CN114195202A - Binary precursor and preparation method thereof, lithium ion battery anode material, lithium ion battery and power utilization equipment - Google Patents

Binary precursor and preparation method thereof, lithium ion battery anode material, lithium ion battery and power utilization equipment Download PDF

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CN114195202A
CN114195202A CN202111625822.5A CN202111625822A CN114195202A CN 114195202 A CN114195202 A CN 114195202A CN 202111625822 A CN202111625822 A CN 202111625822A CN 114195202 A CN114195202 A CN 114195202A
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binary
lithium ion
ion battery
precursor
nickel
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迟珺文
沙金
訚硕
欧宁
张磊
王乐
张雨英
伍兴科
王一乔
艾延龄
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Zhongwei New Materials Co ltd
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Zhongwei New 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
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • C01P2004/51—Particles with a specific particle size distribution
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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 provides a binary precursor and a preparation method thereof, a lithium ion battery anode material, a lithium ion battery and electric equipment. The binary precursor comprises an inner layer area and an outer layer area arranged on the surface of the inner layer area; the inner region includes primary particles arranged in a honeycomb shape, and the outer region includes primary particles arranged in a radial shape. The preparation method comprises the following steps: mixing materials including a complexing agent, hydroxide and water to obtain a base solution, continuously adding the complexing agent, the hydroxide and a nickel-manganese binary mixed salt solution into the base solution at the same time, and carrying out coprecipitation reaction under the stirring condition to obtain a binary precursor. The raw material of the lithium ion battery anode material comprises a binary precursor. The raw material of the lithium ion battery comprises the lithium ion battery cathode material. The electric equipment comprises a lithium ion battery. The anode material prepared from the precursor provided by the application has the advantages of large capacity, high cycle retention rate and high charging and discharging speed.

Description

Binary precursor and preparation method thereof, lithium ion battery anode material, lithium ion battery and power utilization equipment
Technical Field
The application relates to the field of new materials, in particular to a binary precursor and a preparation method thereof, a lithium ion battery anode material, a lithium ion battery and electric equipment.
Background
The lithium battery is a strategic industry which is mainly developed at the present stage and is widely applied to industries such as new energy automobiles, electric vehicles, mobile phones and the like, and the precursor cathode material has the advantages of low cost, large capacitance, excellent cycle performance, good comprehensive performance and the like.
Because of the small reserves of metallic cobalt worldwide, it is only 40 years for human consumption and expensive, without regard to recycling. In view of cost reduction and future large-scale availability, binary precursors without cobalt have been under scrutiny.
The existing cobalt-free precursor has the defects of cycle and rate capability, so that the development of a precursor capable of making up the defects of cycle and rate capability caused by the lack of cobalt element is needed.
Disclosure of Invention
The present application aims to provide a binary precursor, a preparation method thereof, a lithium ion battery anode material, a lithium ion battery and an electric device, so as to solve the above problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a binary precursor comprises an inner layer area and an outer layer area arranged on the surface of the inner layer area;
the inner zone comprises primary particles arranged in a honeycomb shape, and the outer zone comprises primary particles arranged in a radial shape.
Preferably, the porosity of the inner layer region is 5% to 18%;
preferably, the porosity of the outer layer region is 10% to 20%;
preferably, the ratio of the thickness of the inner region to the thickness of the outer region is from 0.8 to 1.5;
preferably, the specific surface area of the binary precursor is 14-25m2/g；
Preferably, the particle size D50 of the binary precursor is 3-5 μm;
preferably, the particle size D90/D50 of the binary precursor is 1.4-1.8.
Preferably, the binary precursor has a chemical formula of NixMny(OH)2Wherein x + y is 1, 1 is more than x and more than or equal to 0.7, and 0.3 is more than or equal to y and more than 0.
The application also provides a preparation method of the binary precursor, which comprises the following steps:
mixing materials including a complexing agent, hydroxide and water to obtain a base solution, continuously adding the complexing agent, the hydroxide and a nickel-manganese binary mixed salt solution into the base solution at the same time, and performing coprecipitation reaction under the stirring condition to obtain the binary precursor.
