CN115385389B - Battery anode material precursor and preparation method thereof - Google Patents

Battery anode material precursor and preparation method thereof Download PDF

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Publication number
CN115385389B
CN115385389B CN202210424592.4A CN202210424592A CN115385389B CN 115385389 B CN115385389 B CN 115385389B CN 202210424592 A CN202210424592 A CN 202210424592A CN 115385389 B CN115385389 B CN 115385389B
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precursor
solution
reaction
salt
battery
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CN115385389A (en
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祖国晶
王鹏峰
赖兰芳
魏国祯
曾雷英
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Xiamen Xiaw New Energy Materials Co ltd
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Xiamen Xiaw New Energy Materials 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
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • 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
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 invention relates to a battery anode material precursor and a preparation method thereof, wherein the preparation method comprises the following steps: s1, preparing a first salt solution; s2, preparing a first base solution; s3, adding the first salt solution into the first base solution, adjusting pH to react to obtain a first solid-liquid mixture, filtering, cleaning and drying to obtain a nucleus; s4, preparing a second salt solution; s5, preparing a second base solution; and S6, adding the nuclear body into the second base solution, adding the second salt solution, the complexing agent and the precipitant into the second base solution for reaction, and filtering, cleaning and drying the obtained second solid-liquid mixture to obtain the precursor of the battery anode material. The precursor comprises a core body and submicron spheres distributed on the surface of the core body, wherein the size of the submicron spheres is less than or equal to 1 mu m, and the positive electrode material obtained after sintering has a unique submicron buffer layer structure, has good cycle performance and has wide application prospect on a lithium power battery.

Description

Battery anode material precursor and preparation method thereof
Technical Field
The invention relates to a lithium battery anode material, in particular to a battery anode material precursor and a preparation method thereof.
Background
The nickel-cobalt-manganese ternary material serving as the positive electrode material of the lithium ion battery has the important advantages of high capacity, good cycle stability, moderate cost and the like, and is successfully applied to various new energy power vehicle types at present. However, the performance of the final excellent performance of the nickel-cobalt-manganese ternary material must depend on perfect matching of each link in the production process, wherein the mixing process of the precursor and the lithium source or the modified additive has an important influence on the uniformity of the sintered product, and the deterioration of uniformity can lead to the deterioration of the performance such as material capacity, circulation and the like. In addition, the enhancement of the compression resistance of the positive electrode material can also reduce the generation of fine powder, effectively reduce the compaction loss rate and further improve the service life and the use safety of the material.
The ternary positive electrode material has high compressive strength, and the corresponding material is not easy to crush, so that the generated fine powder is less, and the compaction loss rate is low. Therefore, the compressive strength of the material is improved, and better electrochemical performance is obtained. At the same time, the uniformity of the material is also a key contributor to electrochemical performance.
Disclosure of Invention
The invention aims to improve the mixing uniformity of the prior battery anode material precursor and a lithium source or a modified additive, and further improve the compression resistance of the anode material, and provides a preparation method of the battery anode material precursor, so as to prepare the battery anode material precursor capable of improving the mixing uniformity. In addition, the submicron spheres form a submicron buffer layer after the precursor is sintered, so that the submicron buffer layer plays a role in buffering in the charge and discharge process, and the cycle performance of the battery is improved.
The inventors believe that the performance of the lithium ion battery cathode material is greatly affected by the precursor performance. Especially in the mixing process of the precursor and the lithium source or the modified additive, the mixing uniformity largely determines the quality of the subsequent calcination process. In addition, the precursor is converted into a corresponding spherical positive electrode material after calcination, and the precursor has strong continuity before and after calcination from the aspects of material structure and morphology, so that the optimization of the precursor structure and morphology has great significance for improving the performance of the positive electrode material. Based on the above consideration, the invention generates uniformly distributed submicron spheres on the surface of the core body by process adjustment (including but not limited to parameter adjustment of second base solution composition, second salt solution flow, precipitant composition, complexing agent concentration, pH, stirring rotation speed, oxygen content and the like) on the premise of not affecting the main structure of the existing precursor (namely the core body in the application), and the whole appearance is kept intact with better consistency. The surface morphology of the original precursor is optimized through the submicron spheres, the surface roughness is improved, the lithiation process or the doping modification process of the obtained precursor of the battery anode material in the subsequent sintering process is smoother and more sufficient, the contact form among material particles can be changed by the anode material calcined by the precursor, the surface (without submicron spheres on the surface) -surface contact is not adopted, and the surface (rich submicron spheres on the surface) -surface contact is adopted, so that the stability of the material is improved.
The invention also protects the battery anode material precursor prepared by the preparation method of the battery anode material precursor, which comprises a core body and submicron spheres distributed on the surface of the core body, wherein the size of the submicron spheres is less than or equal to 1 mu m. The nucleus has a size significantly larger than the submicron sphere, e.g. the nucleus has a size at least 20 times the size of the submicron sphere, and may be 30-300 times, e.g. 50 times, 100 times or 200 times. In morphology, the nucleus is a compact sphere or spheroid formed by aggregation of a plurality of units, the submicron sphere is a sphere or spheroid, and the submicron sphere is dispersedly attached to the surface of the nucleus.
The invention also protects and adopts the battery anode material precursor and lithium source to mix and sinter to obtain the battery anode material, which continues the structural characteristics of the precursor, and has a unique core-shell structure, wherein the core is obtained by reaction based on the core, and the shell is further grown to form a submicron buffer layer structure based on submicron spheres.
The invention also protects a battery containing the battery positive electrode material, which has excellent cycle performance, and the battery positive electrode material can be subjected to charge and discharge test at 1C, and the capacity retention rate (%) of 50 circles is more than or equal to 96.45%.
The specific scheme is as follows:
a preparation method of a battery anode material precursor comprises the following steps:
s1, mixing nickel salt, cobalt salt and manganese salt with deionized water according to the molar ratio of Ni to Co to Mn= (0-1): (0-1) to prepare a first salt solution; wherein the addition amount of nickel salt, cobalt salt and manganese salt is not 0 at the same time;
s2, heating deionized water to a first temperature, and adding a complexing agent and a precipitant to prepare a first base solution;
s3, adding the first salt solution into the first base solution, adjusting pH to react to obtain a first solid-liquid mixture, and filtering, cleaning and drying the first solid-liquid mixture to obtain a nucleus;
s4, mixing nickel salt, cobalt salt and manganese salt with deionized water according to the molar ratio of Ni to Co to Mn= (0-1): (0-1) to prepare a second salt solution; wherein the addition amount of nickel salt, cobalt salt and manganese salt is not 0 at the same time;
s5, heating deionized water to a second temperature, and adding a complexing agent and a precipitator to prepare a second base solution;
and S6, adding the nuclear body into the second base solution, adding the second salt solution, the complexing agent and the precipitator into the second base solution for reaction to obtain a second solid-liquid mixture, and filtering, cleaning and drying the second solid-liquid mixture to obtain the precursor of the battery anode material.
