CN114497534B - Cobalt-free positive electrode material, preparation method and application thereof - Google Patents

Cobalt-free positive electrode material, preparation method and application thereof Download PDF

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CN114497534B
CN114497534B CN202210102361.1A CN202210102361A CN114497534B CN 114497534 B CN114497534 B CN 114497534B CN 202210102361 A CN202210102361 A CN 202210102361A CN 114497534 B CN114497534 B CN 114497534B
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particles
cobalt
positive electrode
plane
electrode material
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CN114497534A (en
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郭丰
乔齐齐
李子郯
杨红新
施泽涛
王鹏飞
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Svolt Energy Technology Maanshan Co Ltd
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    • 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
    • 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
    • H01M4/52—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
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application provides a cobalt-free positive electrode material, a preparation method and application thereof, wherein the cobalt-free positive electrode material comprises plane rectangular particles and plane elliptical particles, and the number of the plane rectangular particles with the shape factor of 0.5-0.6 in the cobalt-free positive electrode material accounts for 50-80% of the total number of the plane rectangular particles; the number of the plane elliptic particles with the shape factor of 0.5-0.8 in the cobalt-free positive electrode material accounts for 50-80% of the total number of the plane elliptic particles. The application improves the charging capacity of the battery by adjusting the particle distribution of the anode material, and ensures the long-term rapid charging use of the lithium ion battery, and simultaneously has good cycle service life and safety.

Description

Cobalt-free positive electrode material, preparation method and application thereof
Technical Field
The application belongs to the technical field of batteries, and relates to a cobalt-free positive electrode material, a preparation method and application thereof.
Background
In the large background of carbon neutralization, along with the transformation of new energy automobiles from fuel automobiles to electric automobiles, lithium batteries are increasingly developed, and it is known that the cost of a positive electrode material occupies more than 40% in the production process of the lithium batteries, and in addition, the price of cobalt is high and the storage quantity is low, so that the development of a cobalt-free positive electrode material is imperative.
Notably, NM (nickel manganese positive electrode) and NCM (nickel cobalt manganese positive electrode) having the same Ni content were equivalent in discharge capacity at 0.1C, while NM exhibited better cycle stability and thermal stability relative to NCM. The cobalt-free positive electrode material is cheaper than the ternary positive electrode material due to the elimination of cobalt element. Therefore, the cobalt-free positive electrode material has a strong application prospect.
However, the fast charge performance of the cobalt-free positive electrode needs to be improved, so how to improve the fast charge performance of the cobalt-free positive electrode material is a technical problem which needs to be solved urgently at present.
Disclosure of Invention
Aiming at the defects existing in the prior art, the application aims to provide a cobalt-free positive electrode material, a preparation method and application thereof, and the particle distribution of the positive electrode material is adjusted to improve the charging capability of a battery, so that the lithium ion battery is ensured to be used for long-term rapid charging and has good cycle service life and safety.
To achieve the purpose, the application adopts the following technical scheme:
in a first aspect, the present application provides a cobalt-free cathode material, where the cobalt-free cathode material includes planar rectangular-like particles and planar elliptical-like particles, and the number of the planar rectangular-like particles with a shape factor of 0.5-0.6 (e.g., 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, or 0.60) in the cobalt-free cathode material accounts for 50-80% (e.g., 50%, 55%, 60%, 65%, 70%, 75%, or 80%) of the total number of the planar rectangular-like particles; the number of the plane elliptic-like particles with the shape factor of 0.5-0.8 (for example, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75 or 0.80) in the cobalt-free positive electrode material accounts for 50-80% (for example, 50%, 55%, 60%, 65%, 70%, 75% or 80%) of the total number of the plane elliptic-like particles.
According to the application, the shape factor value of the positive electrode material is selected, so that the stacking orientation degree of positive electrode material particles in the positive electrode plate is ensured, the compaction density of the positive electrode material can be improved to the greatest extent, and the quick charge performance of the positive electrode material is improved. The application ensures that the dynamics of the positive electrode material of the lithium ion battery in the rapid charge and discharge process is optimal, and the lithium ion battery produced by adopting the positive electrode material has higher cycle retention capacity at high charge speed, can ensure that the lithium ion battery has very good cycle service life and safety when being rapidly charged and used for a long time. If the granularity range of the positive electrode material is not in the range of the application, the particle stacking degree in the positive electrode plate is not very tight, so that the compaction is lower, and the quick charging performance of the positive electrode plate is reduced.
The plane-like rectangular particles in the application are characterized in that after being cut along the axial central plane of the particles, the cross section of the particles is similar to a rectangle, namely, after the edges of the cross section profile are fitted and approximated, the fitted profile is rectangular; the plane elliptic-like particles are characterized in that after being cut along the axial center plane of the particles, the cross section of the particles is similar to an ellipse, namely, after the edge fitting of the profile of the cross section is approximate, the fitting profile is elliptical.
