Google Patents

Ternary precursor and preparation method and application thereof Download PDF

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Publication number
CN114084914A
CN114084914A CN202111307034.1A CN202111307034A CN114084914A CN 114084914 A CN114084914 A CN 114084914A CN 202111307034 A CN202111307034 A CN 202111307034A CN 114084914 A CN114084914 A CN 114084914A
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ternary precursor
nickel
cobalt
solution
particle size
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黄仁忠
郑江峰
高琦
张晨
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Guangdong Jiana Energy Technology Co Ltd
Qingyuan Jiazhi New Materials Research Institute Co Ltd
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Guangdong Jiana Energy Technology Co Ltd
Qingyuan Jiazhi New Materials Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application relates to the technical field of lithium ion batteries, in particular to a ternary precursor and a preparation method and application thereof. The ternary precursor comprises a compact inner core and a loose radial outer shell which is extended and grown from the inner core. The obtained ternary precursor shell is loose and radial, so that stress can be released through the radial shell in the using process, cracks caused by particle fracture in circulation can be avoided, the circulation characteristic of the ternary precursor is improved, the loose shell can increase a diffusion channel of lithium ions, and when the material is used for manufacturing the anode material of the lithium ion battery, the initial charge-discharge performance and the circulation performance of the lithium ion battery can be remarkably improved.

Description

Ternary precursor and preparation method and application thereof
Technical Field
The application belongs to the technical field of lithium ion batteries, and particularly relates to a ternary precursor and a preparation method and application thereof.
Background
The conventional method for synthesizing the ternary cathode material comprises the steps of firstly forming secondary particle balls by agglomeration of primary particles of nickel cobalt manganese hydroxide or nickel cobalt aluminum hydroxide through a coprecipitation reaction, and then synthesizing the ternary cathode material of nickel cobalt lithium manganate or nickel cobalt lithium aluminate through lithium mixing and a high-temperature solid-phase reaction.
In the aspect of precursor synthesis optimization, one current means is to reduce the internal stress in the charge and discharge process by directionally growing primary particles of the material in a radial shape, so as to improve the crushing of the material. Furthermore, radial particle fragmentation generally occurs along the radial direction of the particle, and fragmentation does not occur perpendicular to the radial direction of the particle, thereby preventing some parts of the material from being unusable within the particle.
CN108269995A discloses a ternary precursor with adjustable crystal structure, a positive electrode material and a preparation method thereof, which specifically comprises the following steps: respectively preparing a nickel-cobalt-manganese soluble salt, NaOH, concentrated ammonia water and a growth-oriented surfactant into solutions, and then carrying out coprecipitation reaction to obtain a ternary precursor with an oriented growth structure; and mixing the precursor with a lithium source, and calcining at high temperature to obtain the directionally-grown ternary layered cathode material with a precursor-like structure. According to the invention, the anode material with the crystal structure growing along the direction is obtained by regulating and controlling the growth of the precursor, the order degree and the stability of the growth of the internal structure are improved, the mixed discharge of cations is reduced, the Li & lt + & gt diffusion resistance is reduced, and the Li & lt + & gt diffusion resistance is improved+The diffusion coefficient.
However, the above method has its limitations, and firstly, similar materials are difficult to synthesize, and require the addition of additives to achieve directional growth, and the cost is high; in addition, the Ni content in the alloy can only reach 0.8 at most, and the material cannot avoid the cracking phenomenon of the material at the later stage of the test. The safety and reliability of the lithium ion battery in the later period still have great potential safety hazard.
CN113363497A discloses a preparation method of a ternary anode material with element doped crystal lattices, wherein a special element modifier is introduced into the crystal lattices and on the surface of the crystal lattices to regulate and control the crystal surface energy of the ternary material, thereby realizing the control of the size and the growth direction of crystal grains, optimizing the structure, the size and the arrangement mode of primary particles in the material, relieving the generation of microcracks inside the particles caused by the anisotropic change of the crystal lattice volume, inhibiting the interface side reaction of electrolyte and improving the electrochemical stability of the material; the excellent grain orientation arrangement is beneficial to the diffusion of lithium ions and improves the dynamic performance of the material.
However, the above method requires element doping and secondary sintering on the basis of the precursor, and has complex process and high cost, and the doping method has high cost and large equipment investment, which is not favorable for product industrialization.
Therefore, the existing preparation method of the directionally-grown ternary precursor has certain defects, so that the obtained product is easy to cause microcracks and breakage, and the preparation process is complicated and is not beneficial to the stability of the product property.
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 the conventional preparation method of the directionally-grown ternary precursor has certain defects, so that the obtained product is easy to cause microcracks and breakage, and the preparation process is complicated and is not beneficial to the stability of the product properties.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a ternary precursor comprising a compact core and a loose radial shell extending from the core.