Further, in the step S2, the first temperature is 40-70 ℃, the adding amount of the complexing agent is used for maintaining the concentration of the complexing agent in the first base solution to be 0-1 mol/L, and the adding amount of the precipitant is used for maintaining the pH value of the first base solution to be 10.0-12.5; optionally, in step S5, the second temperature is 40-70 ℃, the adding amount of the complexing agent is used for maintaining the concentration of the complexing agent in the second base solution to be 0.02-1 mol/L, and the adding amount of the precipitant is used for maintaining the pH value of the second base solution to be 10.0-12.5.
Further, in step S3, the first salt solution, ammonia water and sodium hydroxide solution or potassium hydroxide solution are added into the first base solution, and the pH is adjusted to 10.0-12.5 to perform a reaction, wherein the flow rate of the first salt solution is 5-100L/h, the reaction temperature is 48-65 ℃, the reaction time is 35-90 h, the stirring rotation speed is 0-800 rpm, preferably, the oxygen content in the reaction system is 1-20 wt%, and the total concentration of the ammonia water in the reaction solution is 0-1 mol/L.
Further, in the step S6, the adding amount of the nucleus body is 200-950g/L; the flow rate of the second salt solution is 10-100L/h, and the flow rate of the second salt solution is not fixed in the reaction process.
Further, in the step S6, the reaction temperature is 48-65 ℃ and the reaction time is 1-10 h; the pH value of the solution is 10.0-12.5; the stirring rotation speed is changed in a regular wave manner between 0 and 500 rpm; preferably, the oxygen content of the reaction system is 1-20wt%, the total concentration of the complexing agent in the reaction liquid is changed in the range of 0.02-1 mol/L, and the total concentration of the complexing agent is increased along with the reaction time until the reaction is finished.
Further, the nickel salt comprises at least one of sulfate, nitrate, chloride or acetate;
optionally, the cobalt salt comprises at least one of a sulfate, nitrate, chloride, or acetate;
optionally, the manganese salt comprises at least one of a sulfate, nitrate, chloride, or acetate;
optionally, the complexing agent comprises at least one of ammonia, ammonium sulfate, ammonium sulfite, or disodium edetate;
optionally, the precipitant comprises at least one of urea, sodium hydroxide, potassium hydroxide, sodium oxalate, potassium oxalate, sodium carbonate, or potassium carbonate.
The invention also protects the battery anode material precursor prepared by the preparation method of the battery anode material precursor, wherein the battery anode material precursor comprises a nucleus body and submicron spheres distributed on the surface of the nucleus body, and the size of the submicron spheres is less than or equal to 1 mu m.
Further, the morphology of the battery positive electrode material precursor is spherical or spheroid, the median particle diameter D50 of the battery positive electrode material precursor is 1.5-15 μm, the specific surface area is more than or equal to 13.00m < 2 >/g, the D50 loss rate before and after compaction is less than or equal to 2%, preferably, the size of the core body is at least 20 times that of the submicron sphere, the size of the submicron sphere is 0.1-1 μm, and the coverage area of the submicron sphere on the surface of the core body is 20% -80%.
The invention also protects a battery anode material, which is obtained by mixing the battery anode material precursor with a lithium source and then sintering; preferably, the molar ratio of the battery anode material precursor to the lithium source is 1:1.03-1.20, the sintering temperature is 680-950 ℃, and the time is 10-20 h.
The invention also provides a battery, which comprises the battery anode material.
The beneficial effects are that:
according to the preparation method of the battery anode material precursor, the nuclear body is firstly generated, and then the submicron spheres are formed on the surface of the nuclear body, and the obtained precursor guides a target product to form a unique submicron sphere buffer layer on the surface in a further sintering process, so that the microstructure of the material is not easy to change in compaction operation, the stability is better, the compaction loss rate is lower, and the cycle performance of the material can be improved in the charging and discharging processes.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the following brief description will be made on the accompanying drawings, which are given by way of illustration only and not limitation of the present invention.
Fig. 1 is a schematic structural diagram of a precursor of a battery positive electrode material prepared in the present application;
FIG. 2 is an electron microscope image of the overall structure of the battery positive electrode material precursor prepared in example 1 of the present application;
FIG. 3 is an electron microscopic view of the entire structure of the precursor prepared in comparative example 1;
fig. 4 is a graph showing the capacity cycle comparison at 1C rate of the battery assembled from the positive electrode materials obtained in example 1 and comparative example 1 of the present application;
fig. 5 is a graph showing the capacity cycle comparison at 1C rate of the battery assembled from the positive electrode materials obtained in example 2 and comparative example 2 of the present application.
Detailed Description
Definitions of some of the terms used in the present invention are given below, and other terms not mentioned have definitions and meanings well known in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the examples of the application.
In addition, descriptions such as those related to "first," "second," and the like in this application are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.
The following embodiments and features of the embodiments may be combined with each other without collision.
The invention provides a preparation method of a battery anode material precursor, which comprises the following steps:
s1, mixing nickel salt, cobalt salt and manganese salt with deionized water according to the molar ratio of Ni to Co to Mn= (0-1): (0-1) to prepare a first salt solution; wherein the addition amount of nickel salt, cobalt salt and manganese salt is not 0 at the same time;
s2, heating deionized water to a first temperature, and adding a complexing agent and a precipitant to prepare a first base solution;
s3, adding the first salt solution into the first base solution, adjusting pH to react to obtain a first solid-liquid mixture, and filtering, cleaning and drying the first solid-liquid mixture to obtain a nucleus;
s4, mixing nickel salt, cobalt salt and manganese salt with deionized water according to the molar ratio of Ni to Co to Mn= (0-1): (0-1) to prepare a second salt solution; wherein the addition amount of nickel salt, cobalt salt and manganese salt is not 0 at the same time;
s5, heating deionized water to a second temperature, and adding a complexing agent and a precipitator to prepare a second base solution;
and S6, adding the nuclear body into the second base solution, adding the second salt solution, the complexing agent and the precipitator into the second base solution for reaction to obtain a second solid-liquid mixture, and filtering, cleaning and drying the second solid-liquid mixture to obtain the precursor of the battery anode material.
Specifically, the salt solution is mixed in S1, preferably, the nickel salt, the cobalt salt and the manganese salt are mixed according to the mole ratio of Ni to Co to Mn= (0.5-1): (0.1-0.5).
S2, preparing a first base solution, heating deionized water to a first temperature, adding a complexing agent and a precipitant for controlling initial reaction conditions, wherein the first temperature is 40-70 ℃, preferably 48-65 ℃, the adding amount of the complexing agent is used for maintaining the concentration of the complexing agent in the first base solution to be 0-1 mol/L, and the adding amount of the precipitant is used for maintaining the pH of the first base solution to be 10.0-12.5. The sequence of S2 and S1 can be exchanged.