Preferably, the nickel-manganese binary mixed salt solution comprises soluble nickel salt and manganese salt;
preferably, the soluble nickel salt comprises one or more of nickel sulfate, nickel nitrate, nickel acetate;
preferably, the manganese salt comprises one or more of manganese sulfate, manganese nitrate, manganese acetate;
preferably, the concentration of the nickel-manganese binary mixed salt solution is 0.5-2 mol/L;
preferably, the adding speed of the nickel-manganese binary mixed salt solution is 3-5L/h;
preferably, the complexing agent comprises one or more of ammonium bicarbonate, ammonium carbonate and ammonia water;
preferably, the concentration of the complexing agent is 5-10 mol/L;
preferably, the adding speed of the complexing agent is 0.01-0.5L/h;
preferably, the hydroxide comprises sodium hydroxide and/or potassium hydroxide;
preferably, the adding speed of the hydroxide is 1.2-2.0L/h;
preferably, the rate of addition of the hydroxide is increased stepwise.
Preferably, the preparation method of the base solution comprises the following steps:
preheating water, and then adding the complexing agent and the hydroxide;
preferably, the temperature end point of the preheating is 45-65 ℃;
preferably, the pH of the coprecipitation reaction is 11 to 12;
preferably, the stirring speed is 400-1000 r/min.
Preferably, the method for preparing the binary precursor further comprises a post-treatment comprising:
centrifuging the reaction system, washing solids, demagnetizing, drying and sieving to obtain a product;
preferably, the drying temperature is 90-200 ℃ and the drying time is 10-24 h.
The application also provides a lithium ion battery anode material, and the raw material of the lithium ion battery anode material comprises the binary precursor.
The application also provides a lithium ion battery, and the raw material of the lithium ion battery comprises the lithium ion battery anode material.
The application also provides electric equipment which comprises the lithium ion battery.
Compared with the prior art, the beneficial effect of this application includes:
according to the binary precursor, the inner layer area comprises primary particles arranged in a honeycomb shape, and the outer layer area comprises primary particles arranged in a radial shape; the battery capacity, the cycle performance and the rate performance are improved through special shapes; the precursor does not contain cobalt element, and the cost is low;
according to the preparation method of the binary precursor, the complexing agent, the hydroxide and the nickel-manganese binary mixed salt solution are continuously added into the base solution at the same time, and the precursor with the special morphology is obtained through reaction under the stirring condition; the specific principle is as follows: the pH value is rapidly reduced in the early stage of the reaction, so that primary particles of the inner core are in a loose and porous thin sheet shape, and the whole inner layer area is in a honeycomb shape; refining primary particles by the increase of pH in the later period, stirring and the synergistic effect of pH and a complexing agent to enable the external primary particles to be pasty and radially arranged, and finally obtaining the precursor with the special morphology; the process is simple, the cost is low, and the obtained product has good granularity dispersibility;
the lithium ion battery prepared from the lithium ion battery anode material provided by the application has high capacity and good cycle performance and rate capability.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a scanning electron micrograph of the binary precursor obtained in example 1;
FIG. 2 is an enlarged view of a portion of FIG. 1;
FIG. 3 is a sectional electron micrograph of the binary precursor obtained in example 1;
FIG. 4 is a scanning electron micrograph of the binary precursor obtained in example 2;
FIG. 5 is a sectional electron micrograph of the binary precursor obtained in example 2;
FIG. 6 is a scanning electron micrograph of the binary precursor obtained in example 3;
FIG. 7 is a sectional electron micrograph of the binary precursor obtained in example 3;
FIG. 8 is a scanning electron micrograph of the binary precursor obtained in comparative example 1;
FIG. 9 is a sectional electron micrograph of the binary precursor obtained in comparative example 1;
FIG. 10 is a scanning electron micrograph of the binary precursor obtained in comparative example 2;
FIG. 11 is a sectional electron micrograph of the binary precursor obtained in comparative example 2.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A binary precursor comprises an inner layer area and an outer layer area arranged on the surface of the inner layer area;
the inner zone comprises primary particles arranged in a honeycomb shape, and the outer zone comprises primary particles arranged in a radial shape.