In a second aspect, the present application provides a method for preparing a ternary precursor by directional growth, comprising the following steps:
under the condition of inert atmosphere, introducing nickel, cobalt and manganese or nickel, cobalt and aluminum soluble salt, a first complexing agent, a first precipitator and a base solution to prepare a first mixed solution, carrying out a first precipitation reaction, stopping feeding when the median particle size of a first precipitate in the first mixed solution reaches a first target particle size, and carrying out solid-liquid separation after standing to obtain a ternary precursor crystal nucleus;
preparing pure water, a second complexing agent, a second precipitator and a ternary precursor crystal nucleus into a second mixed solution, adjusting the pH value and ammonium concentration condition of the second mixed solution, introducing nickel, cobalt and manganese or nickel, cobalt and aluminum soluble salt, carrying out a second precipitation reaction on the second complexing agent and the second precipitator to obtain a second precipitate, stopping feeding when the median particle size of the second precipitate reaches a second target particle size, and carrying out aftertreatment to obtain a ternary precursor.
In a third aspect, the present application provides a positive electrode material, which is prepared by mixing a ternary precursor and a lithium salt.
In a fourth aspect, the present application provides a lithium ion battery comprising a positive electrode material.
The ternary precursor that this application first aspect provided, this ternary precursor body is including the kernel of inseparable form, and the loose radial shell that is that extends the growth by the kernel, because the ternary precursor shell that obtains is loose radial, in the use, be favorable to stress to release through radial shell, in order to avoid granule fracture to produce the crackle when the circulation, and then improve ternary precursor's cyclic characteristic, and loose shell can increase lithium ion's diffusion channel, when using this material preparation lithium ion battery's positive electrode material, can show improvement lithium ion battery's first charge-discharge performance and cyclic performance.
In the preparation method for the directional growth of the ternary precursor, raw materials are mixed, and feeding is stopped by controlling the target granularity of the obtained crystal nucleus to obtain a small and compact ternary precursor crystal nucleus; and the reaction liquid in the first stage process is removed, the reaction liquid in the second stage process is prepared again for feeding reaction, the full overflow mode of the kettle is adopted, the stability of the solid content of the product is maintained, loose and radial shells are sparsely and directionally grown on the surfaces of crystal nuclei, the preparation of the product can be better realized only by preparing the reaction liquid in different reaction stages in the whole reaction process without introducing other additives, the preparation process is simple, the product can be accurately regulated, the obtained ternary precursor is uniform in growth and proper in tightness, the stress release is facilitated, cracks are not easily generated in later-stage circulation, and the method is suitable for wide application.
According to the positive electrode material provided by the third aspect of the application, the positive electrode material is prepared by mixing a ternary precursor and a lithium salt. The positive electrode material is prepared by mixing the provided ternary precursor and the lithium salt, and the provided ternary precursor can better release stress, avoid particle cracking during circulation and increase a diffusion channel of lithium ions, so that the obtained positive electrode material has high first charge-discharge performance and cycle performance.
In the lithium ion battery provided by the fourth aspect of the present application, the lithium ion battery includes a positive electrode material; based on the fact that the anode material comprises the provided ternary precursor, the ternary precursor has high first charge-discharge performance and cycle performance, and the electrochemical performance and stability 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 shows Ni provided in example 1 of the present application0.96Co0.02Mn0.02(OH)2The particle size D50 was 10 μm in the cross-section of the precursor.
FIG. 2 shows Ni provided in example 2 of the present application0.9Co0.1(OH)2The particle size D50 was 10 μm in the cross-section of the precursor.
FIG. 3 shows Ni provided in example 3 of the present application0.8Co0.0.1Mn0.1(OH)2Precursor sectionThe particle size D50 was 10 μm.
Fig. 4 is an SEM image of the precursor material provided in example 1 of the present application.
Fig. 5 is an SEM image of the precursor material provided in comparative example 1 of the present application.
Fig. 6 is a particle size distribution diagram of the precursor material provided in example 1 of the present application.
Fig. 7 is a graph of the particle size distribution of the precursor material provided in comparative example 1 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.
In a first aspect, embodiments of the present disclosure provide a ternary precursor, which includes a compact inner core and a loose radial outer shell extending from the inner core.
The ternary precursor that this application first aspect provided, this ternary precursor includes the kernel of inseparable form, and the loose radial shell that is that extends the growth by the kernel, because the ternary precursor shell that obtains is loose radial, in the use, be favorable to stress to release through radial shell, in order to avoid granule fracture production crackle when the circulation, and then improve ternary precursor's cyclic characteristic, and loose shell can increase lithium ion's diffusion channel, when using this material preparation lithium ion battery's positive electrode material, can show improvement lithium ion battery's first charge-discharge performance and cyclic performance.
In some embodiments, the ternary precursor has the formula: nixCoyMnz(OH)2Or NixCoyAlz(OH)2(ii) a And, x, y and z satisfy: 0<x≦0.98；0.1≦y<1，0≤z≦0.5，x+y+z＝1。
In some embodiments, the median particle size D of the ternary precursor50The particle size is controlled to be moderate, namely the particle size of the obtained ternary precursor is ensured to be moderate, the battery capacity and the cycle performance are improved, and the reaction effect is ensured to be good. If the particle size is too small, the shell is too thin and the radial shape is not clear; if the particle size is too large, there is a risk of surface cracking, and the product performance may be deteriorated.
