CN111916702B - Coated modified cathode material, preparation method thereof and lithium ion battery - Google Patents

Coated modified cathode material, preparation method thereof and lithium ion battery Download PDF

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CN111916702B
CN111916702B CN202010725717.8A CN202010725717A CN111916702B CN 111916702 B CN111916702 B CN 111916702B CN 202010725717 A CN202010725717 A CN 202010725717A CN 111916702 B CN111916702 B CN 111916702B
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nickel
core
cathode material
coated modified
phosphate
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CN111916702A (en
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袁晶
曾汉民
何巍
刘金成
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Eve Energy 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a coated modified cathode material, a preparation method thereof and a lithium ion battery. The coating modified cathode material comprises a core and a coating layer coated on the surface of the core, wherein the coating layer comprises a nickel ion adsorption material and a side reaction product adsorption material, and the core comprises a nickel-containing cathode material. The preparation method comprises the following steps: and mixing the core, the nickel ion adsorption material and the side reaction product adsorption material in a solid phase to obtain a mixture, and sintering the mixture in an oxygen-containing atmosphere to obtain the coated modified cathode material, wherein the core comprises a nickel-containing cathode material. The coating layer of the coating modified cathode material provided by the invention can adsorb gas generated by side reaction of a high-nickel material and dissolved nickel ions, so that the cycle performance of the cathode material can be improved, and the stored gas and the dissolved nickel ions are improved.

Description

Coated modified cathode material, preparation method thereof and lithium ion battery
Technical Field
The invention belongs to the technical field of batteries, relates to a positive electrode material, a preparation method thereof and a lithium ion battery, and particularly relates to a coated modified positive electrode material, a preparation method thereof and a lithium ion battery.
Background
The trace moisture contained in the lithium ion battery can react with electrolyte lithium hexafluorophosphate to generate HF, so that metal parts in the battery can be corroded, side reactions in the battery can be catalyzed, the gas production of the battery is increased, and the safety and the performance of the battery are influenced. The high nickel material is rich in nickel, so that the dissolution of transition metal ions is serious in the use process of the material, and the dissolved metal ions are reduced and deposited on a negative electrode, so that the stability of an SEI (solid electrolyte interphase) film is influenced, and the gas generation and performance attenuation of a battery are caused. Therefore, the development of a high-nickel anode material capable of inhibiting the gas generation of the battery and the dissolution of transition metal ions has important significance for the development of the lithium ion battery. The material can be modified generally, including doping and cladding, dopingThe surface coating can improve the surface characteristics of the anode material, avoid or reduce the direct contact of the material and the electrolyte, reduce the side reaction of the electrolyte and the anode material, and inhibit the dissolution of transition metal elements in the charge and discharge processes of the material, thereby reducing the deposition of the transition metal on the cathode. In the coating modification method, a common material factory carries out B on the high nickel material2O3Coating, however, B is subject to exfoliation and dissolution after cycling and storage at high temperatures for a period of time.
CN109428077A discloses a method for preparing a high nickel cathode material and a high nickel cathode material obtainable by the method. The method comprises the following steps: (i) doping the substrate with a boron-containing compound, thereby obtaining a boron-doped substrate; and (ii) cladding the boron doped matrix as follows: washing the coated boron-doped substrate with an aqueous solution of a boron-containing compound at a temperature greater than 10 ℃, followed by heat treatment, thereby forming the high-nickel cathode material.
CN110010865A discloses a lithium chloroborate coated high-nickel anode material, a preparation method thereof and a lithium battery, wherein the high-nickel anode material is soaked in a lithium chloroborate solution, solid-liquid separation is carried out under the condition of controlling the humidity, and the solid is taken to be dried, crushed and roasted to obtain the lithium chloroborate coated high-nickel anode material.
CN110931797A discloses a high nickel cathode material with a composite coating layer and a preparation method thereof, the preparation method comprises the following steps: (1) uniformly mixing the high-nickel anode material and the nano coating material, sintering at high temperature in a preheated muffle furnace under the oxygen atmosphere, cooling, crushing and sieving to obtain the high-nickel anode material coated by the nano material; (2) adding the high-nickel anode material coated by the nano material into deionized water in which a soluble lithium compound is dissolved, uniformly stirring, slowly adding soluble phosphate, uniformly stirring, carrying out vacuum filtration, drying and burning in a kiln, cooling, crushing, and sieving to obtain the high-nickel anode material with the composite coating layer.