The shape factor is a factor related to the axial ratio, wherein the axial ratio is defined by that the external parallel line spacing of the positive electrode material particles in a two-dimensional plane graph is defined as Q, and the axial ratioCan be obtained by using the ratio of the maximum Q value to the minimum Q value in all directions, and the shape factor can be calculated by the area S and the perimeter P of the graph, i.e. the shape factor F=4πS/P 2 Is mainly sensitive to the degree of boundary irregularity of the graphic. When the shape factors of the regular shapes (ellipse and rectangle) are calculated, after the long and short axes (side length) of the shape are obtained, one of the axes length (side length) is a, and the other axis length (side length) isPerimeter for rectangular class->And the perimeter of the ellipse can be approximately expressed as:>furthermore, the areas S of the ellipse and rectangle are +.>And->To sum up, the calculation formulas of the ellipse class and rectangle class shape factors can be obtained: (1) Ellipse shape factor/>(2) Rectangular form factor
As a preferred embodiment of the present application, the planar rectangular particles in the cobalt-free cathode material account for 50-90%, such as 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% of the total particles.
Preferably, the planar elliptic particles in the cobalt-free cathode material account for 5-50%, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of the total particle amount.
Preferably, the chemical formula of the cobalt-free positive electrode material comprises Li a Ni x Mn 1-x O 2 ，0.95<a<1.2, e.g. 1.00, 1.05, 1.10 or 1.15,0.5<x<0.95, for example 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85 or 0.90.
Preferably, the cobalt-free cathode material is doped with a doping element.
Preferably, the doping element comprises one or a combination of at least two of Zr, W, ti, mg, ta, mo, nb or Sr.
Preferably, the doping element is doped in an amount of 1500 to 5000ppm, for example, 1500ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm or 5000ppm, based on the total mass of the cobalt-free cathode material.
Preferably, the cobalt-free positive electrode material is coated with a coating layer.
Preferably, the material of the coating layer comprises TiO 2 、TeO 2 、ZrO 2 、Al 2 O 3 、WO 3 、Ta 2 O 5 、MgO、Y 2 O 5 ZnO or B 2 O 3 One or a combination of at least two of the foregoing.
Preferably, the coating layer has a coating amount of 1500 to 5000ppm, for example, 1500ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm or 5000ppm, based on the total mass of the cobalt-free cathode material.
In a second aspect, the present application provides a method for preparing the cobalt-free cathode material according to the first aspect, where the method for preparing the cobalt-free cathode material includes:
and mixing lithium salt and a cobalt-free precursor, and sintering to prepare the cobalt-free positive electrode material.
As a preferred embodiment of the present application, the lithium salt comprises LiCO 3 And/or LiOH.
Preferably, the lithium salt comprises planar elliptical-like particles.
Preferably, the lithium salt has an axial ratio of 1 to 1.2, for example 1.00, 1.02, 1.04, 1.06, 1.08, 1.10, 1.12, 1.14, 1.16, 1.18 or 1.20.
Preferably, the lithium salt comprises more than or equal to 99% of the number of planar elliptic-like particles, for example 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9% or 100.0%.
Preferably, the number of planar elliptic particles in the lithium salt having a shape factor of 0.9 to 1, e.g. of (0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99 or 1.00), is more than 98% of the total number of planar elliptic particles, including 98%, e.g. 98.0%, 98.2%, 98.4%, 98.6%, 98.8%, 99.0%, 99.2%, 99.4%, 99.6%, 99.8% or 100.0%.
As a preferable technical scheme of the application, the chemical formula of the cobalt-free precursor is Ni y Mn 1-y (OH) 2 Y is 0.2.ltoreq.y.ltoreq.0.95, e.g.y is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 0.95.
Preferably, the cobalt-free precursor comprises planar elliptical-like particles.
Preferably, the cobalt free precursor has an axial ratio of 1 to 1.3, for example 1.00, 1.03, 1.06, 1.09, 1.12, 1.15, 1.18, 1.21, 1.24, 1.27 or 1.30.
Preferably, the cobalt free precursor has a proportion of planar ellipsoids of greater than or equal to 99%, such as 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9% or 100.0%.
Preferably, the planar elliptical-like particles in the cobalt-free precursor having a shape factor of 0.8-1 (e.g., 0.80, 0.82, 0.84, 0.86, 0.88, 0.90, 0.92, 0.94, 0.96, 0.98, or 1.00) comprise more than 95%, including 95%, e.g., 95%, 96%, 97%, 98%, 99%, or 100% of the total number of planar elliptical-like particles.
According to the application, by controlling the shape factors of the lithium salt and the cobalt-free precursor, the cobalt-free positive electrode material is ensured to have good shape factor distribution, and if the shape factors of the lithium salt and the cobalt-free precursor are beyond the range of the application, the morphology of raw materials is mostly disordered and nonuniform, the morphology of the synthesized positive electrode material is irregular, and the particle size is polarized, so that the prepared positive electrode material has poor quick charging performance and low capacity retention rate.
As a preferable technical scheme of the application, the stirring speed of the mixing is 2000-4000 r/min, for example 2000r/min, 2200r/min, 2400r/min, 2600r/min, 2800r/min, 3000r/min, 3200r/min, 3400r/min, 3600r/min, 3800r/min or 4000r/min.
Preferably, the mixing time is 10 to 20min, for example 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or 20min.
Preferably, the sintering temperature is 800-1000 ℃, for example 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, 960 ℃, 980 ℃ or 1000 ℃.
Preferably, 0.2.ltoreq.y < 0.6 in the cobalt-free precursor, the sintering temperature is 900 to 1000 ℃, for example 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃ or 1000 ℃.
Preferably, 0.6.ltoreq.y.ltoreq.0.95 in the cobalt-free precursor, the sintering temperature is 800-900 ℃, for example 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃ or 900 ℃.