The second aspect of the embodiments of the present application provides a method for preparing a ternary precursor by directional growth, comprising the following steps:
s01, under the condition of inert atmosphere, introducing nickel, cobalt and manganese or nickel, cobalt and aluminum soluble salt, a first complexing agent, a first precipitator and a base solution to prepare a first mixed solution, carrying out a first precipitation reaction, stopping feeding when the median particle size of a first precipitate in the first mixed solution reaches a first target particle size, and carrying out solid-liquid separation after standing to obtain a ternary precursor crystal nucleus;
s02, preparing pure water, a second complexing agent, a second precipitator and a ternary precursor crystal nucleus into a second mixed solution, adjusting the pH value and ammonium concentration condition of the second mixed solution, introducing nickel, cobalt and manganese or nickel, cobalt and aluminum soluble salts, carrying out a second precipitation reaction on the second complexing agent and the second precipitator to obtain a second precipitate, stopping feeding when the median particle size of the second precipitate reaches a second target particle size, and carrying out post-treatment to obtain a ternary precursor.
In the preparation method for the directional growth of the ternary precursor, raw materials are mixed, and feeding is stopped by controlling the target granularity of the obtained crystal nucleus to obtain a small and compact ternary precursor crystal nucleus; and the reaction liquid in the first stage process is removed, the reaction liquid in the second stage process is prepared again for feeding reaction, the full overflow mode of the kettle is adopted, the stability of the solid content of the product is maintained, loose and radial shells are sparsely and directionally grown on the surfaces of crystal nuclei, the preparation of the product can be better realized only by preparing the reaction liquid in different reaction stages in the whole reaction process without introducing other additives, the preparation process is simple, the product can be accurately regulated, the obtained ternary precursor is uniform in growth and proper in tightness, the stress release is facilitated, cracks are not easily generated in later-stage circulation, and the method is suitable for wide application.
In the step S01, under the condition of inert atmosphere, introducing nickel, cobalt and manganese or nickel, cobalt and aluminum soluble salt, a first complexing agent, a first precipitator and a base solution to prepare a first mixed solution, carrying out a first precipitation reaction, stopping feeding when the median particle size of a first precipitate in the first mixed solution reaches a first target particle size, and carrying out solid-liquid separation after standing to obtain a ternary precursor crystal nucleus; the raw materials are mixed firstly, and the feeding is stopped by controlling the target granularity of the obtained crystal nucleus so as to obtain a small and compact ternary precursor crystal nucleus.
In some embodiments, the inert atmosphere is selected from at least one of an argon atmosphere, a helium atmosphere and a nitrogen atmosphere, and the inert atmosphere is provided, so that no impurities are introduced in the reaction process of the reactants, no impurity molecules are generated, and the purity of the obtained ternary precursor crystal nucleus is high.
In some embodiments, the total concentration of the soluble salt solution of nickel, cobalt and manganese or nickel, cobalt and aluminum is 0.5-3 mol/L, the molar concentration of the soluble salt solution of the mixed ions is controlled to be moderate, the stable formation of the crystal nucleus of the obtained ternary precursor material is ensured, the particle size density is high, and the subsequent use is facilitated. If the concentration of the mixed ion soluble salt solution is too high, the obtained crystal nuclei are too large in number, easy to form agglomeration, not beneficial to particle dispersion and not beneficial to subsequent growth of the radial shell; if the concentration of the mixed ion soluble salt solution is too low, the obtained crystal nucleus is less in quantity, low in forming degree and density, not compact enough and not beneficial to use.
In some embodiments, the nickel, cobalt, manganese or nickel, cobalt, aluminum soluble salt solution has a molar ratio of nickel ions, cobalt ions, manganese ions or aluminum ions of 80-98: 1-10: 0-5. The proportion of the prepared nickel ions is 80-98, 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 nickel, cobalt, manganese, or nickel, cobalt, aluminum soluble salt solution is selected from at least one of a sulfate solution, a nitrate solution, a chloride solution.
In some embodiments, the first complexing agent comprises at least one of ammonia, ammonium sulfate, ammonium chloride, and ammonium nitrate, and is used with a complexing agent solution provided to facilitate complexation of the starting material in order to ensure reaction completion during use.
In some embodiments, the molar ratio of the nickel, cobalt and manganese or the soluble salt of nickel, cobalt and aluminum to the first complexing agent is 1: 0.1-0.8, and the preparation of the ternary precursor crystal nucleus can be promoted by controlling the molar ratio of the soluble salt to the complexing agent.
In some embodiments, the molar ratio of the nickel, cobalt, manganese or nickel, cobalt, aluminum soluble salt to the first precipitator is 1: 1.8-2.5, and the preparation of the ternary precursor crystal nucleus can be promoted by controlling the molar ratio of the soluble salt to the precipitator.