However, the above methods have a problem that elution of nickel ions and deposition of the negative electrode are to be further reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a coated modified cathode material, a preparation method thereof and a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a coated modified cathode material, including a core and a coating layer coated on a surface of the core, where the coating layer includes a nickel ion adsorbing material and a side reaction product adsorbing material, and the core includes a nickel-containing cathode material.
The coated modified anode material provided by the invention has good adsorption capacity on nickel ions dissolved out from a high-nickel anode material through the nickel ion adsorption material, has good adsorption on gas generated by side reaction through the side reaction product adsorption material, and can effectively improve the cycle performance and storage gas generation of the material and reduce the dissolution of the nickel ions through the mutual cooperation of the two materials.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferred embodiment of the present invention, the nickel ion adsorbing material includes any one or a combination of at least two of aluminum phosphate, lithium phosphate, sodium phosphate, potassium phosphate, magnesium phosphate, calcium phosphate, strontium phosphate, and barium phosphate.
Preferably, the nickel ion adsorbing material has a median particle size of 0.8 to 1 μm, such as 0.8 μm, 0.85 μm, 0.9 μm, 0.95 μm, or 1 μm, and the like. In the invention, the purpose of adopting the median diameter is that the coating material can be well filled into the gaps on the surface of the core material, and can penetrate into the surface layer and deep parts of the core material in the subsequent sintering process to fill the crystal lattice gaps of the core material, so as to modify the surface and ensure that the coating is more compact.
Preferably, the mass fraction of the nickel ion adsorbing material is 0.05-0.3%, such as 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, or the like, based on 100% by mass of the core. In the invention, if the mass fraction of the nickel ion adsorbing material is too high, the coating layer is too thick, and the gram capacity exertion of the core material is influenced; if the mass fraction of the nickel ion-adsorbing material is too low, the coating effect is not good, and the eluted nickel ions cannot be effectively adsorbed.
Preferably, the side reaction product sorbent material comprises any one of barium titanate, magnesium titanate, calcium titanate, strontium titanate, lanthanum manganate or lanthanum nickelate, or a combination of at least two thereof.
Preferably, the side reaction product adsorbent material has a median particle size of 0.5 to 0.7 μm, such as 0.5 μm, 0.55 μm, 0.6 μm, 0.65 μm, 0.7 μm, or the like. In the present invention, the median particle size is used for the purpose of further filling the material into the smaller surface voids of the material, so that the coating is more compact.
Preferably, the mass fraction of the side reaction product adsorbent material is 0.05-0.3%, such as 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, or the like, based on 100% by mass of the core. In the invention, if the mass fraction of the side reaction product adsorption material is too high, the coating layer is too thick, and the gram capacity exertion of the core material is influenced; if the mass fraction of the side reaction product adsorbing material is too low, the coating effect is poor, and the side reaction product cannot be effectively adsorbed.
As a preferable technical solution of the present invention, the nickel-containing cathode material is a high nickel cathode material. In the present invention, the high nickel positive electrode material means that the molar content of nickel in the metal elements other than lithium in the positive electrode material is 60% or more.
Preferably, the molecular formula of the high-nickel cathode material is LiNixCoyMZO2Where 0.6. ltoreq. x.ltoreq.1, for example x is 0.6, 0.7, 0.8, 0.9 or 1, etc., x + y + z is 1, and M is manganese and/or aluminum. In the present invention, y and z are both non-negative numbers.
Preferably, the particle size median diameter of the high nickel positive electrode material is 9-12 μm, such as 9 μm, 10 μm, 11 μm, or 12 μm, and the like.
In a second aspect, the present invention provides a method for preparing a high nickel cathode material according to the first aspect, the method comprising the steps of:
and mixing the core, the nickel ion adsorption material and the side reaction product adsorption material in a solid phase to obtain a mixture, and sintering the mixture in an oxygen-containing atmosphere to obtain the coated modified cathode material, wherein the core comprises a nickel-containing cathode material.
The preparation method provided by the invention is simple to operate, short in flow, free of complex liquid phase reaction, capable of obtaining a product only through solid phase reaction, stable in coating of the coating layer and not easy to fall off from the surface of the core.
In the method provided by the invention, the sintering is carried out in the oxygen-containing atmosphere, and the nickel ion adsorption material and the side reaction product adsorption material can not only coat the surface of the core material, but also can penetrate into the deep part of the surface in the sintering process to fill the crystal lattice gap of the core material, so that the coating is more compact and stable.