The application prevents the shape distribution of the positive electrode material from being out of a reasonable range by controlling the sintering temperature to be 900-1000 ℃ and avoiding the temperature from being lower than 900 ℃, thereby influencing the electrochemical performance of the positive electrode material.
As a preferred embodiment of the present application, the doping element is obtained by mixing a dopant into a lithium salt and a cobalt-free precursor, the dopant including planar rectangular-like particles and planar elliptical-like particles.
Preferably, the planar rectangular-like particles in the dopant comprise 70-90%, such as 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88% or 90% of the total particle count.
Preferably, the planar ellipsoidal particles in the dopant comprise 5-30%, such as 5%, 10%, 15%, 20%, 25% or 30% of the total particle number.
In one embodiment of the present application, the dopant includes ZrO 2 、TiO 2 、WO 3 MoO, mgO, srO or Ta 2 O 5 One or a combination of at least two of the foregoing.
Preferably, the planar rectangular-like particles in the dopant having a shape factor of 0.7 to 0.85 comprise more than 95%, including 95%, for example 95%, 96%, 97%, 98%, 99% or 100% of the total number of planar rectangular-like particles.
Preferably, the D50 of the planar rectangular-like particles in the dopant is 100 to 400nm, for example 100nm, 130nm, 160nm, 190nm, 220nm, 250nm, 280nm, 310nm, 340nm, 370nm or 400nm.
Preferably, the planar elliptical particles in the dopant having a shape factor of 0.5 to 0.7 comprise more than 95%, including 95%, for example 95%, 96%, 97%, 98%, 99% or 100% of the total number of planar elliptical particles.
Preferably, the D50 of the planar, elliptical-like particles in the dopant is 200 to 300nm, for example 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm or 300nm.
The application ensures that the doping elements are uniformly distributed by controlling the shape factor of the doping agent, if the shape factor exceeds the range of the application, the morphology of the raw material is irregular, the raw material is difficult to form close fit with cobalt-free precursor and lithium salt phase in the high-temperature doping process, the doping elements are unevenly distributed, the interlayer spacing expansion effect can not be achieved, the positive electrode material is difficult to insert and release, and the quick charging capability is reduced.
As a preferred embodiment of the present application, the coating layer is coated on the surface of the cobalt-free positive electrode material by a coating agent, and the coating agent includes planar rectangular-like particles and planar elliptical-like particles.
Preferably, the planar rectangular-like particles in the coating agent comprise 70 to 90%, such as 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88% or 90% of the total particle count.
Preferably, the planar elliptical-like particles in the coating agent comprise 5 to 30%, for example 5%, 10%, 15%, 20%, 25% or 30% of the total particle count.
Preferably, the coating agent comprises Al 2 O 3 、ZrO 2 、TiO 2 、H 3 BO 3 、MgO、TeO 2 、ZnO、WB、WB 2 、TiN、TiC、Y 2 O 3 、Li 2 ZrO 3 Or Li (lithium) 2 TiO 3 One or a combination of at least two of the foregoing.
Preferably, the temperature of the coating is 500-900 ℃, e.g. 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃.
The application prevents the secondary particles from agglomerating seriously due to overhigh temperature and increasing the granularity and reducing the battery capacity by controlling the coating temperature to be 500-900 ℃.
Preferably, the coating time is 5 to 12 hours, for example 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours.
Preferably, the planar rectangular-like particles with a shape factor of 0.7 to 0.85 in the coating agent comprise more than 95%, including 95%, for example 95%, 96%, 97%, 98%, 99% or 100% of the total number of planar rectangular-like particles.
Preferably, the D50 of the planar rectangular-like particles in the coating agent is 100 to 400nm, for example 100nm, 130nm, 160nm, 190nm, 220nm, 250nm, 280nm, 310nm, 340nm, 370nm or 400nm.
Preferably, the planar elliptical particles with a shape factor of 0.5 to 0.7 in the coating agent comprise more than 95%, including 95%, for example 95%, 96%, 97%, 98%, 99% or 100% of the total number of planar elliptical particles.
Preferably, the D50 of the planar elliptical-like particles in the coating agent is 200-300 nm, for example 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm or 300nm.
The application adopts the coating agent with reasonable shape factor to coat the positive electrode material, so that the coating agent can be uniformly attached to the surface of the positive electrode material, thereby reducing the contact between the positive electrode material and electrolyte, further reducing the gas production risk of the lithium ion battery and improving the cycle stability of the battery.