In some embodiments, the first complexing agent is selected from an aqueous ammonia solution, and the concentration of the aqueous ammonia solution is 0.2-8 mol/L; if the concentration of the complexing agent solution is too low, the complexing action cannot be better carried out; if the concentration of the complexing agent solution is too high, the reaction is too fast, so that the product is precipitated too fast, and the control of the appearance of crystal nuclei is not facilitated.
In some embodiments, the first precipitating agent comprises at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide; in order to ensure the reaction is complete in the using process, a precipitator solution is used, and the provision of the precipitator solution is beneficial to promoting the formation and precipitation of crystal nuclei.
In some embodiments, the first precipitant is selected from a sodium hydroxide solution, and providing a precipitant solution is advantageous in some embodiments, the precipitant solution has a concentration of 5 to 12mol/L, and if the concentration of the precipitant solution is too low, the precipitation effect is poor; if the concentration of the precipitant solution is too high, the reaction is too fast, which leads to the precipitation of the product too fast and is not beneficial to controlling the appearance of the crystal nucleus.
In some embodiments, the base solution is an aqueous alkaline solution that is mixed with a soluble salt solution, a precipitant solution, and a complexing agent solution to adjust the pH and ammonium concentration of the first precipitation reaction as required for the first precipitation reaction, providing optimal conditions for the first precipitation reaction.
In some embodiments, the first mixed solution has a pH of 11.5-12.5, an ammonium concentration of 1-5 g/L, a temperature of 40-70 ℃, and a rotation speed of 100-1000 rpm. In the first precipitation reaction process, the pH of the reaction is controlled to be higher, but the ammonium radical concentration is controlled to be low-concentration ammonium radical ions, so that an alkaline environment is provided at the initial stage of the reaction to act with a proper ammonium radical concentration, a reaction system is prevented from suddenly changing, and a compact crystal nucleus structure can be slowly generated by a ternary precursor core. The pH value of the precipitation reaction is further controlled, so that the condition of the mixed solution is stable, and the generation of the product is more facilitated.
Further, when the median particle size of the first precipitate in the first mixed solution reaches a first target particle size, stopping feeding, and after standing, performing solid-liquid separation to obtain a ternary precursor crystal nucleus.
In some embodiments, the first target particle size is 0.5 to 5.4 μm, and the size of the first target particle size is controlled to be appropriate, that is, the size of the obtained ternary precursor crystal nucleus is controlled to be 10 to 30 percent of the size of the ternary precursor particle, which is beneficial to the subsequent reaction. If the first target granularity is too small, the use of the obtained ternary precursor material is influenced, so that the prepared battery has low capacity and poor cycle performance; if the first target granularity is too large, the obtained ternary precursor product is not favorable for forming a radial shape, is not favorable for releasing stress and influences the action effect.
In some embodiments, after the feeding is stopped, stirring treatment is carried out for 15-30 minutes, and after the reaction is completed, standing is carried out, and then solid-liquid separation is carried out, so as to obtain the ternary precursor crystal nucleus. And removing the supernatant reaction liquid in the first stage process, re-preparing the reaction liquid of the second stage process, and performing feeding reaction, so as to accurately regulate and control the growth of product crystal nuclei and shells by regulating and controlling different reaction conditions.
In step S02, preparing pure water, a second complexing agent, a second precipitating agent, and a ternary precursor crystal nucleus into a second mixed solution, adjusting the pH and ammonium concentration of the second mixed solution, introducing nickel, cobalt, manganese, or nickel, cobalt, and aluminum soluble salts, performing a second precipitation reaction on the second complexing agent and the second precipitating agent to obtain a second precipitate, stopping feeding when the median particle size of the second precipitate reaches a second target particle size, and performing post-treatment to obtain a ternary precursor.
In some embodiments, pure water, a second complexing agent, a second precipitating agent and a ternary precursor crystal nucleus are prepared into a second mixed solution, and the pH and ammonium concentration conditions of the second mixed solution are adjusted.
In some embodiments, the second complexing agent comprises at least one of ammonia, ammonium sulfate, ammonium chloride, and ammonium nitrate, and is used with a complexing agent solution provided to facilitate complexation of the starting material in order to ensure reaction completion during use.
In some embodiments, the molar ratio of the nickel, cobalt, manganese or nickel, cobalt, aluminum soluble salt to the second complexing agent is 1: 0.1-0.8, and the preparation of the ternary precursor can be promoted by controlling the molar ratio of the soluble salt to the complexing agent.
In some embodiments, the molar ratio of the nickel, cobalt, manganese or nickel, cobalt, aluminum soluble salt to the second precipitator is 1: 1.8-2.5, and the preparation of the ternary precursor can be promoted by controlling the molar ratio of the soluble salt to the precipitator.
