CN115043444B - High-nickel ternary cathode material, preparation method thereof and battery - Google Patents

High-nickel ternary cathode material, preparation method thereof and battery Download PDF

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CN115043444B
CN115043444B CN202210978310.5A CN202210978310A CN115043444B CN 115043444 B CN115043444 B CN 115043444B CN 202210978310 A CN202210978310 A CN 202210978310A CN 115043444 B CN115043444 B CN 115043444B
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lithium
source
sintering
zirconium
tantalum
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CN115043444A (en
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罗涵钰
范华军
雷英
范未峰
张彬
王政强
张郑
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Yibin Libao New Materials Co Ltd
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    • 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
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    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a high-nickel ternary cathode material, a preparation method thereof and a battery, and belongs to the technical field of batteries. The preparation method comprises the following steps: mixing a lithium source, a tantalum source, a zirconium source and a silicon source with the alcohol-washed calcined material, drying and sintering for the second time; the mass ratio of lithium element, tantalum element, zirconium element and silicon element is (1-1.5); the total mass of the four additive elements is 1-2wt% of the primary sintering material; the molecular formula of the calcined material is LiNi x Co y Mn 1‑x‑y O 2 Wherein x is more than or equal to 0.7 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.3. The method can form Li on the surface of a sintering material 1+x Ta 1‑ x Zr x SiO 5 The coating layer is beneficial to improving the structure and the thermal stability of the material. The coating layer has high lithium ionThe conductivity can maintain good rate capability. The obtained cathode material can improve the cycling stability and rate capability of the battery.

Description

High-nickel ternary positive electrode material, preparation method thereof and battery
Technical Field
The invention relates to the technical field of batteries, in particular to a high-nickel ternary cathode material, a preparation method thereof and a battery.
Background
The layered nickel-rich oxide is a promising high-energy density lithium ion battery anode material, has the characteristics of high capacity and low cost, and receives more and more extensive attention. But poor cycling performance due to instability of the electrode-electrolyte interface.
Currently, the surface coating of the material is commonly used to solve the problem. However, the rate capability of the material is reduced by the coating method used at present.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
An object of the present invention is to provide a method for preparing a high-nickel ternary cathode material, so as to solve the above technical problems.
The second purpose of the invention is to provide a high-nickel ternary cathode material prepared by the preparation method.
The invention also aims to provide a battery with the raw material comprising the high-nickel ternary cathode material.
The application can be realized as follows:
in a first aspect, the application provides a preparation method of a high-nickel ternary cathode material, comprising the following steps:
mixing a lithium source, a tantalum source, a zirconium source and a silicon source with the calcined material subjected to alcohol washing, drying and sintering for the second time;
wherein, the mass ratio of lithium element contained in the lithium source, tantalum element contained in the tantalum source, zirconium element contained in the zirconium source and silicon element contained in the silicon source is 1-1.5; the total mass of the lithium element, the tantalum element, the zirconium element and the silicon element is 1-2wt% of the calcined material;
the molecular formula of the calcined material is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.7 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.3; the sintering material is obtained by mixing a precursor and a lithium source and then sintering for the first time.
In an alternative embodiment, the lithium element, the tantalum element, the zirconium element and the silicon element are respectively provided by a lithium acetate solution, a tantalum ethoxide solution, a zirconium acetate solution and an ethyl orthosilicate solution.
In alternative embodiments, the lithium acetate solution, tantalum ethoxide solution, zirconium acetate solution, and ethyl orthosilicate solution are each no less than 90wt% pure.
In an optional embodiment, the lithium acetate solution, the tantalum ethoxide solution, the zirconium acetate solution and the tetraethoxysilane solution are firstly mixed with absolute ethyl alcohol to obtain a coating element mixed solution, and then the coating element mixed solution is mixed with the calcined material subjected to alcohol washing; wherein the mass ratio of the absolute ethyl alcohol to the primary sintering material is 0.6-1.
In an alternative embodiment, the mixed solution of the coating elements is added dropwise to the one-fired material after the alcohol washing at a rate of 0.8 to 1.2 g/min.
In an alternative embodiment, the coating element mixed solution and the alcohol-washed one-shot material are mixed under stirring.