In a specific embodiment, S2 may be: and heating deionized water to a first temperature, adding ammonia water, and then adding sodium hydroxide solution or potassium hydroxide solution to prepare a first base solution.
In S3, the first salt solution is added to the first base solution, and the pH is adjusted to perform a reaction, preferably: and adding the first salt solution, ammonia water and sodium hydroxide solution or potassium hydroxide solution into the first base solution, and adjusting the pH value to 10.0-12.5 for reaction. Namely, the method comprises two cases, wherein the first salt solution, the ammonia water and the sodium hydroxide solution are added into the first base solution for reaction, and the second salt solution, the ammonia water and the potassium hydroxide solution are added into the first base solution for reaction. The pH value is regulated to 10.0-12.5, and the purpose of controlling the nucleation speed and the nucleation size can be achieved by matching the dosage of the reaction raw materials. In the step, the base solution reacts on the basis of sodium hydroxide/potassium hydroxide and ammonia water, and the sodium hydroxide/potassium hydroxide and ammonia water and the first salt solution enter a reaction kettle simultaneously in the reaction process, and the main function is 1, the reaction kettle reacts with metal ions in the reaction solution to generate corresponding hydroxide precipitates; 2. controlling the pH of the precipitation process, thereby affecting the precursor morphology. If ammonia and sodium hydroxide/potassium hydroxide are added to the base solution in advance, but not during the reaction, the reaction process is affected. Sodium hydroxide/potassium hydroxide is the precipitant. Ammonia water is a complexing agent, and the main function is to complex metal ions, so as to achieve the purpose of controlling free metal ions, reduce the supersaturation coefficient of the system, and further realize the control of the growth speed and morphology of particles. Both may be replaced by other complexing agents and precipitants as mentioned in the present invention.
In a specific embodiment, the reaction conditions in S3 may be: the flow rate of the first salt solution is 5-100L/h, preferably 10-80L/h; the reaction temperature is 48-65 ℃, the reaction time is 35-90 h, preferably 50-60 ℃, and the reaction time is 40-90 h; the stirring speed is 0 to 800rpm, preferably 50 to 500rpm.
In a specific embodiment, the oxygen content in the reaction system is 1wt% to 20wt%, preferably 5 to 10wt%. The total concentration of the aqueous ammonia in the reaction solution is 0 to 1mol/L, preferably 0.1 to 1mol/L.
And S4, preparing a second salt solution for synthesizing submicron spheres, wherein preferably, nickel salt, cobalt salt and manganese salt are mixed according to the molar ratio of Ni to Mn= (0.5-1) to (0.1-0.5). And S5, preparing a second base solution, wherein the sequence of the second base solution and the sequence of the second base solution can be changed.
In S6, modification of the core body, that is, growing submicron spheres on the surface of the core body, by adding the core body to the second base solution, and adding the second salt solution, the complexing agent and the precipitating agent to the second base solution to perform a reaction, preferably, the flow rate of the second salt solution is 10-100L/h, and the flow rate of the second salt solution is not fixed during the reaction, for example, in a specific embodiment, the flow rate of the second salt solution is preferably 10L/h (0.5 h) to 15L/h (0.5 h to 1 h) to 20L/h (1 h to end).
The addition amount of the complexing agent and the precipitator is dynamically changed, specifically, the total concentration of the complexing agent is changed within the range of 0.02mol/L to 1mol/L, and the total concentration of the complexing agent is always increased along with the reaction time until the reaction is finished; the pH value of the solution is 10.0-12.5, and is controlled by a precipitator.
In a specific embodiment, the reaction conditions in S6 may be: the reaction temperature is 48-65 ℃ and the reaction time is 1-10 h; preferably, the reaction temperature is 50-60 ℃ and the reaction time is 2-9 h. The pH of the solution is 10.0-12.5, preferably 11.0-12.0.
Preferably, the stirring speed of S6 is in a regular wave-like variation between 0 and 500rpm, preferably between 100 and 500 rpm. By wavy it is meant that the magnitude of the rotational speed exhibits a periodic variation, for example: the stirring speed was programmed to be 220rpm (7S) -330rpm (9S) -440rpm (9S) -220rpm (7S) -330rpm (9S) -440rpm (9S) … ….
In a specific embodiment, the oxygen content of the reaction system in S6 is 1wt% to 20wt%, preferably 5 to 10wt%. The total concentration of the complexing agent in the reaction liquid preferably varies within the range of 0.05mol/L to 0.8mol/L, and the total concentration of the complexing agent in the reaction system is increased with the reaction time until the reaction is ended. Preferably, the total concentration of the complexing agent varies in the interval of 0.1mol/L to 1mol/L, and the total concentration of the complexing agent in the reaction system is always increased with the reaction time. That is, the complexing agent is consumed in the reaction at a slower rate in S6 than the new complexing agent is added at S6.
In a specific embodiment, the stirring speed in S6 is 0 to 800rpm, preferably 50 to 500rpm.
The invention is not particularly limited in the types of nickel salt, cobalt salt, manganese salt, precipitant, complexing agent and pH adjusting agent, and can adopt common commercial raw materials of the existing nickel-cobalt-manganese ternary material. According to a preferred embodiment of the present invention, the nickel salt comprises at least one of a sulfate, a nitrate, a chloride or an acetate, the cobalt salt comprises at least one of a sulfate, a nitrate, a chloride or an acetate, and the manganese salt comprises at least one of a sulfate, a nitrate, a chloride or an acetate.
In some embodiments, the complexing agent comprises at least one of ammonia, ammonium sulfate, ammonium sulfite, or disodium edetate.
In some embodiments, the precipitant comprises at least one of urea, sodium hydroxide, potassium hydroxide, sodium oxalate, potassium oxalate, sodium carbonate, or potassium carbonate.
In some embodiments, the complexing agent comprises at least one of ammonia, ammonium sulfate, ammonium sulfite, or disodium edetate;
in some embodiments, the precipitant comprises at least one of urea, sodium hydroxide, potassium hydroxide, sodium oxalate, potassium oxalate, sodium carbonate, or potassium carbonate.
The pH adjusting agent can be aqueous solution of acid or alkali.
The preparation method of the battery anode material precursor provided by the invention is mainly improved in the cooperation of all steps, especially the preparation of the core in S3 and the modification of the core in S6, and other steps such as mixing, filtering, cleaning, drying and the like can be the same as those in the prior art, and can be known to those skilled in the art, and are not repeated herein.