In a preferred embodiment of the present invention, the mixture is sieved before sintering.
In a preferred embodiment of the present invention, the oxygen-containing atmosphere has an oxygen volume concentration of 80% or more, for example, 80%, 82%, 84%, 86%, 88%, or 90%.
Preferably, the mixture is placed in a sagger for sintering.
As a preferred embodiment of the present invention, the sintering temperature is 200-600 ℃, such as 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃.
Preferably, the sintering time is 4-15h, such as 4h, 6h, 8h, 10h, 12h, 13h or 15h, etc.
As a preferred technical solution of the present invention, the preparation method further comprises: after the sintering, the sintered product was cooled, crushed and sieved.
In the preparation method provided by the invention, the nickel ion adsorbing material comprises aluminum phosphate.
Preferably, the nickel ion adsorbing material has a median particle size of 0.8 to 1 μm, such as 0.8 μm, 0.85 μm, 0.9 μm, 0.95 μm, or 1 μm, and the like.
Preferably, the mass fraction of the nickel ion adsorbing material is 0.05-0.3%, such as 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, or the like, based on 100% by mass of the core.
Preferably, the side reaction product adsorbent material comprises barium titanate.
Preferably, the side reaction product adsorbent material has a median particle size of 0.5 to 0.7 μm, such as 0.5 μm, 0.55 μm, 0.6 μm, 0.65 μm, 0.7 μm, or the like.
Preferably, the mass fraction of the side reaction product adsorbent material is 0.05-0.3%, such as 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, or the like, based on 100% by mass of the core.
In the preparation method provided by the invention, the nickel-containing cathode material is a high-nickel cathode material.
Preferably, the molecular formula of the high-nickel cathode material is LiNixCoyMnZO2Where 0.6. ltoreq. x.ltoreq.1, for example x is 0.6, 0.7, 0.8, 0.9 or 1, etc., x + y + z is 1, and M is manganese and/or aluminum.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
mixing the core, the nickel ion adsorbing material and the side reaction product adsorbing material in a solid phase manner to obtain a mixture, sieving the mixture, and sintering the mixture in a sagger at the temperature of 200-600 ℃ in an oxygen-containing atmosphere for 4-15 hours to obtain the coated modified anode material;
the core is a high-nickel anode material, and the molecular formula of the high-nickel anode material is LiNixCoyMZO2Wherein x is more than or equal to 0.6 and less than or equal to 1, x + y + z is 1, and M is manganese and/or aluminum;
the nickel ion adsorbing material is aluminum phosphate, and the side reaction product adsorbing material is barium titanate;
the oxygen volume concentration of the oxygen-containing atmosphere is more than or equal to 80 percent.
In a third aspect, the present invention provides a lithium ion battery comprising the coated modified cathode material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the coating layer of the coating modified cathode material provided by the invention can adsorb gas generated by side reaction of a high-nickel material and dissolved nickel ions, so that the cycle performance of the cathode material can be improved, and the stored gas and the dissolved nickel ions are improved. The gram capacity of the coated modified cathode material provided by the invention can reach 200.3mAh/g, the capacity retention rate after charging and discharging cycles for 200 times can reach 94.2%, the volume increase rate after the storage at the high temperature of 70 ℃ for 30 days can be as low as 38%, and the nickel ion dissolution after the storage at the high temperature of 70 ℃ for 30 days can be as low as 48 ppm.
(2) The preparation method provided by the invention is simple to operate, short in flow, free of complex liquid phase reaction, capable of obtaining a product only through solid phase reaction, stable in coating of the coating layer and not easy to fall off from the surface of the core.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
The embodiment provides a preparation method of a coated modified cathode material, which specifically comprises the following steps:
the method comprises the steps of uniformly mixing a high-nickel anode material, aluminum phosphate and barium titanate to obtain a mixture, sieving the mixture, sintering the sieved mixture in a muffle furnace in a sagger under an oxygen atmosphere (the oxygen volume concentration is 85%), wherein the sintering temperature is 500 ℃, the sintering time is 6 hours, and then cooling, crushing and sieving a sintered product to obtain the coated modified anode material.