The interior of the precursor is in a loose and porous thin sheet shape, the interior of the precursor is in a honeycomb shape, the interior of the precursor is wholly in an inner core, and the interior of the precursor is loose and tight, so that the absorption and storage of lithium ions are facilitated, and due to different appearances, the lithium can be absorbed by different appearances laterally, so that the ion content can be increased, and the capacity can be improved. The external part is gelatinized rough flaky primary particles which are arranged in a radial shape, and the primary particles are closely arranged, so that the structural stability of the high-nickel cobalt-free binary precursor is ensured. The outer layer is in a divergent shape (radial shape) and is beneficial to the de-intercalation of lithium ions, and the rate capability is improved.
In an alternative embodiment, the porosity of the inner region is 5% to 18%;
in an alternative embodiment, the outer region has a porosity of 10% to 20%;
the porosity is high, so that the lithium ion can be conveniently de-intercalated, and the rate capability of the battery can be improved.
Optionally, the porosity of the inner layer region may be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, or any value between 5% and 18%; the porosity of the outer layer region may be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, or any value between 10% and 20%.
In an alternative embodiment, the ratio of the thickness of the inner region to the thickness of the outer region is from 0.8 to 1.5;
note that the thickness of the inner layer region refers to the length from the center point (core) to the surface of the inner layer region; the thickness of the outer region refers to the length from the surface of the inner region to the surface of the outer region.
Optionally, the ratio of the thickness of the inner region to the thickness of the outer region may be 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5 or any value between 0.8 and 1.5;
in an alternative embodiment, the binary precursor has a specific surface area of 14-25m2/g；
In an alternative embodiment, the particle size D50 of the binary precursor is 3-5 μm;
in an alternative embodiment, the particle size of the binary precursor, D90/D50, is 1.4-1.8;
the optimization of the particle size and the specific surface area is beneficial to improving the capacity of the battery.
Optionally, the specific surface area of the binary precursor may be 14m2/g、15m2/g、16m2/g、17m2/g、18m2/g、19m2/g、20m2/g、21m2/g、22m2/g、23m2/g、24m2/g、25m2G or 14 to 25m2Any value between/g; the particle size D50 of the binary precursor can be any value of 3 μm, 4 μm, 5 μm or 3-5 μm; the particle size D90/D50 of the binary precursor may be any value between 1.4, 1.5, 1.6, 1.7, 1.8, or 1.4 and 1.8.
In an alternative embodiment, the binary precursor has the formula NixMny(OH)2Wherein x + y is 1, 1 is more than x and more than or equal to 0.7, and 0.3 is more than or equal to y and more than 0.
Optionally, the value of x may be 0.7, 0.8, 0.9, 0.99, or any value between 0.7 and 1, excluding 1.
The application also provides a preparation method of the binary precursor, which comprises the following steps:
mixing materials including a complexing agent, hydroxide and water to obtain a base solution, continuously adding the complexing agent, the hydroxide and a nickel-manganese binary mixed salt solution into the base solution at the same time, and performing coprecipitation reaction under the stirring condition to obtain the binary precursor.
In an alternative embodiment, the mixed salt solution includes soluble nickel and manganese salts;
in an alternative embodiment, the soluble nickel salt comprises one or more of nickel sulfate, nickel nitrate, nickel acetate;
in an alternative embodiment, the manganese salt comprises one or more of manganese sulfate, manganese nitrate, manganese acetate;
in an alternative embodiment, the concentration of the nickel manganese binary mixed salt solution is 0.5-2 mol/L;
optionally, the concentration of the nickel-manganese binary mixed salt solution may be any value between 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L or 0.5-2 mol/L.