In an alternative embodiment, the stirring speed is from 100 to 800rpm and the stirring time is at least 60min.
In an alternative embodiment, the mass ratio of the absolute ethyl alcohol to the primary fuel used in the alcohol washing process is 0.6 to 1.2.
In an alternative embodiment, the drying is carried out at a temperature of 30-50 ℃ and the moisture content of the dried material after drying is less than or equal to 0.2wt%.
In an alternative embodiment, the second sintering is performed at 600-700 ℃ for 1-4 hours.
In an alternative embodiment, a brown material is made by:
mixing the precursor and a lithium source according to a molar ratio of 1.04-1.08, and then sintering at 700-800 ℃ for 10-12h;
wherein the molecular formula of the precursor is Ni x Co y Mn z (OH) 2 ，x+y+z=1，0.7≤x≤1，0≤y≤0.3；
The lithium source is lithium hydroxide.
In a second aspect, the present application provides a high-nickel ternary cathode material prepared by the preparation method according to any one of the foregoing embodiments;
in an alternative embodiment, a frit has Li formed on the surface thereof 1+x Ta 1-x Zr x SiO 5 And the coating layer, wherein x is more than or equal to 0 and less than or equal to 0.5.
In an alternative embodiment, a frit has Li formed on the surface thereof 1.125 Ta 0.875 Zr 0.125 SiO 5 And (4) coating.
In a third aspect, the present application provides a battery whose raw materials for preparation include the high-nickel ternary positive electrode material of the foregoing embodiments.
The beneficial effect of this application includes:
the method comprises the steps of mixing a lithium source, a tantalum source, a zirconium source, a silicon source and a calcined material (obtained by primary sintering after mixing a precursor and the lithium source) subjected to alcohol washing, drying, and secondary sintering to form Li on the surface of the calcined material 1+x Ta 1-x Zr x SiO 5 The coating layer can be used as a physical barrier layer on the surface of the anode, so that the side reaction between the surface of the material and an electrolyte is avoided, the degradation of a surface interface structure is inhibited, the mechanical stress at the interface is relieved, the possibility of cracking is reduced, and the structure and the thermal stability of the material are improved. Moreover, the coating layer has high lithium ion conductivity, and the surface coating layer does not block Li + And the impedance is reduced by transmission, so that good rate performance is maintained. The obtained cathode material can improve the cycling stability and rate capability of the battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a graph of the specific capacity results of each button cell in test example 1;
fig. 2 is a graph showing the results of capacity retention rate of each button cell in test example 1;
FIG. 3 is an XRD pattern of a cladding layer of each high-nickel ternary positive electrode material in test example 1;
FIGS. 4 and 5 are SEM images of the high-Ni ternary positive electrode material obtained in example 1 of Experimental example 1;
FIGS. 6 and 7 are SEM images of the high-Ni ternary cathode material obtained in example 2 of Experimental example 1;
FIGS. 8 and 9 are scanning electron micrographs of the high-nickel ternary positive electrode material obtained in comparative example 1 of test example 1;
fig. 10 and 11 are scanning electron micrographs of the high-nickel ternary positive electrode material obtained in comparative example 2 of experimental example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. 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 conventional products which are not indicated by manufacturers and are commercially available.
The high-nickel ternary cathode material provided by the present application, and the preparation method and battery thereof are specifically described below.
The inventor proposes through research: the reason that the rate performance of the high-nickel ternary cathode material is reduced by the currently used coating mode is probably that the metal oxide coating adopted in the prior art serves as a physical barrier between the cathode material and the electrolyte, does not participate in electrochemical reaction, but has poor lithium ion conductivity. In some cases, the metal oxide-coated positive electrode material causes cracks to form between particles due to an increase in resistance, resulting in a decrease in rate performance.
Based on this, the application creatively provides a preparation method of a high-nickel ternary cathode material, which comprises the following steps:
mixing a lithium source, a tantalum source, a zirconium source and a silicon source with the calcined material subjected to alcohol washing, drying, and sintering for the second time;
wherein, the mass ratio of lithium element contained in the lithium source, tantalum element contained in the tantalum source, zirconium element contained in the zirconium source and silicon element contained in the silicon source is 1-1.5; the total mass of the lithium element, the tantalum element, the zirconium element and the silicon element is 1-2wt% of the calcined material;
for reference, a frit used in the present application may have the formula LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.7 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.3; the sintering material is obtained by mixing a precursor and a lithium source and then sintering for the first time.