The battery anode material precursor comprises a nucleus body and submicron spheres distributed on the surface of the nucleus body, wherein the size of the submicron spheres is less than or equal to 1 mu m. Further, the precursor has a spherical or spheroidic shape, the median diameter D50 of the precursor of the battery anode material is 1.5-15 mu m, and the specific surface area is more than or equal to 13.00m 2 And/g, the D50 loss rate before and after compaction is less than or equal to 2 percent. Where the loss rate of D50 before and after compaction refers to the ratio of the D50 before compaction to the D50 after compaction, the reduced fraction being the D50 before compaction. The D50 loss rate before and after compaction may reflect the compressive strength of the positive electrode material. Preferably, the size of the nucleus is at least 20 times that of the submicron sphere, the size of the submicron sphere is 0.1-1 μm, and the coverage area of the submicron sphere on the surface of the nucleus is 20% -80%.
The invention also protects the battery positive electrode material prepared by further sintering the battery positive electrode material precursor, which is generally sintered after being mixed with a lithium source, wherein the molar ratio of the battery positive electrode material precursor to the lithium source is 1:1.03-1.20, the sintering temperature is 680-950 ℃, and the time is 10-20 hours. The molar ratio of the battery positive electrode material precursor to the lithium source is preferably 1:1.10-1.20. The sintering temperature is preferably 700-900 ℃ and the sintering time is 12-18 h; more preferably 750 to 850 ℃ for 13 to 17 hours.
The present invention also protects a battery comprising the above-mentioned battery positive electrode material, and generally, the battery positive electrode material is mixed with a conductive agent, an adhesive, etc., and after being made into an active paste, coated on a metal sheet, pressed into a positive electrode sheet, and assembled with a negative electrode, an electrolyte, etc., to form a battery. It should be noted that the composition of the active paste and the method of assembling the battery may be the same as those in the prior art, and those skilled in the art will be aware of the same, and detailed descriptions thereof are omitted herein.
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In the examples below, "%" refers to weight percent, unless explicitly stated otherwise.
Example 1
The preparation method of the battery anode material precursor comprises the following steps:
s1: nickel sulfate, cobalt sulfate and manganese sulfate are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.6 to 0.2 to prepare a first salt solution.
S2: adding deionized water into a reaction kettle, controlling the stirring rotation speed to be 800rpm, heating to 49 ℃ (first temperature), and adding ammonia water and sodium hydroxide solution into the reaction kettle to prepare a first base solution; wherein, the concentration of ammonia water in the first base solution in the reaction kettle is 0.05mol/L, and the initial conditions of the reaction system comprise: the pH value is 11.70+ -0.1, and the oxygen content is 5+ -2 wt.%.
S3: adding a first salt solution, a sodium hydroxide solution and ammonia water into a reaction kettle containing a first base solution in parallel flow for reaction, wherein the reaction conditions are as follows: the flow rate of the first salt solution is 10L/h, the pH value is 11.70+/-0.1, the concentration of ammonia water is 0.35mol/L, the temperature is 49 ℃, the reaction time is 80h, and the feeding is stopped to obtain a first solid-liquid mixture; and filtering, cleaning and drying the obtained first solid-liquid mixture to obtain the nuclear body of the precursor of the battery anode material.
S4: nickel sulfate, cobalt sulfate and manganese chloride are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.6 to 0.2 to prepare a second salt solution.
S5: adding deionized water into a reaction kettle, setting 200rpm (6S) -300rpm (8S) -400rpm (10S) -200rpm (6S) -300rpm (8S) -400rpm (10S) … … circularly according to a program, heating to 51 ℃ (second temperature), and adding ammonium sulfate (complexing agent) and sodium hydroxide (precipitant) into the reaction kettle to prepare a second base solution; wherein the concentration of ammonium sulfate in the second base solution in the reaction kettle is 0.1mol/L, the pH value is 11.40+/-0.1, and the oxygen content is 5+/-2 wt%.
S6: the nuclear body is put into a reaction kettle containing second base solution, and second salt solution, ammonium sulfate and sodium hydroxide are added into the reaction kettle in parallel flow for reaction under the following reaction conditions: the flow rate of the second salt solution is 15L/h from the reaction time of 0-40min, the pH value is 11.40+/-0.1 from the reaction time of 41-240min, the concentration of ammonium sulfate is increased from 0.1mol/L to 0.25mol/L from the beginning to the end of the reaction, the temperature is 51 ℃, the total reaction time is 4h, and the feeding is stopped to obtain a second solid-liquid mixture; and filtering, cleaning and drying the obtained second solid-liquid mixture to obtain the battery anode material precursor with uniformly distributed submicron spheres generated on the surface of the nuclear body.
The precursor of the obtained battery anode material comprises a nucleus body and submicron spheres distributed on the surface of the nucleus body, as shown in figure 1; the positive electrode material obtained by further sintering the precursor continues the structure that the submicron spheres encircle the core body, so that points (the surface is rich in submicron spheres) -surface contact are formed under certain external pressure, and compared with the conventional surface (the surface is free of submicron spheres) -surface contact, the positive electrode material has higher structural stability.
Uniformly mixing a battery anode material precursor with uniformly distributed submicron spheres generated on the surface of the nuclear body obtained in the step S6 with a lithium source, wherein the molar ratio of the precursor to the lithium source is 1:1.08, and then sintering for 15 hours at 810 ℃ to obtain ternary material LiNi 1-x-y Co x Mn y O 2 Wherein x=y=0.2.
The prepared ternary material LiNi 1-x-y Co x Mn y O 2 As the positive electrode, the following positive electrode materials are used according to the mass ratio: carbon black: binder = 92:3:5. and assembling the CR2016 button battery in a flaking process of the button electricity manufacturing process in a drying room and an argon-filled glove box. The battery cathode is a lithium sheet, and the electrolyte is a conventional commercial lithium hexafluorophosphate material. The separator is a PP film. Electrochemical performance testing was performed at room temperature. The charge-discharge interval is 3.0-4.3V, and the cycle performance of the material is evaluated by performing a 1C cycle performance test.
The prepared ternary material LiNi 1-x-y Co x Mn y O 2 A50 MPa compaction experiment was performed to test the D50 size change of the material before and after compaction, thereby evaluating the compressive strength of the material.
An electron microscopic image of the precursor of the battery cathode material prepared in example 1 is shown in fig. 2. As can be seen from fig. 2, the morphology of the battery cathode material precursor prepared in example 1 is spherical or spheroid, the median particle diameter D50 is approximately 1.5 μm to 15 μm, the surface is coated with submicron spheres with the size of approximately 0.1 μm to 1 μm, and the coverage area of the submicron spheres on the surface of the core body is 20% -80%.
The precursor of the battery cathode material prepared in the example 1 is subjected to specific surface area test by a dynamic method specific surface meter, and the specific surface area is 13.34m 2 /g。
Example 2
S1: nickel sulfate, cobalt sulfate and manganese sulfate are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.5 to 0.2 to 0.3 to prepare a first salt solution.