In an optional embodiment, the adding speed of the nickel-manganese binary mixed salt solution is 3-5L/h;
in an alternative embodiment, the complexing agent comprises one or more of ammonium bicarbonate, ammonium carbonate, aqueous ammonia;
in an alternative embodiment, the concentration of the complexing agent is 5 to 10 mol/L;
optionally, the concentration of the complexing agent may be 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L or any value between 5 and 10 mol/L;
in an alternative embodiment, the addition rate of the complexing agent is 0.01-0.5L/h;
optionally, the addition speed of the complexing agent can be any value of 0.01L/h, 0.05L/h, 0.1L/h, 0.2L/h, 0.3L/h, 0.4L/h, 0.5L/h or 0.01-0.5L/h;
in an alternative embodiment, the hydroxide comprises sodium hydroxide and/or potassium hydroxide;
in an alternative embodiment, the hydroxide concentration is 5 to 15 mol/L;
in an alternative embodiment, the rate of addition of the hydroxide is 1.2 to 2.0L/h;
optionally, the hydroxide concentration may be any value between 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L, 14mol/L, 15mol/L or 5-15 mol/L; the adding speed of the hydroxide can be any value of 1.2L/h, 1.3L/h, 1.4L/h, 1.5L/h, 1.6L/h, 1.7L/h, 1.8L/h, 1.9L/h, 2.0L/h or 1.2-2.0L/h;
in an alternative embodiment, the rate of addition of the hydroxide is increased stepwise.
In an alternative embodiment, the method of preparing the base solution comprises:
preheating water, and then adding the complexing agent and the hydroxide;
in an alternative embodiment, the pre-heating temperature endpoint is 45-65 ℃;
in an alternative embodiment, the pH of the co-precipitation reaction is between 11 and 12;
in an alternative embodiment, the rate of agitation is 400-1000 r/min.
It will be appreciated that the preheating of the water in the reaction vessel is only one way to obtain water at a particular temperature, and that the hot water may be obtained in other ways and then added to the vessel.
Optionally, the temperature endpoint of the preheating may be any value between 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 45-65 ℃, the pH of the coprecipitation reaction may be any value between 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12 or 11-12, and the stirring rate may be any value between 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min or 400-1000 r/min.
In an alternative embodiment, the method for preparing the binary precursor further comprises a post-treatment comprising:
centrifuging the reaction system, washing solids, demagnetizing, drying and sieving to obtain a product;
in an alternative embodiment, the drying temperature is 90-200 ℃ and the drying time is 10-24 h;
optionally, the drying temperature may be any value between 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ or between 90 ℃ and 200 ℃, and the time may be any value between 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h or between 10h and 24 h.
The application also provides a lithium ion battery anode material, and the raw material of the lithium ion battery anode material comprises the binary precursor.
The application also provides a lithium ion battery, and the raw material of the lithium ion battery comprises the lithium ion battery anode material.
The application also provides electric equipment which comprises the lithium ion battery.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Preparing nickel and manganese sulfate crystals (the molar ratio is 0.75:0.25) into a uniform binary metal salt mixed solution of 2 mol/L; mixing 10mol/L sodium hydroxide solution and 8mol/L ammonia water to prepare a base solution with the pH value of 11.7; adding the base solution into a reaction kettle with a stirring device, slowly adding ammonia water, a sodium hydroxide solution and a binary metal salt mixed solution according to a certain proportion at a stirring speed of 600r/min, wherein the temperature of deionized water in the reaction kettle is 55 ℃, the adding speed of the binary metal salt mixed solution is 3-4-5L/h, the adding speed of the sodium hydroxide solution is 1.2-1.6-2.0L/h, the adding speed of the ammonia water is 0.15L/h, and obtaining the high-nickel cobalt-free binary precursor under the condition of consuming 319L of the binary metal salt mixed solution.