The coated modified cathode material provided by the embodiment comprises a high-nickel cathode material core and a coating layer coated on the surface of the core. The chemical formula of the high-nickel anode material is LiNi0.8Co0.1Mn0.1O2The median particle size of the high-nickel anode material core is 9-12 mu m. The coating layer is composed of aluminum phosphate and barium titanate, the median particle size of the aluminum phosphate is 0.9 mu m, and the median particle size of the barium titanate is 0.6 mu m; the mass fraction of the aluminum phosphate is 0.20 percent and the mass fraction of the barium titanate is 0.15 percent, wherein the mass of the high-nickel cathode material core is 100 percent.
The performance test results of the coated modified cathode material provided in this example are shown in table 1.
Example 2
The embodiment provides a preparation method of a coated modified cathode material, which specifically comprises the following steps:
the method comprises the steps of uniformly mixing a high-nickel anode material, sodium phosphate and magnesium titanate to obtain a mixture, sieving the mixture, sintering the sieved mixture in a muffle furnace in a sagger under an oxygen atmosphere (the oxygen volume concentration is 90%), wherein the sintering temperature is 400 ℃, the sintering time is 10 hours, and then cooling, crushing and sieving a sintered product to obtain the coated modified anode material.
The coated modified cathode material provided by the embodiment comprises a high-nickel cathode material core and a coating layer coated on the surface of the core. The chemical formula of the high-nickel anode material is LiNi0.8Co0.1Mn0.1O2The median particle size of the high-nickel anode material core is 9-12 mu m. The coating layer is composed of sodium phosphate and magnesium titanate, the median particle size of the sodium phosphate is 0.85 mu m, and the median particle size of the magnesium titanate is 0.65 mu m; the mass fraction of the sodium phosphate is 0.15 percent and the mass fraction of the magnesium titanate is 0.20 percent, based on 100 percent of the mass of the high-nickel anode material core.
The performance test results of the coated modified cathode material provided in this example are shown in table 1.
Example 3
The embodiment provides a preparation method of a coated modified cathode material, which specifically comprises the following steps:
the method comprises the steps of uniformly mixing a high-nickel anode material, magnesium phosphate and strontium titanate to obtain a mixture, sieving the mixture, sintering the sieved mixture in a muffle furnace in a sagger under an oxygen atmosphere (oxygen volume concentration is 80%), wherein the sintering temperature is 200 ℃, the sintering time is 15h, cooling, crushing and sieving a sintered product to obtain the coated modified anode material.
The coated modified cathode material provided by the embodiment comprises a high-nickel cathode material core and a coating layer coated on the surface of the core. The chemical formula of the high-nickel anode material is LiNi0.6Co0.2Mn0.2O2The median particle size of the high-nickel anode material core is 9-12 mu m. The coating layer is composed of magnesium phosphate and strontium titanate, the median particle size of the magnesium phosphate is 0.8 mu m, and the median particle size of the strontium titanate is 0.5 mu m; the mass fraction of the magnesium phosphate is 0.05 percent and the mass fraction of the strontium titanate is 0.3 percent, wherein the mass of the high-nickel cathode material core is 100 percent.
The performance test results of the coated modified cathode material provided in this example are shown in table 1.
Example 4
The embodiment provides a preparation method of a coated modified cathode material, which specifically comprises the following steps:
the method comprises the steps of uniformly mixing a high-nickel anode material, aluminum phosphate and barium titanate to obtain a mixture, sieving the mixture, sintering the sieved mixture in a muffle furnace in a sagger under an oxygen atmosphere (oxygen volume concentration is 80%), wherein the sintering temperature is 600 ℃, the sintering time is 4h, cooling, crushing and sieving a sintered product to obtain the coated modified anode material.
The coated modified cathode material provided by the embodiment comprises a high-nickel cathode material core and a coating layer coated on the surface of the core. The chemical formula of the high-nickel anode material is LiNi0.6Co0.2Al0.2O2The median particle size of the high-nickel anode material core is 9-12 mu m. The coating layer is composed of aluminum phosphate and barium titanate, the median particle size of the aluminum phosphate is 1 mu m, and the median particle size of the barium titanate is 0.7 mu m; the mass fraction of the aluminum phosphate is 0.3% and the mass fraction of the barium titanate is 0.05% based on 100% of the mass of the high-nickel cathode material core.
The performance test results of the coated modified cathode material provided in this example are shown in table 1.
Example 5
The coating modified cathode material provided in this example is the same as the coating modified cathode material provided in example 1, except that the mass fraction of aluminum phosphate is 0.5% based on 100% by mass of the core of the high nickel cathode material.
The performance test results of the coated modified cathode material provided in this example are shown in table 1.