As a preferable technical scheme of the application, the preparation method of the cobalt-free positive electrode material specifically comprises the following steps:
selecting lithium salt with an axial ratio of 1-1.2, wherein the quantity of plane elliptic like particles in the lithium salt is more than or equal to 99%, and the quantity of plane elliptic like particles with a shape factor of 0.9-1 is more than or equal to 98%;
selecting cobalt-free precursor Ni with axial ratio of 1-1.3 x Mn 1-x (OH) 2 X is more than or equal to 0.2 and less than or equal to 0.95, the proportion of plane elliptic particles in the cobalt-free precursor is more than or equal to 99%, and the quantity proportion of plane elliptic particles with the shape factor of 0.8-1 is more than or equal to 95%;
selecting a doping agent, wherein the doping agent comprises plane rectangular particles and plane elliptic particles, the plane rectangular particles with the shape factor of 0.7-0.85 account for more than 95% of the total number of the plane rectangular particles, the doping agent comprises 95%, and the D50 of the plane rectangular particles in the doping agent is 100-400 nm; the plane elliptic-like particles with the shape factor of 0.5-0.7 account for more than 95 percent of the total number of the plane elliptic-like particles, including 95 percent, and the D50 of the plane elliptic-like particles in the doping agent is 200-300 nm;
selecting a coating agent, wherein the coating agent comprises plane rectangular particles and plane elliptic particles, the plane rectangular particles with the shape factor of 0.7-0.85 account for more than 95% of the total number of the plane rectangular particles, the coating agent comprises 95%, and the D50 of the plane rectangular particles in the coating agent is 100-400 nm; the plane elliptic-like particles with the shape factor of 0.5-0.7 account for more than 95 percent of the total quantity of the plane elliptic-like particles, including 95 percent, and the D50 of the plane elliptic-like particles in the coating agent is 200-300 nm;
mixing the selected lithium salt, the cobalt-free precursor and the doping agent for 10-20 min at 2000-4000 r/min, and sintering at 800-1000 ℃ to obtain the cobalt-free anode material with doping elements;
and mixing the cobalt-free positive electrode material with the doping element with a coating agent, and coating for 5-12 hours at 500-900 ℃ to prepare the cobalt-free positive electrode material.
The cobalt-free positive electrode material prepared by the method is crushed and screened, and the mesh number of the screen is 400-2000 meshes.
In a third aspect, the application provides a battery comprising a positive electrode, a negative electrode and a separator, the positive electrode material of the positive electrode comprising the cobalt-free positive electrode material of the first aspect.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present application is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the application has the beneficial effects that:
according to the application, the shape factor value of the positive electrode material is selected, so that the stacking orientation degree of positive electrode material particles in the positive electrode plate is ensured, the compaction density of the positive electrode material can be improved to the greatest extent, and the quick charge performance of the positive electrode material is improved. The application ensures that the dynamics of the positive electrode material of the lithium ion battery in the rapid charge and discharge process is optimal, and the lithium ion battery produced by adopting the positive electrode material has higher cycle retention capacity at high charge speed, can ensure that the lithium ion battery has very good cycle service life and safety when being rapidly charged and used for a long time. If the granularity range of the positive electrode material is not in the range of the application, the particle stacking degree in the positive electrode plate is not very tight, so that the compaction is lower, and the quick charging performance of the positive electrode plate is reduced.
Detailed Description
For better illustrating the present application, the technical scheme of the present application is convenient to understand, and the present application is further described in detail below. The following examples are merely illustrative of the present application and are not intended to represent or limit the scope of the application as defined in the claims.
The technical scheme of the application is further described by the following specific embodiments.
Example 1
The embodiment provides a cobalt-free positive electrode material, wherein the chemical formula of the cobalt-free positive electrode material is Li 1.05 Ni 0.56 Mn 0.44 O 2 The number of the plane type rectangular particles with the shape factor of 0.5-0.6 in the cobalt-free positive electrode material accounts for 80% of the total number of the plane type rectangular particles, and the number of the plane type elliptical particles with the shape factor of 0.5-0.8 in the cobalt-free positive electrode material accounts for 80% of the total number of the plane type elliptical particles, wherein the number ratio of the plane type elliptical particles, the plane type rectangular particles and the other shape particles is 45:53:2.
The cobalt-free positive electrode material is also doped with 2000ppm of Zr and coated with 2000ppm of Y 2 O 3 。
The embodiment also provides a preparation method of the cobalt-free positive electrode material, which specifically comprises the following steps:
li with an axial ratio of 1.1 is selected 2 CO 3 Wherein the number of the plane elliptic like particles is 100 percent, and the number of the plane elliptic like particles with the shape factor of 0.9-1 is 99 percent;
selecting cobalt-free precursor Ni with axial ratio of 1.15 0.56 Mn 0.44 (OH) 2 The ratio of the plane elliptic-like particles in the cobalt-free precursor is 100%, and the number of the plane elliptic-like particles with the shape factor of 0.9-1 is 99%;
selecting ZrO 2 Dopants comprising planar rectangular-like particlesAnd plane elliptic like particles, wherein the plane elliptic like particles with the shape factor of 0.7-0.8 account for 95% of the total number of the plane elliptic like particles, and the D50 of the plane elliptic like particles in the dopant is 250nm; the plane elliptic-like particles with the shape factor of 0.5-0.7 account for 95% of the total number of the plane elliptic-like particles, the D50 of the plane elliptic-like particles in the dopant is 250nm, and the number ratio of the plane elliptic-like particles, the plane elliptic-like rectangular particles and the other shape particles is 22:76:2;
selecting Y 2 O 3 The coating agent comprises plane rectangular particles and plane elliptic particles, wherein the plane rectangular particles with the shape factor of 0.7-0.8 account for 95% of the total number of the plane rectangular particles, and the D50 of the plane rectangular particles in the coating agent is 250nm; the plane elliptic-like particles with the shape factor of 0.5-0.7 account for 95% of the total number of the plane elliptic-like particles, the D50 of the plane elliptic-like particles in the coating agent is 250nm, and the number ratio of the plane elliptic-like particles, the plane elliptic-like rectangular particles and the other shape particles is 22:76:2;
mixing the selected lithium salt, the cobalt-free precursor and the doping agent for 15min at 3000r/min, and sintering at 990 ℃ to obtain a cobalt-free anode material with doping elements;
and mixing the cobalt-free positive electrode material with the doping elements with a coating agent, coating for 8 hours at 650 ℃, crushing, sieving on a 400-mesh screen, and taking out the screen lower matter to prepare the cobalt-free positive electrode material.