Carrying out centrifugal washing and drying in an oven on the precipitate to obtain a dried material; and crushing the obtained dried material in a grinding device, and then carrying out treatment such as sieving, demagnetizing and the like to obtain the high-nickel cobalt-free binary precursor.
Fig. 1 is a scanning electron microscope image of a high-nickel cobalt-free binary precursor obtained in example 1, and fig. 2 is a partially enlarged view of fig. 1; fig. 3 is a sectional electron microscope image of the high nickel cobalt-free binary precursor obtained in example 1, fig. 4 is an XRD image of the high nickel cobalt-free binary precursor obtained in example 1, and fig. 5 is a particle size distribution diagram of the high nickel cobalt-free binary precursor obtained in example 1.
As can be seen from fig. 1 to 3, the outer layer of the high nickel cobalt-free binary precursor obtained in example 1 presents radially arranged gelatinized coarse flaky primary particles, and the primary particles are closely arranged; the interior is loose and porous thin sheet shape, the interior is honeycomb shape, and the whole interior is inner core and outer core loose and tight.
And (3) mixing the obtained precursor according to the element molar ratio (Ni + Mn) and Li (1: 1.05), heating to 850 ℃ in a muffle furnace at the heating rate of 3 ℃/min, calcining for 8 hours, cooling, crushing, sieving, assembling into a battery, and testing the battery performance.
Example 2
Preparing nickel and manganese sulfate crystals (the molar ratio is 0.75:0.25) into a uniform binary metal salt mixed solution of 2 mol/L; mixing 10mol/L sodium hydroxide solution and 6mol/L ammonia water to prepare a base solution with the pH value of 11.7; adding the base solution into a reaction kettle with a stirring device, slowly adding ammonia water, a sodium hydroxide solution and a binary metal salt mixed solution according to a certain proportion at a stirring speed of 600r/min, wherein the temperature of deionized water in the reaction kettle is 55 ℃, the stirring speed is 600 plus one liter of water at 500r/min, the adding speed of the binary metal salt mixed solution is 3-4-5L/h, the adding speed of the sodium hydroxide solution is 1.2-1.6-2.0L/h, the adding speed of the ammonia water is 0.15L/h, and obtaining the high-nickel cobalt-free binary precursor under the condition of consuming 423L of the binary metal salt mixed solution.
Carrying out centrifugal washing and drying in an oven on the precipitate to obtain a dried material; and crushing the obtained dried material in a grinding device, and then carrying out treatment such as sieving, demagnetizing and the like to obtain the high-nickel cobalt-free binary precursor.
Fig. 4 is a scanning electron microscope image of the high-nickel cobalt-free binary precursor obtained in example 2, and fig. 5 is a sectional electron microscope image of the high-nickel cobalt-free binary precursor obtained in example 2.
As can be seen from fig. 4 and 5, the outer layer of the high nickel cobalt-free binary precursor obtained in example 2 presents radially arranged gelatinized coarse flaky primary particles, and the primary particles are closely arranged; the interior is loose and porous thin sheet shape, the interior is honeycomb shape, and the whole interior is inner core and outer core loose and tight.
And (3) mixing the obtained precursor according to the element molar ratio (Ni + Mn) and Li (1: 1.05), heating to 850 ℃ in a muffle furnace at the heating rate of 3 ℃/min, calcining for 8 hours, cooling, crushing, sieving, assembling into a battery, and testing the battery performance.
Example 3
Preparing nickel and manganese sulfate crystals (the molar ratio is 0.80:0.20) into a uniform binary metal salt mixed solution of 2 mol/L; mixing 10mol/L sodium hydroxide solution and 8mol/L ammonia water to prepare a base solution with the pH value of 11.8; adding the base solution into a reaction kettle with a stirring device, slowly adding ammonia water, a sodium hydroxide solution and a binary metal salt mixed solution according to a certain proportion at the stirring speed of 700r/min, wherein the temperature of deionized water in the reaction kettle is 58 ℃, the adding speed of the binary metal salt mixed solution is 3-4-5L/h, the adding speed of the sodium hydroxide solution is 1.2-1.6-2.0L/h, the adding speed of the ammonia water is 0.15L/h, and obtaining the high-nickel cobalt-free binary precursor under the condition of consuming 332L of the binary metal salt mixed solution.