Example 6
The coating-modified cathode material provided in this example is the same as the coating-modified cathode material provided in example 1, except that the mass fraction of aluminum phosphate is 0.03% based on 100% by mass of the core of the high-nickel cathode material.
The performance test results of the coated modified cathode material provided in this example are shown in table 1.
Example 7
The coating-modified cathode material provided in this example is the same as the coating-modified cathode material provided in example 1, except that the mass fraction of barium titanate is 0.5% based on 100% of the mass of the high-nickel cathode material core.
The performance test results of the coated modified cathode material provided in this example are shown in table 1.
Example 8
The coating-modified positive electrode material provided in this example was the same as the coating-modified positive electrode material provided in example 1, except that the mass fraction of barium titanate was 0.03% based on 100% by mass of the high-nickel positive electrode material core.
The performance test results of the coated modified cathode material provided in this example are shown in table 1.
Comparative example 1
The coated modified positive electrode material provided in this comparative example was the same as the coated modified positive electrode material provided in example 1, except that the coating layer was composed of only aluminum phosphate, and did not contain barium titanate, and the mass fraction of aluminum phosphate was 0.35% based on 100% by mass of the high-nickel positive electrode material core.
The performance test results of the coated modified cathode material provided in this comparative example are shown in table 1.
Comparative example 2
The coating-modified positive electrode material provided in this comparative example was the same as the coating-modified positive electrode material provided in example 1, except that the coating layer was composed of only barium titanate, and did not contain aluminum phosphate, and the mass fraction of barium titanate was 0.35% based on 100% by mass of the high-nickel positive electrode material core.
The performance test results of the coated modified cathode material provided in this comparative example are shown in table 1.
Comparative example 3
The coating modified cathode material provided by the present comparative example consists of B having a median particle diameter of 0.8 μm except for the coating layer2O3The composition of B is calculated by taking the mass of the high nickel anode material core as 100 percent2O3Except for 0.35%, the other aspects are the same as those of the coated modified positive electrode material provided in example 1.
The performance test results of the coated modified cathode material provided in this comparative example are shown in table 1.
Test method
The coated modified positive electrode materials provided in the examples and comparative examples were used as positive electrode active materials to prepare test cells for electrochemical tests. The preparation method of the test battery comprises the following steps: adding a certain amount of NMP into a conductive agent and a binder according to a certain proportion, fully stirring in a vacuum stirrer, adding a positive active substance (the positive active substance: the binder: the conductive agent: 95:2:5), uniformly stirring to prepare slurry, coating the slurry on an aluminum foil, drying and rolling to prepare a positive plate, welding an aluminum strip tab and mixing with pre-prepared stoneLaminating the black cathode plate and the diaphragm, then packaging the core package into a soft package aluminum plastic film of 396389 type, baking for 8h in vacuum, and using LiPF6Injecting electrolyte solution of/EC + DEC + DMC (the volume ratio of EC, DEC and DMC is 1:1:1), aging at normal temperature for 24h, forming, aging at high temperature, evacuating, sealing, and grading to obtain the battery. The gram volume, cycle and high temperature storage test is carried out by using a Xinwei tester, and the test method is as follows:
gram volume: a thermostat at 25 ℃, charging to 4.25V at a constant current and a constant voltage of 0.33 ℃, and discharging to 2.8V at a constant current of 0.33 ℃;
and (3) circulation: charging to 4.25V at constant current and constant voltage of 1C and discharging to 2.8V at constant current of 1C in a constant temperature box at 45 ℃, and circulating for 200 weeks;
and (3) high-temperature storage: 033C is charged at constant current and constant voltage to 4.25V, then the battery cell is placed in a constant temperature box at 70 ℃ for storage for 30 days, the volume of the battery cell is tested by adopting a drainage method before and after storage to represent the gas generated by the material, and the battery cell is discharged for electricity, and negative plate powder is taken to test the nickel ion dissolution condition by adopting ICP after storage.
The test results are shown in the following table:
TABLE 1
Figure BDA0002601584370000111
It can be known from the above examples and comparative examples that the coating layers of the coated and modified cathode materials provided in examples 1 to 4 can adsorb gas generated by the side reaction of the high nickel material and dissolved nickel ions, so that the cycle performance of the cathode material can be improved, and the storage gas generation and the nickel ion dissolution can be improved.
Example 5 because the nickel ion adsorbing material, aluminum phosphate, was too high, the material had a lower gram capacity.