S2: adding deionized water into a reaction kettle, controlling the stirring rotation speed at 700rpm, heating to 55 ℃ (first temperature), adding ammonia water and potassium hydroxide solution into the reaction kettle, and preparing a first base solution; wherein the concentration of ammonia water in the first base solution in the reaction kettle is 0.04mol/L, the pH value is 11.50+/-0.1, and the oxygen content is 6+/-2 wt%.
S3: adding the first salt solution, the potassium hydroxide solution and ammonia water into a reaction kettle containing a first base solution in parallel flow for reaction, wherein the reaction conditions are as follows: the flow rate of the first salt solution is 20L/h, the pH value is 11.50+/-0.1, the concentration of ammonia water is 0.30mol/L, the temperature is 55 ℃, the reaction time is 68h, and the feeding is stopped to obtain a first solid-liquid mixture; and filtering, cleaning and drying the obtained first solid-liquid mixture to obtain the nuclear body of the precursor of the battery anode material.
S4: nickel sulfate, cobalt sulfate and manganese sulfate are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.5 to 0.2 to 0.3 to prepare a second salt solution.
S5: adding deionized water into a reaction kettle, setting 220rpm (7S) -330rpm (9S) -440rpm (9S) -220rpm (7S) -330rpm (9S) -440rpm (9S) … … circularly, heating to 50 ℃ (second temperature), adding ammonia water (complexing agent) and sodium hydroxide (precipitant) into the reaction kettle, and preparing a second base solution; wherein the concentration of ammonia water in the second base solution in the reaction kettle is 0.15mol/L, the pH value is 11.50+/-0.1, and the oxygen content is 3+/-2 wt%.
S6: the nuclear body is put into a reaction kettle containing second base solution, and second salt solution, ammonia water and sodium hydroxide are added into the reaction kettle in parallel flow for reaction under the following reaction conditions: the flow rate of the second salt solution is 12L/h from 0 to 30min, the pH value is 11.50+/-0.1 from 31 to 120min, the concentration of ammonia water is increased from 0.15mol/L to 0.28mol/L from the beginning to the end of the reaction, the temperature is 50 ℃, the total reaction is carried out for 2h, and the feeding is stopped, so that a second solid-liquid mixture is obtained; and filtering, cleaning and drying the obtained second solid-liquid mixture to obtain the battery anode material precursor with uniformly distributed submicron spheres generated on the surface of the nuclear body.
The precursor of the battery anode material obtained in the step S6 is uniformly mixed with a lithium source for sintering, the molar ratio of the precursor to the lithium source is 1:1.08, and then the mixture is sintered for 15 hours at 860 ℃ to obtain the ternary material LiNi 1-x-y Co x Mn y O 2 Wherein x=0.2 and y=0.3.
The prepared ternary material LiNi 1-x-y Co x Mn y O 2 As the positive electrode, a CR2016 button cell was assembled in a glove box filled with argon gas in a tabletting process performed in a drying room, and electrochemical performance was tested at room temperature by a specific method referring to example 1. Charge-discharge intervalThe cycle performance of the material was evaluated by performing a 1C cycle performance test at 3.0-4.3V.
The prepared ternary material LiNi 1-x-y Co x Mn y O 2 A50 MPa compaction experiment was performed to test the D50 size change of the material before and after compaction, thereby evaluating the compressive strength of the material.
The battery cathode material precursor prepared in example 2 was subjected to a specific surface area test by a dynamic method specific surface meter, and the specific surface area was 13.83m 2 /g。
Comparative example 1
A comparative precursor was prepared, with reference to example 1, as follows:
s1: nickel sulfate, cobalt sulfate and manganese sulfate are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.6 to 0.2 to prepare a first salt solution.
S2: adding deionized water into a reaction kettle, controlling the stirring rotation speed to be 800rpm, heating to 49 ℃, and adding ammonia water and sodium hydroxide solution into the reaction kettle to prepare a first base solution; wherein the concentration of ammonia water in the first base solution in the reaction kettle is 0.05mol/L, the pH value is 11.70+/-0.1, and the oxygen content is 5+/-2 wt%.
S3: adding a first salt solution, a sodium hydroxide solution and ammonia water into a reaction kettle containing a first base solution in parallel flow for reaction, wherein the reaction conditions are as follows: the flow rate of the first salt solution is 10L/h, the pH value is 11.60+/-0.1, the concentration of ammonia water is 0.35mol/L, the temperature is 49 ℃, the reaction time is 80h, and the feeding is stopped to obtain a first solid-liquid mixture; and filtering, cleaning and drying the obtained first solid-liquid mixture to obtain a precursor.
S4: uniformly mixing a precursor and a lithium source, wherein the molar ratio of the precursor to the lithium source is 1:1.08, and then sintering for 15h at 810 ℃ to obtain the LiNi 1-x-y Co x Mn y O 2 The prepared ternary material LiNi 1-x-y Co x Mn y O 2 As a positive electrode, a CR2016 button cell was assembled in a glove box filled with argon gas and subjected to electrochemical performance testing at room temperature by referring to the method in example 1, and a tabletting process was performed in a dry room. The charge-discharge interval is 3.0-4.3V1C, thereby evaluating the cycle performance of the material. The prepared ternary material LiNi 1-x-y Co x Mn y O 2 A50 MPa compaction experiment was performed to test the D50 size change of the material before and after compaction, thereby evaluating the compressive strength of the material.
An electron micrograph of the precursor prepared in comparative example 1 is shown in fig. 3. As can be seen from fig. 3, the precursor prepared in comparative example 1 has a substantially spherical morphology, and the primary particles have a substantially columnar shape.
The precursor prepared in comparative example 1 was subjected to a specific surface area measurement by a dynamic method and a specific surface area meter, and the specific surface area was measured to be 12.93m 2 /g。
Comparative example 2
A comparative precursor was prepared, with reference to example 2, as follows:
s1: nickel sulfate, cobalt sulfate and manganese sulfate are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.5 to 0.2 to 0.3 to prepare a first salt solution.
S2: adding deionized water into a reaction kettle, controlling the stirring rotation speed at 700rpm, heating to 55 ℃ (first temperature), adding ammonia water and potassium hydroxide solution into the reaction kettle, and preparing a first base solution; wherein the concentration of ammonia water in the first base solution in the reaction kettle is 0.04mol/L, the pH value is 11.50+/-0.1, and the oxygen content is 6+/-2 wt%.
S3: adding the first salt solution, the potassium hydroxide solution and ammonia water into a reaction kettle containing a first base solution in parallel flow for reaction, wherein the reaction conditions are as follows: the flow rate of the first salt solution is 20L/h, the pH value is 11.50+/-0.1, the concentration of ammonia water is 0.30mol/L, the temperature is 55 ℃, the reaction time is 68h, and the feeding is stopped to obtain a first solid-liquid mixture; and filtering, cleaning and drying the obtained first solid-liquid mixture to obtain a precursor.