Carrying out centrifugal washing and drying in an oven on the precipitate to obtain a dried material;
and crushing the obtained dried material in a grinding device, and then carrying out treatment such as sieving, demagnetizing and the like to obtain the high-nickel cobalt-free binary precursor.
As can be seen from fig. 6 and 7, the outer layer of the high nickel cobalt-free binary precursor obtained in example 3 presents radially arranged gelatinized coarse flaky primary particles, and the primary particles are closely arranged; the interior is loose and porous thin sheet shape, the interior is honeycomb shape, and the whole interior is inner core and outer core loose and tight.
And (3) mixing the obtained precursor according to the element molar ratio (Ni + Mn) and Li (1: 1.05), heating to 850 ℃ in a muffle furnace at the heating rate of 3 ℃/min, calcining for 8 hours, cooling, crushing, sieving, assembling into a battery, and testing the battery performance.
Comparative example 1
Preparing nickel and manganese sulfate crystals (the molar ratio is 0.75:0.25) into a uniform binary metal salt mixed solution of 2 mol/L; mixing 10mol/L sodium hydroxide solution and 7mol/L ammonia water to prepare a base solution with the pH value of 11.9; adding the base solution into a reaction kettle with a stirring device, slowly adding ammonia water, a sodium hydroxide solution and a binary metal salt mixed solution according to a certain proportion at the stirring speed of 300r/min, wherein the temperature of deionized water in the reaction kettle is 55 ℃, the adding speed of the binary metal salt mixed solution is 3-4-5L/h, the adding speed of the sodium hydroxide solution is 1.2-1.6-2.0L/h, the adding speed of the ammonia water is 0.15L/h, and obtaining the high-nickel cobalt-free binary precursor under the condition of consuming 384L of the binary metal salt mixed solution.
And (3) centrifugally washing the precipitate, carrying out alkali washing by using 0.5mol/L sodium hydroxide solution, and then washing by using deionized water at 70 ℃ to ensure that Na is less than or equal to 150ppm and S is less than or equal to 1000 ppm.
Dispersing the centrifugally washed materials, putting the dispersed materials into a blast type oven, drying and dehydrating the materials for 12 hours at the temperature of 180 ℃, taking out the materials, and sealing and storing the materials;
and crushing the obtained dried material in a grinding device, and then carrying out treatment such as sieving, demagnetizing and the like to obtain the high-nickel cobalt-free binary precursor. Fig. 8 is a scanning electron microscope image of the high nickel cobalt-free binary precursor obtained in comparative example 1, and fig. 9 is a sectional electron microscope image of the high nickel cobalt-free binary precursor obtained in comparative example 1.
As can be seen from fig. 8 and 9, the outer layer of the high nickel cobalt-free binary precursor obtained in comparative example 1 does not exhibit radially aligned gelatinized coarse platelet-shaped primary particles, but exhibits thick acicular primary particles; the interior of the bag is not in a loose and porous thin sheet shape, but in a dense net structure, and the whole structure is tight inside and loose outside.
And (3) mixing the obtained precursor according to the element molar ratio (Ni + Mn) and Li (1: 1.05), heating to 850 ℃ in a muffle furnace at the heating rate of 3 ℃/min, calcining for 8 hours, cooling, crushing, sieving, assembling into a battery, and testing the battery performance.