Example 2
The embodiment provides a cobalt-free positive electrode material, wherein the chemical formula of the cobalt-free positive electrode material is Li 1.05 Ni 0.66 Mn 0.34 O 2 The number of the plane type rectangular particles with the shape factor of 0.5-0.6 in the cobalt-free positive electrode material accounts for 50% of the total number of the plane type rectangular particles, and the number of the plane type elliptical particles with the shape factor of 0.5-0.8 in the cobalt-free positive electrode material accounts for 70% of the total number of the plane type elliptical particles, wherein the number ratio of the plane type elliptical particles, the plane type rectangular particles and the other shape particles is 45:53:2.
The cobalt-free positive electrode material is also doped with 1500ppm of W and coated with 1500ppm of Al 2 O 3 。
The embodiment also provides a preparation method of the cobalt-free positive electrode material, which specifically comprises the following steps:
li with an axial ratio of 1.2 is selected 2 CO 3 Wherein the number of the plane elliptic like particles is 99 percent, and the number of the plane elliptic like particles with the shape factor of 0.9-1 is 100 percent;
selecting cobalt-free precursor Ni with axial ratio of 1.3 0.66 Mn 0.34 (OH) 2 The ratio of the plane elliptic-like particles in the cobalt-free precursor is 99%, and the number of the plane elliptic-like particles with the shape factor of 0.9-1 is 100%;
WO is selected 3 The dopant comprises plane rectangular particles and plane elliptic particles, wherein the plane rectangular particles with the shape factor of 0.7-0.85 account for 97% of the total number of the plane rectangular particles, and the D50 of the plane rectangular particles in the dopant is 100nm; the plane elliptic-like particles with the shape factor of 0.5-0.7 account for 96% of the total number of the plane elliptic-like particles, the D50 of the plane elliptic-like particles in the dopant is 200nm, and the number ratio of the plane elliptic-like particles, the plane elliptic-like rectangular particles and the other shape particles is 22:76:2;
selecting Al 2 O 3 The coating agent comprises plane rectangular particles and plane elliptic particles, wherein the plane rectangular particles with the shape factor of 0.7-0.85 account for 98% of the total number of the plane rectangular particles, and the D50 of the plane rectangular particles in the coating agent is 400nm; the plane elliptic-like particles with the shape factor of 0.5-0.7 account for 98 percent of the total number of the plane elliptic-like particles, the D50 of the plane elliptic-like particles in the coating agent is 300nm, wherein the number ratio of the plane elliptic-like particles, the plane elliptic-like rectangular particles and the other shape particles is 22:76:2;
mixing the selected lithium salt, the cobalt-free precursor and the doping agent for 10min at 4000r/min, and sintering at 850 ℃ to obtain the cobalt-free anode material with doping elements;
and mixing the cobalt-free positive electrode material with the doping elements with a coating agent, coating for 12 hours at 700 ℃, crushing, sieving on a 400-mesh screen, and taking out the screen lower matter to prepare the cobalt-free positive electrode material.
Example 3
The embodiment provides a cobalt-free positive electrode material, wherein the chemical formula of the cobalt-free positive electrode material is Li 1.05 Ni 0.9 Mn 0.1 O 2 The number of the plane type rectangular particles with the shape factor of 0.5-0.6 in the cobalt-free positive electrode material accounts for 70% of the total number of the plane type rectangular particles, and the number of the plane type elliptical particles with the shape factor of 0.5-0.8 in the cobalt-free positive electrode material accounts for 50% of the total number of the plane type elliptical particles, wherein the number ratio of the plane type elliptical particles, the plane type rectangular particles and the other shape particles is 45:53:2.
The cobalt-free positive electrode material was also doped with 5000ppm Mg, and coated with 5000ppm ZnO.
The embodiment also provides a preparation method of the cobalt-free positive electrode material, which specifically comprises the following steps:
li with an axial ratio of 1 is selected 2 CO 3 Wherein the number of the plane elliptic like particles is 100%, and the number of the plane elliptic like particles with the shape factor of 0.8-1 is 100%;
selecting cobalt-free precursor Ni with axial ratio of 1 0.9 Mn 0.1 (OH) 2 The ratio of the plane elliptic-like particles in the cobalt-free precursor is 100%, and the number of the plane elliptic-like particles with the shape factor of 0.9-1 is 100%;
selecting MgO doping agent, wherein the MgO doping agent comprises plane rectangle-like particles and plane ellipse-like particles, the plane rectangle-like particles with the shape factor of 0.7-0.85 account for 99% of the total number of the plane rectangle-like particles, and the D50 of the plane rectangle-like particles in the doping agent is 400nm; the plane elliptic-like particles with the shape factor of 0.5-0.7 account for 98 percent of the total number of the plane elliptic-like particles, the D50 of the plane elliptic-like particles in the doping agent is 300nm, and the number ratio of the plane elliptic-like particles, the plane elliptic-like rectangular particles and the other shape particles is 22:76:2;
selecting a ZnO coating agent, wherein the ZnO coating agent comprises plane rectangular particles and plane elliptic particles, the plane rectangular particles with the shape factor of 0.7-0.85 account for 96% of the total number of the plane rectangular particles, and the D50 of the plane rectangular particles in the coating agent is 200nm; the plane elliptic-like particles with the shape factor of 0.5-0.7 account for 97% of the total number of the plane elliptic-like particles, the D50 of the plane elliptic-like particles in the coating agent is 200nm, and the number ratio of the plane elliptic-like particles, the plane elliptic-like rectangular particles and the other shape particles is 22:76:2;
mixing the selected lithium salt, the cobalt-free precursor and the doping agent for 20min at 2000r/min, and sintering at 950 ℃ to obtain the cobalt-free anode material with doping elements;
and mixing the cobalt-free positive electrode material with the doping elements with a coating agent, coating for 5 hours at 900 ℃, crushing, sieving on a 400-mesh screen, and taking out the screen lower matter to prepare the cobalt-free positive electrode material.