Specifically, the above-mentioned primary sintering material can be prepared by the following steps:
mixing the precursor with a lithium source in a molar ratio of 1.04-1.08 (such as 1.
Wherein the molecular formula of the precursor is Ni x Co y Mn z (OH) 2 X + y + z =1,0.7 is more than or equal to x and less than or equal to 1,0 is more than or equal to y and less than or equal to 0.3; the lithium source is lithium hydroxide.
In some embodiments, the precursor and the lithium source may be mixed for 5-10min at 550-650rpm, then mixed for 15-20min at 800-900rpm, poured out, and then poured back into the mixing apparatus, and mixed for 10-15min at 800-900rpm to obtain a fully uniform mixture of the precursor and the lithium source.
For reference, the lithium element, the tantalum element, the zirconium element, and the silicon element are provided by a lithium acetate solution, a tantalum ethoxide solution, a zirconium acetate solution, and an ethyl orthosilicate solution, respectively. Namely, the lithium source, the tantalum source, the zirconium source and the silicon source are respectively a lithium acetate solution, a tantalum ethoxide solution, a zirconium acetate solution and an ethyl orthosilicate solution.
The purity of the lithium acetate solution, tantalum ethoxide solution, zirconium acetate solution and tetraethoxysilane solution is not less than 90wt%, and may be, for example, 90wt%, 92wt%, 95wt%, 98wt% or 100 wt%.
In the present application, the ratio of the amount of lithium element to tantalum element may be 1.
The mass ratio of the lithium element to the zirconium element may be 1.
The mass ratio of lithium element to silicon element may be 1, 1.05.
In some preferred embodiments, the ratio of the amounts of species of elemental lithium, elemental tantalum, elemental zirconium, and elemental silicon is 1.125.
Li is formed by mixing the lithium element, the tantalum element, the zirconium element and the silicon element according to the mass ratio 1+x Ta 1-x Zr x SiO 5 And (4) coating.
For reference, the total mass of the lithium element, the tantalum element, the zirconium element, and the silicon element may be 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, or the like of one frit, and may be any other value within a range of 1 to 2wt%.
In some preferred embodiments, the total mass of the lithium element, the tantalum element, the zirconium element and the silicon element is 1wt% of the one-fired material.
It should be noted that the total mass of the lithium element, the tantalum element, the zirconium element and the silicon element affects the rate capability of the material. If the total mass of the lithium element, the tantalum element, the zirconium element and the silicon element is less than 1wt% of the primary sintering material, the rate performance improved by cladding is easy to cause poor performance.
In the specific operation process, the lithium acetate solution, the tantalum ethoxide solution, the zirconium acetate solution and the tetraethoxysilane solution are firstly mixed with absolute ethyl alcohol to obtain a coating element mixed solution, and then the coating element mixed solution is mixed with the calcined material subjected to alcohol washing.
Preferably, each of the above solutions is mixed at a temperature not exceeding 50 ℃, e.g., 15-50 ℃ (not included), to avoid decomposition of the substance.
According to the method, each coating element solution is mixed with absolute ethyl alcohol, so that the coating element solution is dispersed in the absolute ethyl alcohol which can be regarded as a solvent, and then a calcined material is infiltrated under the assistance of the absolute ethyl alcohol, so that the coating element solution is effectively adsorbed and combined with the surface site of the calcined material on an atomic level. On the basis, a thin and tightly combined solid electrolyte layer can be formed on the surface of the material through a second sintering treatment at high temperature for a short time. The method well overcomes the defects of large particles of metal oxide doping seeds and low compatibility with the surface of the material in the prior art.
It should be noted that, the amount of each coating element solution used in the present application is small, and if the coating element solution is not dispersed with absolute ethyl alcohol first, but directly mixed with a sintering material, the coating element cannot form a complete and uniform coating layer on the surface of the sintering material, and may only form a coating layer on a partial region of the sintering material, rather than forming a coating layer on the entire surface.