Comparative example 2
Preparing nickel and manganese sulfate crystals (the molar ratio is 0.75:0.25) into a uniform binary metal salt mixed solution of 2 mol/L; mixing 10mol/L sodium hydroxide solution and 5mol/L ammonia water to prepare a base solution with the pH value of 12.1; adding the base solution into a reaction kettle with a stirring device, slowly adding ammonia water, a sodium hydroxide solution and a binary metal salt mixed solution according to a certain proportion at a stirring speed of 500r/min, wherein the temperature of deionized water in the reaction kettle is 55 ℃, the stirring speed is 500-400r/min, the adding speed of the binary metal salt mixed solution is 3-4-5L/h, the adding speed of the sodium hydroxide solution is 1.2-1.6-2.0L/h, the adding speed of the ammonia water is 0.15L/h, and obtaining the high-nickel cobalt-free binary precursor under the condition of consuming 509L of the binary metal salt mixed solution.
Carrying out centrifugal washing and drying in an oven on the precipitate to obtain a dried material; and crushing the obtained dried material in a grinding device, and then carrying out treatment such as sieving, demagnetizing and the like to obtain the high-nickel cobalt-free binary precursor.
Fig. 10 is a scanning electron microscope image of the high nickel cobalt-free binary precursor obtained in comparative example 2, and fig. 11 is a sectional electron microscope image of the high nickel cobalt-free binary precursor obtained in comparative example 2.
As can be seen from fig. 10 and 11, the outer layer of the high nickel cobalt-free binary precursor obtained in comparative example 2 does not exhibit radially aligned gelatinized coarse platelet-shaped primary particles, but exhibits thick acicular primary particles; the interior of the bag is not in a loose and porous thin sheet shape, but in a dense net structure, and the whole structure is tight inside and loose outside.
And (3) mixing the obtained precursor according to the element molar ratio (Ni + Mn) and Li (1: 1.05), heating to 850 ℃ in a muffle furnace at the heating rate of 3 ℃/min, calcining for 8 hours, cooling, crushing, sieving, assembling into a battery, and testing the battery performance.
The test results of the examples and comparative examples are shown in table 1 below:
TABLE 1 physicochemical data and Battery Performance of examples and comparative examples
Figure BDA0003439989970000131
Figure BDA0003439989970000141
As can be seen from table 1, D90/D50 and BET of example 1 are significantly higher than those of comparative example 1, under the condition that the 1C condition is similar to 100-cycle retention rate, the primary discharge efficiency of the cathode material is 9.5% higher than that of comparative example 1, and the capacity at 1C rate is 10.6% higher than that of comparative example 1, and the main reasons for the difference in battery performance are that the outer layer of example 1 presents radially arranged gelatinized coarse flaky primary particles, and the primary particles are tightly arranged; the interior of the bag is in a loose and porous thin sheet shape, and the interior of the bag is in a honeycomb shape; while the outer layer of comparative example 1 does not exhibit radially arranged gelatinized coarse plate-like primary particles but exhibits thick acicular primary particles; the interior of the material does not present loose and porous fine sheets, but rather presents a dense net structure; secondly, the difference between BET, inner core porosity, outer layer porosity and the length ratio of the inner core to the outer layer is that the BET ratio of example 1 is 136% larger than the BET ratio of comparative example 1, the inner core porosity of example 1 is 207% larger than the inner core porosity of comparative example 1, the length of the inner core and the outer layer of example 1 is 25% larger than the comparative example 1, and compared with the structure of comparative example 1, the structure of example 1 has the characteristics of more loose and porous inside and tighter outside, and the morphological characteristics enable lithium ions to be absorbed and stored more easily, and the gram capacity of the battery is higher. The outer layer of example 2 exhibited radially arranged gelatinized coarse flaky primary particles, and the primary particles were closely arranged; the interior of the bag is in a loose and porous thin sheet shape, and the interior of the bag is in a honeycomb shape; the outer layer of comparative example 2 does not present radially aligned gelatinized coarse flaky primary particles but present thick acicular primary particles; the interior of the battery is not in a loose and porous fine sheet shape, but in a dense net structure, the structural difference exists, the porosity of the inner core of the embodiment 2 is 750% greater than that of the comparative example 2, the length of the inner core and the outer layer of the embodiment 2 is 178% greater than that of the comparative example 2, the battery electrical property is better due to the porous structure with the inner tightness and the outer tightness, the first discharge efficiency of the positive electrode material is 6% higher than that of the positive electrode material of the comparative example 2, the capacity at the 1C rate is 10.4% higher than that of the positive electrode material of the comparative example 2, and the 1C condition 100-week cycle retention rate of the positive electrode material is 1.23% higher than that of the comparative example 2.