Example 4
This example provides a cobalt-free positive electrode material, which differs from the preparation method of example 1 in that the dopant is Ta 2 O 5 The remaining parameters and steps are exactly the same as in example 1.
Example 5
The embodiment provides a cobalt-free cathode material, and compared with the preparation method of embodiment 1, the coating agent is Al 2 O 3 The remaining parameters and steps are exactly the same as in example 1.
Example 6
This example provides a cobalt-free positive electrode material, which has a sintering temperature of 850 ℃ compared to the preparation method of example 1, and the remaining parameters and steps are exactly the same as those of example 1.
Example 7
This example provides a cobalt-free positive electrode material, and compared with the preparation method of example 1, the coating temperature is 800 ℃, and the other parameters and steps are identical to those of example 1.
Example 8
The present embodiment provides a cobalt-free positive electrode material, and compared with the preparation method of embodiment 1, the number of planar elliptic particles with a shape factor of 0.9-1 in the cobalt-free precursor is 80%, and the other parameters and steps are identical to those of embodiment 1.
Example 9
The present example provides a cobalt-free positive electrode material, and compared with the preparation method of example 1, the number of planar elliptic particles with a shape factor of 0.9-1 in the lithium salt is 80%, and the other parameters and steps are identical to those of example 1.
Example 10
The present example provides a cobalt-free cathode material, and compared with the preparation method of example 1, the number of planar elliptic particles with a shape factor of 0.7-0.8 in the dopant is 82%, the number of planar rectangular particles with a shape factor of 0.5-0.7 is 85%, and the other parameters and steps are identical to those of example 1.
Example 11
The present embodiment provides a cobalt-free cathode material, compared with the preparation method of embodiment 1, the number of the planar elliptic particles with the shape factor of 0.7-0.8 in the coating agent is 80%, the number of the planar rectangular particles with the shape factor of 0.5-0.7 is 75%, and the other parameters and steps are identical to those of embodiment 1.
Comparative example 1
The comparative example provides a cobalt-free cathode material, in which the number of planar elliptic-like particles with a shape factor of 0.5 to 0.6 is 40% and the number of planar rectangular-like particles with a shape factor of 0.5 to 0.8 is 40% compared with the preparation method of example 1, and the remaining parameters and steps are exactly the same as those of example 1.
The number ratio is: in the same class of shapes, the number of particles whose shape factor is within range is a ratio.
The application also provides a battery, which comprises a positive electrode, a negative electrode and a diaphragm, wherein the positive electrode material in the positive electrode comprises the cobalt-free positive electrode material.
The cobalt-free positive electrode materials prepared in the examples and the comparative examples are prepared to obtain a positive electrode sheet, a lithium sheet is used as a counter electrode, a cobalt-free positive electrode half battery is obtained, and electrochemical performance test is carried out under the following test conditions:
the charge cut-off voltage was 4.5V, the discharge cut-off voltage was 3.0V, the nominal gram capacity was 200mAh/g, and the test results are shown in Table 1.
TABLE 1
3C/0.1C(％) Capacity retention at 50 weeks at 1C (%)
Example 1 85.0 96.4
Example 2 84.8 96.2
Example 3 84.9 96.1
Example 4 84.3 95.8
Example 5 83.8 94.9
Example 6 84.4 95.2
Examples7 83.9 95.7
Example 8 82.0 91.3
Example 9 80.7 91.8
Example 10 79.8 92.3
Example 11 80.3 90.7
Comparative example 1 80.1 91.6
As can be seen from the table above:
(1) Compared with examples 8 and 9, it can be seen that the shape factors of the lithium salt and the cobalt-free precursor are controlled to ensure that the cobalt-free positive electrode material has good shape factor distribution, and if the shape factors of the lithium salt and the cobalt-free precursor are beyond the scope of the application, the morphology of the raw materials is mostly disordered and nonuniform, the morphology of the synthesized positive electrode material is irregular, and the particle sizes are polarized, so that the prepared positive electrode material has poor quick charging performance and low capacity retention rate.
(2) Compared with the embodiment 10, the embodiment 1 can be seen that by controlling the shape factor of the dopant, the application ensures that the doping elements are uniformly distributed, if the shape of the raw material is irregular, the raw material is difficult to form close fit with the cobalt-free precursor and the lithium salt in the high-temperature doping process, the doping elements are unevenly distributed, the interlayer spacing cannot be enlarged, the anode material is difficult to insert and remove, and the quick charge capability is reduced.