In example 6, the nickel ion adsorbing material aluminum phosphate is too low, so that the nickel ion adsorbing effect is poor, the nickel ions are dissolved out more, and the cycle performance is poor.
Example 7 the gram capacity of the material is low because the side reaction product, namely the absorbing material lithium titanate, is too high.
Example 8 the side reaction product, namely the adsorption material lithium titanate, is too low, so that the improvement of gas generation during high-temperature storage is not obvious.
In comparative example 1, the side reaction product, namely, lithium titanate, is not used in the coating layer, so that the material after high-temperature storage generates more gas, and the increase rate of the cell volume is higher.
Comparative example 2 because the nickel ion adsorbing material aluminum phosphate was not used in the clad layer, the nickel ion was eluted seriously after the storage at high temperature.
Comparative example 3 because B is used as the coating layer2O3The coating layer causes poor material cycle performance, and gas generation in high-temperature storage and nickel ion dissolution are serious.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (15)

1. The coated modified cathode material is characterized by comprising a core and a coating layer coated on the surface of the core, wherein the coating layer comprises a nickel ion adsorbing material and a side reaction product adsorbing material, and the core comprises a nickel-containing cathode material;
the nickel ion adsorbing material comprises any one or a combination of at least two of aluminum phosphate, lithium phosphate, sodium phosphate, potassium phosphate, magnesium phosphate, calcium phosphate, strontium phosphate or barium phosphate;
the side reaction product adsorbing material comprises any one or a combination of at least two of barium titanate, magnesium titanate, calcium titanate, strontium titanate, lanthanum manganate or lanthanum nickelate;
the mass fraction of the nickel ion adsorbing material is 0.05-0.3% by taking the mass of the core as 100%;
the mass fraction of the side reaction product adsorbing material is 0.05-0.3% based on 100% of the mass of the core.
2. The coated modified positive electrode material according to claim 1, wherein the nickel ion-adsorbing material has a median particle diameter of 0.8 to 1 μm.
3. The coated modified positive electrode material according to claim 1, wherein the side-reaction-product-adsorbing material has a median particle diameter of 0.5 to 0.7 μm.
4. The coated modified cathode material according to claim 1 or 2, wherein the nickel-containing cathode material is a high nickel cathode material.
5. The coated modified cathode material according to claim 4, wherein the molecular formula of the high-nickel cathode material is LiNixCoyMZO2Wherein x is more than or equal to 0.6 and less than or equal to 1, x + y + z is 1, and M is manganese and/or aluminum.
6. The coated modified positive electrode material according to claim 5, wherein the high nickel positive electrode material has a particle size median diameter of 9 to 12 μm.
7. A method of preparing the coated modified positive electrode material of any one of claims 1 to 6, comprising the steps of:
and mixing the core, the nickel ion adsorption material and the side reaction product adsorption material in a solid phase to obtain a mixture, and sintering the mixture in an oxygen-containing atmosphere to obtain the coated modified cathode material, wherein the core comprises a nickel-containing cathode material.
8. The method of claim 7, wherein the mixture is sieved prior to sintering.
9. The method according to claim 7 or 8, wherein the oxygen-containing atmosphere has an oxygen volume concentration of 80% or more.
10. The method of claim 7 or 8, wherein the mixture is placed in a sagger for sintering.
11. The method as claimed in claim 7 or 8, wherein the sintering temperature is 200-600 ℃.
12. The method according to claim 7 or 8, wherein the sintering time is 4 to 15 hours.
13. The production method according to claim 7 or 8, characterized by further comprising: after the sintering, the sintered product was cooled, crushed and sieved.
14. The method for preparing according to claim 7 or 8, characterized in that it comprises the following steps:
mixing the core, the nickel ion adsorbing material and the side reaction product adsorbing material in a solid phase manner to obtain a mixture, sieving the mixture, and sintering the mixture in a sagger at the temperature of 200-600 ℃ in an oxygen-containing atmosphere for 4-15 hours to obtain the coated modified anode material;
the core is a high-nickel anode material, and the molecular formula of the high-nickel anode material is LiNixCoyMZO2Wherein x is more than or equal to 0.6 and less than or equal to 1, x + y + z is 1, and M is manganese and/or aluminum;
the nickel ion adsorbing material is aluminum phosphate, and the side reaction product adsorbing material is barium titanate;
the oxygen volume concentration of the oxygen-containing atmosphere is more than or equal to 80 percent.
15. A lithium ion battery comprising the coated modified positive electrode material according to any one of claims 1 to 6.
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