The anode material prepared from the precursor has the first discharge of more than 210mAh/g, the 1C capacity of more than 190mAh/g, the 100-cycle retention rate of more than 89% under the 1C condition, and the charge-discharge rate is high under the condition of high cycle efficiency.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (10)

1. A binary precursor is characterized by comprising an inner layer region and an outer layer region arranged on the surface of the inner layer region;
the inner zone comprises primary particles arranged in a honeycomb shape, and the outer zone comprises primary particles arranged in a radial shape.
2. The binary precursor according to claim 1, wherein the porosity of said inner layer region is between 5% and 18%; preferably, the porosity of the outer layer region is 10% to 20%;
preferably, the ratio of the thickness of the inner region to the thickness of the outer region is from 0.8 to 1.5;
preferably, the specific surface area of the binary precursor is 14-25m2/g；
Preferably, the particle size D50 of the binary precursor is 3-5 μm;
preferably, the particle size D90/D50 of the binary precursor is 1.4-1.8.
3. Binary precursor according to claim 1, characterized in that it has the chemical formula NixMny(OH)2Wherein x + y is 1, 1 is more than x and more than or equal to 0.7, and 0.3 is more than or equal to y and more than 0.
4. A method for preparing a binary precursor according to any one of claims 1 to 3, comprising:
mixing materials including a complexing agent, hydroxide and water to obtain a base solution, continuously adding the complexing agent, the hydroxide and a nickel-manganese binary mixed salt solution into the base solution at the same time, and performing coprecipitation reaction under the stirring condition to obtain the binary precursor.
5. The method of preparing a binary precursor according to claim 4, wherein said binary mixed nickel-manganese salt solution comprises soluble nickel and manganese salts;
preferably, the soluble nickel salt comprises one or more of nickel sulfate, nickel nitrate, nickel acetate;
preferably, the manganese salt comprises one or more of manganese sulfate, manganese nitrate, manganese acetate;
preferably, the concentration of the nickel-manganese binary mixed salt solution is 0.5-2 mol/L;
preferably, the adding speed of the nickel-manganese binary mixed salt solution is 3-5L/h;
preferably, the complexing agent comprises one or more of ammonium bicarbonate, ammonium carbonate and ammonia water;
preferably, the concentration of the complexing agent is 5-10 mol/L;
preferably, the adding speed of the complexing agent is 0.01-0.5L/h;
preferably, the hydroxide comprises sodium hydroxide and/or potassium hydroxide;
preferably, the concentration of the hydroxide is 5-15 mol/L;
preferably, the adding speed of the hydroxide is 1.2-2.0L/h;
preferably, the rate of addition of the hydroxide is increased stepwise.
6. The method of preparing a binary precursor according to claim 4, wherein the method of preparing the base solution comprises:
preheating water, and then adding the complexing agent and the hydroxide;
preferably, the temperature end point of the preheating is 45-65 ℃;
preferably, the pH of the coprecipitation reaction is 11 to 12;
preferably, the stirring speed is 400-1000 r/min.
7. Method for the preparation of a binary precursor according to any one of claims 4 to 6, further comprising a post-treatment comprising:
centrifuging the reaction system, washing solids, demagnetizing, drying and sieving to obtain a product;
preferably, the drying temperature is 90-200 ℃ and the drying time is 10-24 h.
8. A positive electrode material for a lithium ion battery, characterized in that the raw material thereof comprises the binary precursor according to any one of claims 1 to 3.
9. A lithium ion battery characterized in that its raw material comprises the positive electrode material for lithium ion batteries according to claim 8.
10. An electric device comprising the lithium ion battery according to claim 9.
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