(3) Example 1 compared with example 11, it can be seen that the coating agent with a reasonable shape factor is adopted to coat the positive electrode material, so that the coating agent can be uniformly attached to the surface of the positive electrode material, and the contact between the positive electrode material and the electrolyte is reduced, thereby reducing the gas production risk of the lithium ion battery and improving the cycle stability of the battery.
Through the embodiment and the comparative example, the application ensures the stacking orientation degree of the positive electrode material particles in the positive electrode plate by selecting the shape factor value of the positive electrode material, and can furthest improve the compaction density of the positive electrode material, thereby improving the quick charge performance of the positive electrode material. The application ensures that the kinetics of the positive electrode material of the lithium ion battery in the rapid charge and discharge process is optimal, the lithium ion battery produced by adopting the positive electrode material has higher cycle retention capacity at high charge speed, can ensure good cycle service life and safety when the lithium ion battery is used for long-term rapid charge, can reach 85% at 3C/0.1C, and can reach 96.4% at 50 weeks capacity retention rate at 1C. If the granularity range of the positive electrode material is not in the range of the application, the particle stacking degree in the positive electrode plate is not very tight, so that the compaction is lower, and the quick charging performance of the positive electrode plate is reduced.
The applicant declares that the above is only a specific embodiment of the present application, but the scope of the present application is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present application disclosed by the present application fall within the scope of the present application and the disclosure.

Claims (44)

1. A cobalt-free cathode material, characterized in that the cobalt-free cathode material comprises planar rectangular-like particles and planar elliptical-like particles;
the chemical formula of the cobalt-free positive electrode material comprises Li a Ni x Mn 1-x O 2 ，0.95<a<1.2，0.5<x<0.95；
The number of the plane rectangular particles with the shape factor of 0.5-0.6 in the cobalt-free positive electrode material accounts for 50-80% of the total number of the plane rectangular particles;
the number of plane elliptic like particles with the shape factor of 0.5-0.8 in the cobalt-free positive electrode material accounts for 50-80% of the total number of the plane elliptic like particles;
the calculation formula of the shape factor of the plane rectangular-like particles is as follows
The shape factor calculation formula of the plane elliptic-like particles is
Wherein the method comprises the steps ofThe ratio of the maximum value to the minimum value of the circumscribed parallel line spacing of the rectangular particles or the elliptic particles of the positive electrode material in the two-dimensional plane graph is represented.
2. The cobalt-free positive electrode material according to claim 1, wherein the planar rectangular-like particles in the cobalt-free positive electrode material account for 50 to 90% of the total particles.
3. The cobalt-free positive electrode material according to claim 1, wherein the planar elliptical particles in the cobalt-free positive electrode material account for 5-50% of the total particles.
4. The cobalt-free positive electrode material according to claim 1, wherein the cobalt-free positive electrode material is doped with a doping element.
5. The cobalt-free positive electrode material according to claim 4, wherein the doping element comprises one or a combination of at least two of Zr, W, ti, mg, ta, mo, nb or Sr.
6. The cobalt-free positive electrode material according to claim 4, wherein the doping amount of the doping element is 1500 to 5000ppm based on the total mass of the cobalt-free positive electrode material.
7. The cobalt-free positive electrode material according to claim 1, wherein the cobalt-free positive electrode material is coated with a coating layer.
8. The cobalt-free positive electrode material according to claim 7, wherein the material of the coating layer comprises TiO 2 、TeO 2 、ZrO 2 、Al 2 O 3 、WO 3 、Ta 2 O 5 、MgO、Y 2 O 5 ZnO or B 2 O 3 One or a combination of at least two of the foregoing.
9. The cobalt-free positive electrode material according to claim 7, wherein the coating layer is coated in an amount of 1500 to 5000ppm based on the total mass of the cobalt-free positive electrode material.
10. A method for preparing the cobalt-free cathode material according to any one of claims 1 to 9, wherein the method for preparing the cobalt-free cathode material comprises the steps of:
mixing lithium salt, a cobalt-free precursor and an optional doping agent, and sintering, and optionally coating a coating agent on the surface of the cobalt-free positive electrode material to prepare the cobalt-free positive electrode material.
11. The method of claim 10, wherein the lithium salt comprises LiCO 3 And/or LiOH.
12. The method of claim 10, wherein the lithium salt comprises planar elliptical-like particles.
13. The method according to claim 10, wherein the lithium salt has an axial ratio of 1 to 1.2.
14. The method of claim 12, wherein the lithium salt comprises greater than or equal to 99% of the number of planar elliptic particles.
15. The method of claim 12, wherein the number of planar elliptical-like particles in the lithium salt having a shape factor of 0.9 to 1 is 98% or more, including 98% of the total number of planar elliptical-like particles.
16. The method of claim 10, wherein the cobalt-free precursor has a chemical formula of Ni y Mn 1-y (OH) 2 ，0.2≤y≤0.95。
17. The method of preparing according to claim 10, wherein the cobalt-free precursor comprises planar elliptical-like particles.
18. The method of claim 10, wherein the cobalt-free precursor has an axial ratio of 1 to 1.3.
19. The method of claim 17, wherein the planar ellipsoidal particles comprise greater than or equal to 99% of the cobalt-free precursor.
20. The method of claim 17, wherein the planar elliptical particles having a shape factor of 0.8 to 1 in the cobalt-free precursor comprise greater than 95%, including 95%, of the total number of planar elliptical particles.