In some embodiments, the second complexing agent is selected from an aqueous ammonia solution, and the concentration of the aqueous ammonia solution is 0.2-8 mol/L; if the concentration of the complexing agent solution is too low, the complexing action cannot be better carried out; if the concentration of the complexing agent solution is too high, the reaction is too fast, so that the product is precipitated too fast, and the control of the appearance of crystal nuclei is not facilitated.
In some embodiments, the second precipitating agent comprises at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide; in order to ensure the reaction is complete in the using process, a precipitator solution is used, and the provision of the precipitator solution is beneficial to promoting the formation and precipitation of crystal nuclei.
In some embodiments, the second precipitant is selected from sodium hydroxide solution, and providing the precipitant solution is advantageous in some embodiments, the concentration of the precipitant solution is 5-12 mol/L, and if the concentration of the precipitant solution is too low, the precipitation effect is poor; if the concentration of the precipitant solution is too high, the reaction is too fast, which leads to the precipitation of the product too fast and is not beneficial to controlling the appearance of the crystal nucleus.
In some embodiments, the second mixture has a pH of 10.5-11.5, an ammonium concentration of 5-10 g/L, a temperature of 50-70 ℃, and a rotation speed of 100-500 rpm. In the second mixed solution, the pH of the reaction is controlled to be lower than that of the first mixed solution, but the ammonium concentration is controlled to be high-concentration ammonium ions, so that the reaction can be promoted in the second precipitation reaction process, a radial loose shell grows on the surface of a crystal nucleus, the growth of a product is accurately regulated, and the obtained ternary precursor grows uniformly and appropriately.
And further, introducing nickel, cobalt and manganese or nickel, cobalt and aluminum soluble salt, and carrying out a second precipitation reaction on a second complexing agent and a second precipitator to obtain a second precipitate.
Further, in the process of carrying out the second precipitation reaction, nickel, cobalt and manganese or nickel, cobalt and aluminum soluble salts, a second complexing agent and a second precipitator are introduced, and the solid content of the product is maintained stably by adopting an overflow mode, so that the shell of the product is loose and is radial. In some embodiments, the solid content is 100-300 g/L, the solid content is controlled to be moderate, the loosening and radial shape of the outer shell of the product can be stably realized, and the formed product is ensured to be uniform in appearance.
And further, stopping feeding when the median particle size of the second precipitate reaches a second target particle size, and performing post-treatment to obtain the ternary precursor.
In some embodiments, the second target particle size is 5-18 μm, and the particle size of the second target particle size is controlled to be moderate, i.e., the particle size of the obtained ternary precursor is ensured to be moderate, which is beneficial to improving the battery capacity and cycle performance, and ensuring a good reaction effect. If the particle size is too small, the shell is too thin and the radial shape is not clear; if the particle size is too large, there is a risk of surface cracking, and the product performance may be deteriorated.
In some embodiments, after the feeding is stopped, stirring is performed for 15-30 minutes, and then post-treatment is performed to obtain the ternary precursor. And further carrying out post-treatment including filtering, washing and drying to obtain the ternary precursor.
In a third aspect of the embodiments of the present application, a positive electrode material is provided, where the positive electrode material is prepared by mixing a ternary precursor and a lithium salt.
According to the positive electrode material provided by the third aspect of the application, the positive electrode material is prepared by mixing a ternary precursor and a lithium salt. The positive electrode material is prepared by mixing the provided ternary precursor and the lithium salt, and the provided ternary precursor can better release stress, avoid particle cracking during circulation and increase a diffusion channel of lithium ions, so that the obtained positive electrode material has high first charge-discharge performance and cycle performance.
In some embodiments, the ternary precursor and the lithium salt are mixed in a suitable ratio, and after the mixing is completed, the reaction is carried out at a high temperature and in a solid phase.
In some embodiments, the lithium salt includes, but is not limited to, lithium hydroxide or lithium carbonate; and mixing the lithium salt and the ternary precursor for reaction.
In some embodiments, the ratio of the lithium salt to the ternary precursor is 1.0-1.3: 1, and the ratio of the lithium salt to the ternary precursor is controlled to be moderate, so that the lithium salt and the ternary precursor can react to generate the cathode material.
In some embodiments, the reaction temperature for performing the high-temperature solid-phase reaction is 700-1000 ℃, and the reaction temperature is controlled to be higher, so that the two can be sintered, and the ternary cathode material is obtained.
In a fourth aspect of the present application, a 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 a positive electrode material; based on the fact that the anode material comprises the provided ternary precursor, the ternary precursor has high first charge-discharge performance and cycle performance, and the electrochemical performance and stability of the lithium ion battery are improved.
The following description will be given with reference to specific examples.