S4: uniformly mixing the precursor with a lithium source, and then sintering for 15 hours at 860 ℃ to obtain the LiNi 1-x-y Co x Mn y O 2 The prepared ternary material LiNi 1-x-y Co x Mn y O 2 As a positive electrode, CR20 was assembled in a tableting step in which a buckling process was performed in a drying room and in an argon-filled glove box by the method described in example 116 button cell, electrochemical performance test was performed at room temperature. The charge-discharge interval is 3.0-4.3V, and the cycle performance of the material is evaluated by performing a 1C cycle performance test. The prepared ternary material LiNi 1-x-y Co x Mn y O 2 A50 MPa compaction experiment was performed to test the D50 size change of the material before and after compaction, thereby evaluating the compressive strength of the material.
The precursor prepared in comparative example 2 was subjected to a specific surface area measurement by a dynamic method and a specific surface area meter, and the specific surface area was measured to be 12.18m 2 /g。
The results of specific surface area data of the battery positive electrode material precursor prepared in the above examples 1-2 and the precursor prepared in the comparative examples 1-2 are shown in Table 1, and ternary material LiNi prepared from the battery positive electrode material precursor prepared in the examples 1-2 1-x- y Co x Mn y O 2 And ternary material LiNi prepared from precursor prepared in comparative examples 1-2 1-x-y Co x Mn y O 2 The results of the performance test of (2) are shown in Table 2.
Table 1 results of specific surface area test table
Specific surface area (m) 2 /g)
Example 1 13.34
Comparative example 1 12.93
Example 2 13.83
Comparative example 2 12.18
Table 2 battery performance test results table
As can be seen from comparison of examples 1-2 and comparative examples 1-2, comparative examples 1-2 produced a precursor having a specific surface area smaller than that of the battery positive electrode material precursor prepared in examples 1-2 due to the lack of the step of forming submicron spheres, and ternary material LiNi produced from the battery positive electrode material precursor prepared in examples 1-2 of the present application 1-x-y Co x Mn y O 2 Is excellent in both compressive strength and cycle performance.
According to the preparation method, on the premise that the main structure of the existing precursor (namely the nuclear body in the application) is not affected, submicron spheres with uniform distribution are generated on the surface of the nuclear body through a regulation and control process (including but not limited to parameters such as second base solution composition, second salt solution flow, precipitator composition, complexing agent concentration, pH, stirring rotation speed, oxygen content and the like), the production process is simple and controllable, the overall morphology of the prepared battery positive electrode material precursor is kept intact, and the consistency is good. The surface morphology of the original precursor is optimized through the submicron spheres, the specific surface area of the material is further increased, the surface roughness is improved, the lithiation process or the doping modification process of the obtained battery anode material precursor in the subsequent sintering process is smoother and more sufficient, and the performance of the battery anode material is improved.
Example 3
The preparation method of the battery anode material precursor comprises the following steps:
s1: nickel sulfate, cobalt sulfate and manganese sulfate are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.6 to 0.2 to prepare a first salt solution.
S2: adding deionized water into a reaction kettle, controlling the stirring rotation speed to be 800rpm, heating to 55 ℃ (first temperature), and adding ammonia water and sodium hydroxide solution into the reaction kettle to prepare a first base solution; wherein, the concentration of ammonia water in the first base solution in the reaction kettle is 0.05mol/L, and the initial conditions of the reaction system comprise: the pH value is 11.70+ -0.1, and the oxygen content is 5+ -2 wt.%.
S3: adding a first salt solution, a sodium hydroxide solution and ammonia water into a reaction kettle containing a first base solution in parallel flow for reaction, wherein the reaction conditions are as follows: the flow rate of the first salt solution is 30L/h, the pH value is 12.00+/-0.1, the concentration of ammonia water is 0.35mol/L, the temperature is 55 ℃, the reaction time is 50h, and the feeding is stopped to obtain a first solid-liquid mixture; and filtering, cleaning and drying the obtained first solid-liquid mixture to obtain the nuclear body of the precursor of the battery anode material.
S4: nickel sulfate, cobalt sulfate and manganese chloride are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.6 to 0.2 to prepare a second salt solution.
S5: adding deionized water into a reaction kettle, setting 200rpm (6S) -300rpm (8S) -400rpm (10S) -200rpm (6S) -300rpm (8S) -400rpm (10S) … … circularly according to a program, heating to 60 ℃ (second temperature), and adding ammonium sulfate (complexing agent) and sodium hydroxide (precipitant) into the reaction kettle to prepare a second base solution; wherein the concentration of ammonium sulfate in the second base solution in the reaction kettle is 0.5mol/L, the pH value is 11.40+/-0.1, and the oxygen content is 5+/-2 wt%.
S6: the nuclear body is put into a reaction kettle containing second base solution, and second salt solution, ammonium sulfate and sodium hydroxide are added into the reaction kettle in parallel flow for reaction under the following reaction conditions: the flow rate of the second salt solution is 20L/h from the reaction time of 0-40min, the pH value is 11.40+/-0.1 from the reaction time of 41-240min, the concentration of ammonium sulfate is increased from 0.2mol/L to 0.5mol/L from the beginning to the end of the reaction, the temperature is 60 ℃, the total reaction time is 4h, and the feeding is stopped to obtain a second solid-liquid mixture; and filtering, cleaning and drying the obtained second solid-liquid mixture to obtain the battery anode material precursor with uniformly distributed submicron spheres generated on the surface of the nuclear body.
Example 4
The preparation method of the battery anode material precursor comprises the following steps:
s1: nickel sulfate, cobalt sulfate and manganese sulfate are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.4 to 0.3 to prepare a first salt solution.
S2: adding deionized water into a reaction kettle, controlling the stirring rotation speed to be 800rpm, heating to 60 ℃ (first temperature), and adding ammonia water and sodium hydroxide solution into the reaction kettle to prepare a first base solution; wherein, the ammonia water concentration in the first base solution in the reaction kettle is 0.3mol/L, and the initial condition of the reaction system comprises: the pH value is 11.70+ -0.1, and the oxygen content is 5+ -2 wt.%.
S3: adding a first salt solution, a sodium hydroxide solution and ammonia water into a reaction kettle containing a first base solution in parallel flow for reaction, wherein the reaction conditions are as follows: the flow rate of the first salt solution is 25L/h, the pH value is 11.70+/-0.1, the concentration of ammonia water is 0.35mol/L, the temperature is 60 ℃, the reaction time is 50h, and the feeding is stopped to obtain a first solid-liquid mixture; and filtering, cleaning and drying the obtained first solid-liquid mixture to obtain the nuclear body of the precursor of the battery anode material.