In addition, the coating element solutions are not mixed with water, so that substances such as tetraethoxysilane can be prevented from being decomposed in water.
Preferably, the mixed solution of the coating element is added dropwise to a calcined material after alcohol washing at a rate of 0.8-1.2g/min (e.g., 1 g/min).
The coating and the surface site of the sintering material are fully and effectively adsorbed and combined by dripping at the speed. If the dropping speed is too high, non-uniform bonding is likely to occur.
In the present application, the coating element mixed solution and the alcohol-washed primary sintering material are mixed under stirring.
The stirring speed may be 100-800rpm, such as 100rpm, 200rpm, 300rpm, 400 rpm, 500rpm, 600rpm, 700 rpm, 800rpm, etc., or may be any other value within the range of 100-800 rpm.
It should be noted that, if the rotation speed is too high, the material is easy to be crushed; if the rotating speed is too slow, the materials can be mixed unevenly.
The stirring time is at least 60min, such as 60min, 70min, 80min, 90min or 100 min.
For reference, the mass ratio of the absolute ethanol used in the alcohol washing process of the primary fuel may be 0.6-1.2.
After the primary sintering material is subjected to alcohol washing, the coating element can be adsorbed and combined with the surface of the primary sintering material more favorably, and the adsorption capacity of the coating element on the surface of the primary sintering material is improved.
Further, the drying can be carried out at 30-50 ℃, and the water content of the dried material after drying is less than or equal to 0.2wt%.
And drying to remove the solvent in the mixed system of the sintering material and the coating element mixed solution, wherein the coating element is remained on the surface of the sintering material.
Further, a second sintering is performed.
The second sintering may be performed at 600-700 deg.c for 1-4 hr, and the process may be performed in an atmosphere box furnace.
The second sintering temperature may be 600 ℃, 620 ℃, 650 ℃, 680 ℃, 700 ℃ or the like, or may be any other value within the range of 600-700 ℃.
The second sintering time may be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, or the like, or may be any other value within a range of 1 to 4 hours.
The second sintering conditions provided by the present application enable the ions to react rapidly to obtain the desired electrolyte coating.
It should be noted that the second sintering temperature of the conventional coating layer is about 200-300 ℃, while the second sintering temperature in the present application is lower than 600 ℃, so that the required solid electrolyte cannot be formed at all. Moreover, too long a sintering time can result in too large a particle growth, which affects cycle stability.
In summary, the present application forms Li by preparing on the surface of a calcined material after alcohol washing 1+x Ta 1-x Zr x SiO 5 The coating layer is used as a physical barrier layer on the surface of the anode, so that the side reaction between the surface of the material and an electrolyte is avoided, the degradation of a surface interface structure is inhibited, the mechanical stress at the interface is relieved, the possibility of cracking is reduced, and the improvement of the structure and the thermal stability of the material is facilitated. At this time, the surface coating layer does not block Li due to good lithium ion conductivity + And the impedance is reduced by transmission, so that the favorable rate performance is maintained.
Correspondingly, the application also provides a high-nickel ternary cathode material which is prepared by the preparation method.
In the high-nickel ternary cathode material, li is formed on the surface of a sintering material 1+x Ta 1-x Zr x SiO 5 And the coating layer, wherein x is more than or equal to 0 and less than or equal to 0.5.
In some preferred embodiments, the surface of the primary sintered material is formed with Li 1.125 Ta 0.875 Zr 0.125 SiO 5 And (4) coating.
The Li 1.125 Ta 0.875 Zr 0.125 SiO 5 The coating layer has the advantages of rapid Li diffusion, good phase stability and Li + Good ionic conductivity (Li) + Conductivity > 10 -5 S/cm）。
By contrast, in the prior art, the nickel-cobalt-manganese material is mixed with some inert metal oxides (aluminum oxide, titanium oxide, zirconium oxide and the like) to be coated and sintered, and the coating layer has poor interface compatibility with the nickel-cobalt-manganese material, high interface impedance and no electrochemical activity, and is not beneficial to ion transmission and rate performance improvement.