Example 1
A preparation method of directional growth of a ternary precursor comprises the following steps:
(1) providing a nickel, cobalt and manganese soluble salt solution, a complexing agent solution, a precipitator solution and a base solution; wherein the total concentration of the soluble salt solution of nickel, cobalt and manganese is 1.5mol/L, and the molar ratio of nickel, cobalt and manganese is 96:2: 2; the complexing agent solution is selected from 7mol/L ammonia water solution, the precipitator solution is selected from 12mol/L sodium hydroxide solution, and the base solution is selected from alkaline aqueous solution containing ammonium ions;
(2) adding a base solution with certain pH, temperature and ammonium concentration into a reaction kettle, keeping introducing nitrogen, controlling a certain rotating speed, adding a metal salt solution, a precipitator and a complexing agent into the reaction kettle in a parallel flow manner, and controlling the stable pH, ammonium concentration and temperature to perform a first precipitation reaction within a target range to obtain a first mixture, wherein the pH, ammonium concentration and temperature of the base solution are kept consistent with the stably controlled pH, ammonium concentration and temperature to serve as first-stage reaction conditions, the pH is 11.5, the ammonium concentration is 2g/L, the temperature is 40 ℃, and the rotating speed is 200 rpm;
stopping feeding when the median particle size of the precipitate of the first mixture reaches 3.0 mu m, standing, and then extracting the supernatant of the first mixture to obtain a ternary precursor crystal nucleus;
(3) adding water, a complexing agent solution and a precipitator solution into the ternary precursor crystal nucleus to perform a second precipitation reaction to obtain a second mixture, wherein the following reaction conditions are controlled in the second precipitation reaction: the pH value is 10.5, the concentration of ammonium radicals is 5g/L, the temperature is 50 ℃, and the rotating speed is 200 rpm; and starting overflow to control solid content, controlling the solid content to be 100g/L, stopping feeding when the median particle size of the precipitate of the second mixture reaches 10 mu m, and then filtering, washing and drying to obtain the ternary precursor.
The resulting ternaryThe precursor is Ni0.96Co0.02Mn0.02(OH)2(ii) a As shown in FIG. 1, the core-shell structure is provided, wherein the core is compact, the shell is loose and radial, and the particle size D is50＝10.0μm。
Example 2
A preparation method of directional growth of a ternary precursor comprises the following steps:
(1) providing a nickel, cobalt and aluminum soluble salt solution, a complexing agent solution, a precipitator solution and a base solution; wherein the total concentration of the nickel, cobalt and aluminum soluble salt solution is 1.5mol/L, and the molar ratio of the nickel element to the cobalt element is 90: 10; the complexing agent solution is selected from 7mol/L ammonia water solution, the precipitator solution is selected from 12mol/L sodium hydroxide solution, and the base solution is selected from alkaline aqueous solution containing ammonium ions;
(2) adding a base solution with certain pH, temperature and ammonium concentration into a reaction kettle, keeping introducing nitrogen, controlling a certain rotating speed, adding a metal salt solution, a precipitator and a complexing agent into the reaction kettle in a parallel flow manner, and controlling the stable pH, ammonium concentration and temperature to perform a first precipitation reaction within a target range to obtain a first mixture, wherein the pH, ammonium concentration and temperature of the base solution are kept consistent with the stably controlled pH, ammonium concentration and temperature to serve as first-stage reaction conditions, the pH is 12, the ammonium concentration is 4g/L, the temperature is 50 ℃, and the rotating speed is 300 rpm;
stopping feeding when the median particle size of the precipitate of the first mixture reaches 3 mu m, standing, and then extracting the supernatant of the first mixture to obtain a ternary precursor crystal nucleus;
(3) adding water, a complexing agent solution and a precipitator solution into the ternary precursor crystal nucleus to perform a second precipitation reaction to obtain a second mixture, wherein the following reaction conditions are controlled in the second precipitation reaction: the pH value is 11, the ammonium radical concentration is 7g/L, the temperature is 60 ℃, and the rotating speed is 200 rpm; and starting overflow to control solid content, controlling the solid content to be 150g/L, stopping feeding when the median particle size of the precipitate of the second mixture reaches 10 mu m, and then filtering, washing and drying to obtain the ternary precursor.
The obtained ternary precursor is Ni0.9Co0.1(OH)2(ii) a As shown in FIG. 2, the core-shell structure is provided, wherein the core is compact, the shell is loose and radial, and the particle size D is50＝10.0μm。
Example 3
A preparation method of directional growth of a ternary precursor comprises the following steps:
(1) providing a nickel and cobalt soluble salt solution, a complexing agent solution, a precipitator solution and a base solution; wherein the total concentration of the nickel and cobalt soluble salt solution is 1.5mol/L, and the molar ratio of nickel, cobalt and manganese is 8: 1: 1; the complexing agent solution is selected from 7mol/L ammonia water solution, the precipitator solution is selected from 12mol/L sodium hydroxide solution, and the base solution is selected from alkaline aqueous solution containing ammonium ions;
(2) adding a base solution with certain pH, temperature and ammonium concentration into a reaction kettle, keeping introducing nitrogen, controlling a certain rotating speed, adding a metal salt solution, a precipitator and a complexing agent into the reaction kettle in a parallel flow manner, and controlling the stable pH, ammonium concentration and temperature to perform a first precipitation reaction within a target range to obtain a first mixture, wherein the pH, ammonium concentration and temperature of the base solution are kept consistent with the stably controlled pH, ammonium concentration and temperature to serve as first-stage reaction conditions, the pH is 12.5, the ammonium concentration is 5g/L, the temperature is 60 ℃, and the rotating speed is 600 rpm;
stopping feeding when the median particle size of the precipitate of the first mixture reaches 3 mu m, standing, and then extracting the supernatant of the first mixture to obtain a ternary precursor crystal nucleus;
(3) adding water, a complexing agent solution and a precipitator solution into the ternary precursor crystal nucleus to perform a second precipitation reaction to obtain a second mixture, wherein the following reaction conditions are controlled in the second precipitation reaction: the pH value is 11.5, the concentration of ammonium radicals is 10g/L, the temperature is 70 ℃, and the rotating speed is 500 rpm; and starting overflow to control solid content, controlling the solid content to be 300g/L, stopping feeding when the median particle size of the precipitate of the second mixture reaches 10 mu m, and then filtering, washing and drying to obtain the ternary precursor.