S4: nickel sulfate, cobalt sulfate and manganese chloride are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.4 to 0.3 to prepare a second salt solution.
S5: adding deionized water into a reaction kettle, setting the stirring rotation speed to be 100rpm (6S) -200rpm (8S) -400rpm (10S) -100rpm (6S) -200rpm (8S) -400rpm (10S) … … circularly, heating to 62 ℃ (second temperature), and adding ammonium sulfate (complexing agent) and sodium hydroxide (precipitant) into the reaction kettle to prepare a second base solution; wherein the concentration of ammonium sulfate in the second base solution in the reaction kettle is 0.6mol/L, the pH value is 11.40+/-0.1, and the oxygen content is 5+/-2 wt%.
S6: the nuclear body is put into a reaction kettle containing second base solution, and second salt solution, ammonium sulfate and sodium hydroxide are added into the reaction kettle in parallel flow for reaction under the following reaction conditions: the flow rate of the second salt solution is 30L/h from the reaction time of 0-40min, 15L/h from the reaction time of 41-240min, the pH value is 11.40+/-0.1, the concentration of ammonium sulfate is increased from 0.2mol/L to 0.8mol/L from the beginning to the end of the reaction, the temperature is 62 ℃, the total reaction time is 4h, and the feeding is stopped to obtain a second solid-liquid mixture; and filtering, cleaning and drying the obtained second solid-liquid mixture to obtain the battery anode material precursor with uniformly distributed submicron spheres generated on the surface of the nuclear body.
Example 5
The preparation method of the battery anode material precursor comprises the following steps:
s1: nickel sulfate, cobalt sulfate and manganese sulfate are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.3 to 0.3 to 0.4 to prepare a first salt solution.
S2: adding deionized water into a reaction kettle, controlling the stirring rotation speed to be 500rpm, heating to 45 ℃ (first temperature), and adding ammonia water and sodium hydroxide solution into the reaction kettle to prepare a first base solution; wherein, the ammonia water concentration in the first base solution in the reaction kettle is 0.4mol/L, and the initial conditions of the reaction system include: the pH value is 11.70+ -0.1, and the oxygen content is 5+ -2 wt.%.
S3: adding a first salt solution, a sodium hydroxide solution and ammonia water into a reaction kettle containing a first base solution in parallel flow for reaction, wherein the reaction conditions are as follows: the flow rate of the first salt solution is 50L/h, the pH value is 11.70+/-0.1, the concentration of ammonia water is 0.6mol/L, the temperature is 45 ℃, the reaction time is 80h, and the feeding is stopped to obtain a first solid-liquid mixture; and filtering, cleaning and drying the obtained first solid-liquid mixture to obtain the nuclear body of the precursor of the battery anode material.
S4: nickel sulfate, cobalt sulfate and manganese chloride are mixed with deionized water according to the mol ratio of Ni to Co to Mn=0.3 to 0.3 to 0.4 to prepare a second salt solution.
S5: adding deionized water into a reaction kettle, setting the stirring rotation speed to be 100rpm (6S) -300rpm (8S) -500rpm (10S) -100rpm (6S) -300rpm (8S) -500rpm (10S) … … circularly, heating to 55 ℃ (second temperature), and adding ammonium sulfate (complexing agent) and sodium hydroxide (precipitant) into the reaction kettle to prepare a second base solution; wherein the concentration of ammonium sulfate in the second base solution in the reaction kettle is 0.3mol/L, the pH value is 11.40+/-0.1, and the oxygen content is 5+/-2 wt%.
S6: the nuclear body is put into a reaction kettle containing second base solution, and second salt solution, ammonium sulfate and sodium hydroxide are added into the reaction kettle in parallel flow for reaction under the following reaction conditions: the flow rate of the second salt solution is 60L/h from the reaction time of 0-40min, the pH value is 11.40+/-0.1 from the reaction time of 41-240min, the concentration of ammonium sulfate is increased from 0.3mol/L to 0.5mol/L from the beginning to the end of the reaction, the temperature is 55 ℃, the total reaction time is 4h, and the feeding is stopped to obtain a second solid-liquid mixture; and filtering, cleaning and drying the obtained second solid-liquid mixture to obtain the battery anode material precursor with uniformly distributed submicron spheres generated on the surface of the nuclear body.
Comparative example 3
Referring to example 1, the difference was that the stirring speed was fixed at 400rpm in S5 and the flow rate of the second salt solution was fixed at 20L/h in S6. Other conditions were the same as in example 1, and it was found that submicron spheres could not be formed on the surface of the nucleus.
Comparative example 4
Referring to example 1, except that the flow rate of the second salt solution in S6 was fixed at 18L/h and the concentration of the complexing agent was fixed at 0.35mol/L, the other conditions were the same as in example 1, and it was found that submicron spheres could not be formed on the surface of the core.
Comparative example 5
With reference to example 1, except that the stirring speed was set at 500rpm in S5 and the complexing agent concentration was set at 0.3mol/L in S6, the other steps were the same as in example 1. Specifically, S5 and S6 are as follows:
S5: adding deionized water into a reaction kettle, stirring at a rotation speed of 500rpm, heating to 51 ℃ (second temperature), and adding ammonia water (complexing agent) and sodium hydroxide (precipitant) into the reaction kettle to prepare a second base solution; wherein the concentration of ammonia water in the second base solution in the reaction kettle is 0.3mol/L, the pH value is 11.40+/-0.1, and the oxygen content is 5+/-2 wt%.
S6: the nuclear body is put into a reaction kettle containing second base solution, and second salt solution, ammonia water and sodium hydroxide are added into the reaction kettle in parallel flow for reaction under the following reaction conditions: the flow rate of the second salt solution is 15L/h from the reaction time of 0-40min, the pH value is 11.40+/-0.1 from the reaction time of 41-240min, the concentration of ammonia water is maintained to be 0.3mol/L, the temperature is 51 ℃, the total reaction time is 4h, and the feeding is stopped to obtain a second solid-liquid mixture; and filtering, cleaning and drying the obtained second solid-liquid mixture to obtain the battery anode material precursor with uniformly distributed submicron spheres generated on the surface of the nuclear body.