The method well avoids the defects of large particles and low compatibility with the surface of the material of the metal oxide doping species, reduces the impedance of the obtained material and slightly increases the capacity. Moreover, the thin solid electrolyte layer has good lithium ion conductivity, and reduces Li at the interface of the material and the coating layer + The ion transmission resistance promotes the lithium ion diffusion and improves the rate capability of the material. In addition, based on the compact coating layer formed at the surface interface of the material, the corrosion of electrolyte to the surface of the material is effectively blocked, the side reaction of the interface is prevented, and the integrity of the surface interface of the material is favorably maintained, so that the cycle performance of the material is improved.
Furthermore, the application also provides a battery, and the preparation raw material of the battery comprises the high-nickel ternary cathode material. The battery has good cycle stability, rate performance and capacity retention rate.
In reference, after coating and secondary sintering, the 0.1C specific capacity variation amplitude of the material is less than 5%; compared with a nickel-cobalt-manganese (Ni/(Ni + Co + Mn) product which is not coated with nickel or cobalt or manganese (Ni/(Ni + Co + Mn)) and is more than or equal to 0.75), the multiplying power performance is improved, and the capacity retention rate at 1C is more than or equal to 91% relative to that at 0.1C; compared with the nickel-cobalt-manganese product without coating, the cycle stability is improved by more than or equal to 5 percent.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a high-nickel ternary cathode material, which is prepared by the following method:
(1) Preparing a sintering material:
mixing Ni 0.92 Co 0.04 Mn 0.04 (OH) 2 Adding the lithium hydroxide and the lithium hydroxide into a high-speed mixer according to the mol ratio of 1.08, mixing for 5min under the condition of the rotating speed of 600rpm, then mixing for 15min under the condition of the rotating speed of 900rpm, pouring out, pouring back into the mixing equipment again, and mixing for 10min under the condition of 900 rpm.
Then sintering (first sintering) for 12h in an atmosphere box furnace at 750 ℃ to obtain a sintering material.
(2) Alcohol washing is carried out on the primary fuel:
washing the calcined material by using anhydrous ethanol according to a mass ratio of 0.8.
(3) Preparing a coating element mixed solution:
and mixing the lithium acetate solution, the tantalum ethoxide solution, the zirconium acetate solution, the tetraethoxysilane solution and the absolute ethyl alcohol at the temperature of 20 ℃ to obtain a coating element mixed solution.
Wherein, the ratio of the lithium element contained in the lithium source, the tantalum element contained in the tantalum source, the zirconium element contained in the zirconium source and the silicon element contained in the silicon source is 1.125. The total mass of the lithium element, the tantalum element, the zirconium element and the silicon element is 1wt% of the calcined material.
The purity of lithium acetate solution, tantalum ethoxide solution, zirconium acetate solution and tetraethoxysilane solution is 99%.
(4) Mixing the coating element mixed solution with the alcohol-washed calcined material:
and (3) dropwise adding the coating element mixed solution into the alcohol-washed calcined material at the speed of 1g/min, and mixing for 60min at the speed of 500 rpm.
(5) And (3) drying:
and evaporating a mixed system of the coating element mixed solution and the one-time-fired material subjected to alcohol washing to dryness at 50 ℃ so as to ensure that the water content of the dried material is less than or equal to 0.2wt%.
(6) And (3) second sintering:
and sintering the dried material in an atmosphere box furnace at 650 ℃ for 4h.
By the above treatment, li is formed on the surface of the primary fired material 1.125 Ta 0.875 Zr 0.125 SiO 5 And (4) coating.
Example 2
This example differs from example 1 in that: the second sintering temperature was 700 ℃.
Example 3
This example differs from example 1 in that: the second sintering time is 1h.
Example 4
This example differs from example 1 in that: the mass ratio of the absolute ethyl alcohol to the first sintering material used in the alcohol washing process is 0.6.
Example 5
The present example differs from example 1 in that: the coating element mixed solution and the one-time sintered material after the alcohol washing are mixed under the condition of 800 rpm.
Example 6
This example differs from example 1 in that: the coating element mixed solution is dripped into the alcohol-washed calcined material at the speed of 0.8 g/min.
Example 7
This example differs from example 1 in that: the coating element mixed solution is dripped into the alcohol-washed calcined material at the speed of 1.2 g/min.