The obtained ternary precursor is Ni0.8Co0.0.1Mn0.1(OH)2(ii) a As shown in FIG. 3, and is a nucleusA shell structure, wherein the inner core is compact, the outer shell is loose and radial, and the granularity D50＝10.0μm。
Comparative example 1
(1) Providing a nickel, cobalt and manganese soluble salt solution, a complexing agent solution, a precipitator solution and a base solution; wherein the total concentration of the soluble salt solution of nickel, cobalt and manganese is 1.5mol/L, and the molar ratio of nickel, cobalt and manganese is 96:2: 2; the complexing agent solution is selected from 7mol/L ammonia water solution, the precipitator solution is selected from 12mol/L sodium hydroxide solution, and the base solution is selected from alkaline aqueous solution containing ammonium ions;
(2) adding a base solution with certain pH, temperature and ammonium concentration into a reaction kettle, keeping introducing nitrogen, controlling a certain rotating speed, adding a metal salt solution, a precipitator and a complexing agent into the reaction kettle in a parallel flow manner, and controlling the stable pH, ammonium concentration and temperature to perform a first precipitation reaction within a target range to obtain a first mixture, wherein the pH, ammonium concentration and temperature of the base solution are kept consistent with the stably controlled pH, ammonium concentration and temperature to serve as first-stage reaction conditions, the pH is 11.5, the ammonium concentration is 2g/L, the temperature is 40 ℃, and the rotating speed is 200 rpm;
(3) when the median particle size of the precipitate of the first mixture reaches 3.0 μm, water, a complexing agent solution and a precipitant solution are added into a reaction kettle to carry out a second precipitation reaction, and the following reaction conditions are controlled: the pH value is 10.5, the concentration of ammonium radicals is 5g/L, the temperature is 50 ℃, and the rotating speed is 200 rpm; and when the median particle size of the precipitate of the second mixture reaches 10 mu m, stopping feeding, and then filtering, washing and drying to obtain the ternary precursor.
The obtained ternary precursor is Ni0.96Co0.02Mn0.02(OH)2(ii) a And has a core-shell structure, wherein the core is compact, the shell is loose and radial, and the granularity D50＝10.0μm。
Positive electrode material of lithium ion battery
Providing the ternary precursors obtained in the embodiments 1-3 and the comparative example 1, 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: mixing the ternary precursor obtained in the embodiments 1-3 and the comparative example 1 with lithium hydroxide according to a metering molar ratio of 1:1.07 to obtain mixed powder;
(2) and (3) calcining: and carrying out high-temperature solid-phase reaction on the mixed powder at 700-800 ℃ to obtain the lithium ion battery anode material.
Lithium ion battery
According to the lithium ion battery, the lithium ion battery anode materials corresponding to the preparation examples 1-3 and the comparative example 1 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 the positive electrode material with acetylene black and polyvinylidene fluoride according to the weight ratio of 9: 0.5: mixing the materials according to the proportion of 0.5 to prepare positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, drying the positive electrode current collector in vacuum to form a positive electrode, and assembling the battery corresponding to the examples 1-3 and the comparative example 1 in a glove box by using a lithium sheet as a negative electrode, polypropylene as a diaphragm and lithium hexafluorophosphate as an electrolyte.
Performance testing and results analysis
(1) Taking the ternary precursor obtained in example 1 and the ternary precursor obtained in comparative example 1 as examples, SEM images of the obtained ternary precursor materials were analyzed respectively. Where fig. 4 is an SEM image of the precursor material provided in example 1 of the present application, and fig. 5 is an SEM image of the precursor material provided in comparative example 1 of the present application, it can be seen that the ternary precursor of example 1 is in a loose radial shape, and the ternary precursor of comparative example 1 is in a compact shape. Further, fig. 6 is a particle size distribution diagram of the precursor material provided in example 1 of the present application, and fig. 7 is a particle size distribution diagram of the precursor material provided in comparative example 1 of the present application, and it can be seen that the particle sizes of the ternary precursors obtained in example 1 and comparative example 1 are similar.