Other process conditions were the same as in example 1, and it was found that submicron spheres could not be formed on the surface of the nuclei.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (14)

1. A preparation method of a battery anode material precursor is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing nickel salt, cobalt salt and manganese salt with deionized water according to the molar ratio of Ni to Co to Mn= (0-1): (0-1) to prepare a first salt solution; wherein the addition amount of nickel salt, cobalt salt and manganese salt is not 0 at the same time;
s2, heating deionized water to a first temperature, and adding a complexing agent and a precipitant to prepare a first base solution;
s3, adding the first salt solution into the first base solution, adjusting pH to react to obtain a first solid-liquid mixture, and filtering, cleaning and drying the first solid-liquid mixture to obtain a nucleus; in the step S3, the first salt solution, ammonia water and sodium hydroxide solution or potassium hydroxide solution are added into the first base solution, the pH is regulated to 10.0-12.5 for reaction, wherein the flow rate of the first salt solution is 5-100L/h, the reaction temperature is 48-65 ℃, the reaction time is 35-90 h, the stirring rotation speed is 0-800 rpm,
S4, mixing nickel salt, cobalt salt and manganese salt with deionized water according to a molar ratio of Ni to Co to Mn= (0-1): (0-1) to prepare a second salt solution; wherein the addition amount of nickel salt, cobalt salt and manganese salt is not 0 at the same time;
s5, heating deionized water to a second temperature, and adding a complexing agent and a precipitator to prepare a second base solution;
s6, adding the nuclear body into the second base solution, adding the second salt solution, the complexing agent and the precipitator into the second base solution for reaction to obtain a second solid-liquid mixture, and filtering, cleaning and drying the second solid-liquid mixture to obtain the precursor of the battery anode material; in the step S6, the flow rate of the second salt solution is 10-100L/h, and the flow rate of the second salt solution is not fixed in the reaction process; the reaction temperature is 48-65 ℃ and the reaction time is 1-10 h; the pH value of the solution is 10.0-12.5; the stirring rotation speed is changed in a regular wave manner between 0 and 500 rpm; the total concentration of the complexing agent in the reaction liquid changes within the range of 0.02mol/L to 1mol/L, and the total concentration of the complexing agent is always increased along with the reaction time until the reaction is finished;
the battery positive electrode material precursor comprises a nucleus body and submicron spheres distributed on the surface of the nucleus body, the shape of the battery positive electrode material precursor is spherical or spheroid, the median particle diameter D50 of the battery positive electrode material precursor is 1.5-15 mu m, and the specific surface area is more than or equal to 13.00 mu m 2 And/g, wherein the D50 loss rate before and after compaction is less than or equal to 2%, the size of the nucleus body is at least 20 times that of the submicron sphere, the size of the submicron sphere is 0.1-1 mu m, and the coverage area of the submicron sphere on the surface of the nucleus body is 20% -80%.
2. The method for preparing a precursor of a battery cathode material according to claim 1, wherein: in the step S2, the first temperature is 40-70 ℃, the adding amount of the complexing agent is used for maintaining the concentration of the complexing agent in the first base solution to be 0-1 mol/L, and the adding amount of the precipitant is used for maintaining the pH value of the first base solution to be 10.0-12.5; optionally, in step S5, the second temperature is 40-70 ℃, the adding amount of the complexing agent is used for maintaining the concentration of the complexing agent in the second base solution to be 0.02-1 mol/L, and the adding amount of the precipitant is used for maintaining the pH of the second base solution to be 10.0-12.5.
3. The method for preparing a precursor of a battery cathode material according to claim 1, wherein: in the step S3, the oxygen content in the reaction system is 1-20wt%, and the total concentration of ammonia water in the reaction solution is 0-1 mol/L.
4. A method for preparing a precursor of a battery positive electrode material according to any one of claims 1 to 3, characterized in that: in step S6, the adding amount of the nucleus body is 200-950g/L.
5. The method for preparing a precursor of a battery cathode material according to claim 4, wherein: in the step S6, the oxygen content of the reaction system is 1-20wt%.
6. A method for preparing a precursor of a battery positive electrode material according to any one of claims 1 to 3, characterized in that: the nickel salt includes at least one of sulfate, nitrate, chloride, or acetate.
7. The method for preparing a precursor of a positive electrode material for a battery according to claim 6, wherein: the cobalt salt includes at least one of sulfate, nitrate, chloride, or acetate.
8. The method for preparing a precursor of a positive electrode material for a battery according to claim 6, wherein: the manganese salt includes at least one of sulfate, nitrate, chloride or acetate.
9. The method for preparing a precursor of a positive electrode material for a battery according to claim 6, wherein: the complexing agent comprises at least one of ammonia water, ammonium sulfate, ammonium sulfite or disodium ethylene diamine tetraacetate.
10. The method for preparing a precursor of a positive electrode material for a battery according to claim 6, wherein: the precipitant comprises at least one of urea, sodium hydroxide, potassium hydroxide, sodium oxalate, potassium oxalate, sodium carbonate or potassium carbonate.
11. A battery positive electrode material precursor prepared by the preparation method of the battery positive electrode material precursor according to any one of claims 1 to 10, characterized in that: the battery positive electrode material precursor comprises a core body and submicron spheres distributed on the surface of the core body.
12. A battery positive electrode material obtained by mixing the battery positive electrode material precursor according to claim 11 with a lithium source and sintering.
13. The battery positive electrode material according to claim 12, wherein: the molar ratio of the battery anode material precursor to the lithium source is 1:1.03-1.20, the sintering temperature is 680-950 ℃, and the time is 10-20 h.
14. A battery comprising the battery cathode material of claim 12 or 13.
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FR2041750A1 (en) * 1969-05-21 1971-02-05 Reynolds Metals Co Crystalline alumina hydrate of predetd - particle size
JP2002047303A (en) * 2000-08-01 2002-02-12 Heidon Kk Method of suspension polymerization for controlling average particle diameter and distribution of particle diameter
JP2006143766A (en) * 2004-11-16 2006-06-08 Dainippon Ink & Chem Inc Method for producing water-absorbing resin
CN109314231A (en) * 2017-02-22 2019-02-05 林奈（中国）新能源有限公司 Core-shell structure copolymer electroactive material
CN113428910A (en) * 2021-06-25 2021-09-24 广东佳纳能源科技有限公司 Ternary precursor with core-shell structure and preparation method and application thereof
CN113929156A (en) * 2021-10-19 2022-01-14 厦门厦钨新能源材料股份有限公司 Battery anode material precursor and preparation method and application thereof

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* Cited by examiner, † Cited by third party
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FR2041750A1 (en) * 1969-05-21 1971-02-05 Reynolds Metals Co Crystalline alumina hydrate of predetd - particle size
JP2002047303A (en) * 2000-08-01 2002-02-12 Heidon Kk Method of suspension polymerization for controlling average particle diameter and distribution of particle diameter
JP2006143766A (en) * 2004-11-16 2006-06-08 Dainippon Ink & Chem Inc Method for producing water-absorbing resin
CN109314231A (en) * 2017-02-22 2019-02-05 林奈（中国）新能源有限公司 Core-shell structure copolymer electroactive material
CN113428910A (en) * 2021-06-25 2021-09-24 广东佳纳能源科技有限公司 Ternary precursor with core-shell structure and preparation method and application thereof
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