Example 8
The present example differs from example 1 in that: the ratio of the lithium element contained in the lithium source, the tantalum element contained in the tantalum source, the zirconium element contained in the zirconium source and the silicon element contained in the silicon source is 1.1.
Example 9
The present example differs from example 1 in that: the ratio of the lithium element contained in the lithium source, the tantalum element contained in the tantalum source, the zirconium element contained in the zirconium source and the silicon element contained in the silicon source is, in order, 1.5.
Example 10
This example differs from example 1 in that: the total mass of the lithium element, the tantalum element, the zirconium element and the silicon element is 1.8wt% of the calcined material.
Example 11
This example differs from example 1 in that: the total mass of the lithium element, the tantalum element, the zirconium element and the silicon element is 1.5wt% of the calcined material.
Comparative example 1
The comparative example differs from example 1 in that: and (4) directly drying the calcined material subjected to alcohol washing and sintering for the second time without coating, namely without the step (3) and the step (4).
Comparative example 2
This comparative example differs from example 1 in that: the coating substance and manner are different.
That is, in this comparative example, the alcohol-washed calcined material obtained in the step (2) of example 1 was directly subjected to the drying in the step (5), and then the dried material was mixed with TiO 2 Mixing for 15min at the rotating speed of 600rpm in a high-speed mixer according to the mass ratio of 99. Then sintering for 6h at 280 ℃.
Comparative example 3
The comparative example differs from example 1 in that: and washing the calcined material by using absolute ethyl alcohol according to a mass ratio of 0.5.
Test example 1
The high nickel ternary positive electrode materials obtained in examples 1-11 and comparative examples 1-3 were prepared into button cells as follows:
the modified NCM electrode material was mixed and uniformly ground as an active material with a binder, polyvinylidene fluoride (PVDF), and a conductive agent, acetylene black, at a mass ratio of 90. And drying the coated electrode material in a vacuum oven at 110 ℃, rolling the dried electrode material by a double-roller machine, and drying in the vacuum oven at 120 ℃ for 12 hours. And punching the dried electrode material, weighing, and assembling the battery in a glove box. Wherein the electrolyte used for assembling the battery is prepared by using a solution containing 1M LiPF 6 DMC + EC solvent of lithium source. Wherein LiNi x Co y Mn 1-x-y O 2 The electrode plate and the lithium plate of the ternary material are respectively used as a working electrode and a counter electrode. This is achieved byAnd the ternary positive plates and the lithium plates are assembled into a button type half cell through a glove box. And carrying out alternating current impedance test, cyclic voltammetry test, charge and discharge test under different multiplying powers and stability test on the assembled battery. The charging and discharging and stability tests of the battery are to test the charging and discharging curves (1C =200mA/g) of the battery under different multiplying powers through a battery testing system.
(1) The button cells prepared from the high-nickel ternary positive electrode materials obtained in examples 1 to 11 and comparative examples 1 to 3 were subjected to performance tests in terms of specific capacity and capacity retention rate, and the results are shown in table 1, fig. 1 and fig. 2.
TABLE 1 Performance results
0.1C Capacity of Charge gram (mAh/g) 0.1C gram capacity (mAh/g) 1C gram Capacity (mAh/g) 1C, 50-cycle retention (%)
Example 1 240.7 216.8 195.1 79.33
Example 2 244.4 218.1 196.9 75.86
Example 3 238.9 214.3 193.7 75.45
Example 4 239.2 212.7 190.5 73.92
Example 5 239.4 213.8 191.9 74.88
Example 6 239.1 214.8 192.9 75.12
Example 7 239.2 215.1 193.2 74.98
Example 8 239.0 214.4 190.8 74.15
Example 9 239.7 215.3 192.9 75.20
Example 10 239.5 214.8 192.4 74.68
Example 11 239.2 215.8 194.8 75.77
Comparative example 1 237.7 206.4 179.2 51.17
Comparative example 2 238.8 207.8 181.9 59.19
Comparative example 3 236.5 205.1 175.6 50.33
As can be seen from table 1, fig. 1 and fig. 2, the button cells prepared from the high-nickel ternary positive electrode materials obtained in examples 1 to 11 are significantly better than those prepared from the high-nickel ternary positive electrode materials obtained in comparative examples 1 to 3 in both 1 cc capacity and 1c cycle retention at 50 cycles. Specifically, the specific capacity and the capacity retention rate are higher.