21. The method according to claim 10, wherein the stirring speed of the mixing is 2000 to 4000r/min.
22. The method of claim 10, wherein the mixing is for a period of 10 to 20 minutes.
23. The method of claim 10, wherein the sintering temperature is 800-1000 ℃.
24. The method of claim 10, wherein y is 0.2 < 0.6 in the cobalt-free precursor, and the sintering temperature is 900-1000 ℃.
25. The method of claim 10, wherein y is 0.6.ltoreq.0.95 in the cobalt-free precursor, and the sintering temperature is 800-900 ℃.
26. The method of claim 10, wherein the dopant comprises planar rectangular-like particles and planar elliptical-like particles.
27. The method of claim 26, wherein the planar rectangular-like particles in the dopant comprise 70-90% of the total particles.
28. The method of claim 26, wherein the planar ellipsoidal particles comprise 5-30% of the total particles in the dopant.
29. The method of claim 26, wherein the planar rectangular-like particles having a shape factor of 0.7 to 0.85 in the dopant comprise greater than 95%, including 95%, of the total number of planar rectangular-like particles.
30. The method of claim 26, wherein the dopant medium planar rectangular-like particles have a D50 of 100-400 nm.
31. The method of claim 26, wherein the planar ellipsoidal particles having a shape factor of 0.5-0.7 in the dopant comprise greater than 95%, including 95%, of the total number of planar ellipsoidal particles.
32. The method of claim 26, wherein the dopant is a mid-plane ellipsoidal particle having a D50 of 200-300 nm.
33. The method of claim 10, wherein the coating agent comprises planar rectangular-like particles and planar oval-like particles.
34. The method of claim 33, wherein the planar rectangular-like particles in the coating agent comprise 70-90% of the total particles.
35. The method of claim 33, wherein the planar ellipsoidal particles comprise about 5% to about 30% of the total particles in the coating.
36. The method of claim 10, wherein the coating agent comprises Al 2 O 3 、ZrO 2 、TiO 2 、H 3 BO 3 、MgO、TeO 2 、ZnO、WB、WB 2 、TiN、TiC、Y 2 O 3 、Li 2 ZrO 3 Or Li (lithium) 2 TiO 3 One or a combination of at least two of the foregoing.
37. The method according to claim 10, wherein the coating temperature is 500 to 900 ℃.
38. The method according to claim 10, wherein the coating time is 5 to 12 hours.
39. The method of claim 33, wherein the planar rectangular-like particles having a shape factor of 0.7 to 0.85 comprise 95% or more, including 95% of the total number of planar rectangular-like particles in the coating agent.
40. The method of claim 33, wherein the D50 of the planar rectangular-like particles in the coating agent is 100-400 nm.
41. The method of claim 33, wherein the planar ellipsoidal particles having a shape factor of 0.5-0.7 comprise greater than 95%, including 95%, of the total number of planar ellipsoidal particles in the coating agent.
42. The method of claim 33, wherein the D50 of the planar ellipsoidal particles in the coating agent is 200-300 nm.
43. The method of any one of claims 10-42, wherein the method of preparing a cobalt-free positive electrode material specifically comprises the steps of:
selecting lithium salt with an axial ratio of 1-1.2, wherein the quantity of plane elliptic like particles in the lithium salt is more than or equal to 99%, and the quantity of plane elliptic like particles with a shape factor of 0.9-1 is more than or equal to 98%;
selecting cobalt-free precursor Ni with axial ratio of 1-1.3 y Mn 1-y (OH) 2 Y is more than or equal to 0.2 and less than or equal to 0.95, the proportion of plane elliptic particles in the cobalt-free precursor is more than or equal to 99%, and the quantity proportion of plane elliptic particles with the shape factor of 0.8-1 is more than or equal to 95%;
selecting a doping agent, wherein the doping agent comprises plane rectangular particles and plane elliptic particles, the plane rectangular particles with the shape factor of 0.7-0.85 account for more than 95% of the total number of the plane rectangular particles, the doping agent comprises 95%, and the D50 of the plane rectangular particles in the doping agent is 100-400 nm; the plane elliptic-like particles with the shape factor of 0.5-0.7 account for more than 95 percent of the total number of the plane elliptic-like particles, including 95 percent, and the D50 of the plane elliptic-like particles in the doping agent is 200-300 nm;
selecting a coating agent, wherein the coating agent comprises plane rectangular particles and plane elliptic particles, the plane rectangular particles with the shape factor of 0.7-0.85 account for more than 95% of the total number of the plane rectangular particles, the coating agent comprises 95%, and the D50 of the plane rectangular particles in the coating agent is 100-400 nm; the plane elliptic-like particles with the shape factor of 0.5-0.7 account for more than 95 percent of the total quantity of the plane elliptic-like particles, including 95 percent, and the D50 of the plane elliptic-like particles in the coating agent is 200-300 nm;
mixing the selected lithium salt, the cobalt-free precursor and the doping agent for 10-20 min at 2000-4000 r/min, and sintering at 800-1000 ℃ to obtain the cobalt-free anode material with doping elements;
and mixing the cobalt-free positive electrode material with the doping element with a coating agent, and coating for 5-12 hours at 500-900 ℃ to prepare the cobalt-free positive electrode material.
44. A battery comprising a positive electrode, a negative electrode and a separator, wherein the positive electrode material of the positive electrode comprises the cobalt-free positive electrode material of any one of claims 1 to 9.
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