(2) Taking the lithium ion battery anode materials corresponding to the examples 1-3 and the comparative example 1 as the lithium ion battery anode; the lithium ion battery anode material is assembled into a button cell according to the following method, and the obtained battery is subjected to property test. Results are shown in table 1, and it can be seen from the data results in table 1 above that comparative example 1 and example 1 use raw materials with the same ratio of nickel, cobalt and manganese to synthesize precursors, and the particle size distribution is substantially consistent. However, in example 1, because the precursor is loose and radial, and the prepared ternary material well inherits the structure, in the charge and discharge cycle process, stress is released through the radial shell, the generation of particle cracking is reduced, and the side reaction of the electrolyte to the internal material is relieved, and in addition, the loose and radial material is beneficial to the transmission of lithium ions, and the occurrence of irreversible reaction is reduced, so after the cycle is performed for 100 weeks under the multiplying power of 1C and 2C, the capacity retention rate of example 1 is much higher than that of comparative example 1. In addition, due to the different contents of nickel, cobalt and manganese metals in the examples 1, 2 and 3, the capacity retention rate after the first circulation and the circulation for 100 weeks are different, but the capacity retention rate is better than that of the comparative example 1.
TABLE 1
Figure BDA0003340507900000161
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 by comprising a compact inner core and a loose radial outer shell which is formed by extending and growing from the inner core.
2. The ternary precursor according to claim 1, having the chemical formula: nixCoyMnz(OH)2Or NixCoyAlz(OH)2(ii) a And, x, y and z satisfy: 0<x≦0.98；0.1≦y<1，0≤z≦0.5，x+y+z＝1。
3. A method for the directional growth of a ternary precursor according to claim 1, comprising the steps of:
under the condition of inert atmosphere, introducing nickel, cobalt and manganese or nickel, cobalt and aluminum soluble salt, a first complexing agent, a first precipitator and a base solution to prepare a first mixed solution, carrying out a first precipitation reaction, stopping feeding when the median particle size of a first precipitate in the first mixed solution reaches a first target particle size, and carrying out solid-liquid separation after standing to obtain a ternary precursor crystal nucleus;
preparing pure water, a second complexing agent, a second precipitator and the ternary precursor crystal nucleus into a second mixed solution, adjusting the pH value and ammonium concentration condition of the second mixed solution, introducing the nickel, cobalt and manganese or nickel, cobalt and aluminum soluble salt, carrying out a second precipitation reaction on the second complexing agent and the second precipitator to obtain a second precipitate, stopping feeding when the median particle size of the second precipitate reaches a second target particle size, and carrying out post-treatment to obtain the ternary precursor.
4. The method for preparing the directional growth of the ternary precursor according to claim 3, wherein the first mixed solution has a pH of 11.5 to 12.5, an ammonium concentration of 1 to 5g/L, a temperature of 40 to 70 ℃ and a rotation speed of 100 to 1000 rpm.
5. The method for preparing the directional growth of the ternary precursor according to claim 3, wherein the pH of the second mixed solution is 10.5 to 11.5, the ammonium concentration is 5 to 10g/L, the temperature is 50 to 70 ℃, and the rotation speed is 100 to 500 rpm.
6. The method for preparing a directional growth of a ternary precursor according to claim 3, wherein the first target particle size is 0.5-5.4 μm; and/or the presence of a gas in the gas,
the second target particle size is 5-18 μm.
7. The method for preparing the directional growth of the ternary precursor according to any one of claims 3 to 6, wherein the total concentration of the nickel, cobalt, manganese or nickel, cobalt, aluminum soluble salt solution is 0.5 to 3 mol/L; and/or the presence of a gas in the gas,
in the soluble salt solution of nickel, cobalt and manganese or nickel, cobalt and aluminum, the molar ratio of nickel ions to cobalt ions to manganese ions or aluminum ions is 80-98: 1-10: 0-5.
8. The method for preparing the ternary precursor of any one of claims 3 to 6, wherein the first complexing agent and/or the second complexing agent comprises at least one of ammonia water, ammonium sulfate, ammonium chloride and ammonium nitrate; and/or the presence of a gas in the gas,
the first precipitator and/or the second precipitator comprise at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide; and/or the presence of a gas in the gas,
the molar ratio of the nickel, cobalt and manganese or the soluble salt of nickel, cobalt and aluminum to the first complexing agent or the second complexing agent is 1: 0.1-0.8;
the molar ratio of the nickel, cobalt and manganese or the soluble salt of nickel, cobalt and aluminum to the first precipitator or the second precipitator is 1: 1.8-2.5.
9. A positive electrode material, which is prepared by mixing the ternary precursor of claim 1 or 2 or the ternary precursor obtained by the preparation method of directional growth of the ternary precursor of any one of claims 3 to 8 with a lithium salt.
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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