(2) The XRD patterns of the high-nickel ternary cathode materials obtained after coating in the examples 1-2 and the comparative examples 1-2 are shown in figure 3.
As can be seen from fig. 3, the clad layers in examples 1 to 2 of the present application exhibited a good layered structure.
(3) The results of electron microscope scanning of the high-nickel ternary positive electrode materials coated in examples 1-2 and comparative examples 1-2 are shown in fig. 4 to 11. Fig. 5 is a partially enlarged view of fig. 4, fig. 7 is a partially enlarged view of fig. 6, fig. 9 is a partially enlarged view of fig. 8, and fig. 11 is a partially enlarged view of fig. 10.
As can be seen from fig. 4 to 11: the primary particles coated in examples 1-2 are denser than those coated in comparative examples 1-2, and the corresponding secondary spheres are more rounded (the material morphology after the second sintering is better). In the above figures, the corresponding particles are all secondary particles formed by agglomeration of primary particles.
In summary, the present application provides Li by forming Li on the surface of a frit 1+x Ta 1-x Zr x SiO 5 The coating layer can be used as a physical barrier layer on the surface of the anode, so that the side reaction between the surface of the material and an electrolyte is avoided, the degradation of a surface interface structure is inhibited, the mechanical stress at the interface is relieved, the possibility of cracking is reduced, and the structure and the thermal stability of the material are improved. And the coating layer has high lithium ion conductivity, and the surface coating layer does not block Li + And the impedance is reduced by transmission, so that good rate performance is maintained.The obtained cathode material can improve the cycling stability and rate capability of the battery.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a high-nickel ternary cathode material is characterized by comprising the following steps of:
mixing a lithium source, a tantalum source, a zirconium source, a silicon source and absolute ethyl alcohol to obtain a coating element mixed solution, mixing the coating element mixed solution with a calcined material subjected to alcohol washing, drying, and sintering for the second time; wherein, the mass ratio of lithium element contained in the lithium source, tantalum element contained in the tantalum source, zirconium element contained in the zirconium source and silicon element contained in the silicon source is 1-1.5; the total mass of the lithium element, the tantalum element, the zirconium element and the silicon element is 1-2wt% of the primary sintering material;
the molecular formula of the primary sintering material is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.7 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.3; the sintering material is obtained by mixing a precursor and a lithium source and then sintering for the first time.
2. The method according to claim 1, wherein the lithium element, the tantalum element, the zirconium element and the silicon element are provided by a lithium acetate solution, a tantalum ethoxide solution, a zirconium acetate solution and an ethyl orthosilicate solution, respectively.
3. The preparation method according to claim 2, wherein the lithium acetate solution, tantalum ethoxide solution, zirconium acetate solution and tetraethoxysilane solution are mixed with absolute ethyl alcohol to obtain a coating element mixed solution, and then mixed with the alcohol-washed calcined material; wherein the mass ratio of the absolute ethyl alcohol to the primary sintering material is 0.6-1.
4. The method according to claim 3, wherein the coating element mixed solution and the alcohol-washed one-shot material are mixed under stirring.
5. The preparation method according to claim 1, wherein the mass ratio of the absolute ethyl alcohol to the primary fuel used in the alcohol washing process is 0.6-1.2.
6. The method as claimed in claim 1, wherein the drying is carried out at 30-50 ℃ and the water content of the dried material after drying is less than or equal to 0.2wt%.
7. The method of claim 1, wherein the second sintering is performed at 600-700 ℃ for 1-4 hours.
8. The method according to any one of claims 1 to 7, wherein the primary sintering material is prepared by:
mixing the precursor and a lithium source according to a molar ratio of 1.04-1.08, and then sintering at 700-800 ℃ for 10-12h;
wherein the molecular formula of the precursor is Ni x Co y Mn z (OH) 2 ，x+y+z=1，0.7≤x≤1，0≤y≤0.3；
The lithium source is lithium hydroxide.
9. A high-nickel ternary positive electrode material, which is prepared by the preparation method of any one of claims 1 to 8.
10. A battery prepared from a feedstock comprising the high-nickel ternary positive electrode material of claim 9.
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