CN111600024B - Aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material and preparation method and application thereof - Google Patents

Aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material and preparation method and application thereof Download PDF

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CN111600024B
CN111600024B CN202010273887.7A CN202010273887A CN111600024B CN 111600024 B CN111600024 B CN 111600024B CN 202010273887 A CN202010273887 A CN 202010273887A CN 111600024 B CN111600024 B CN 111600024B
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positive electrode
ternary
aluminum oxide
lithium battery
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CN111600024A (en
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孙伟
葛鹏
胡岳华
纪效波
张丽敏
赵文青
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Central South University
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 invention discloses an alumina-coated Ni-Co-Mn ternary lithium battery positive electrode material and a preparation method and application thereof. The method overcomes the defects that the alumina coating of the alumina-coated Ni-Co-Mn ternary positive electrode material prepared by the existing hydrolysis precipitation method is uneven and too thick, the surface activity is damaged by introducing acid media and water, the interface structure is unstable and the like, and overcomes the defects that the existing atomic deposition method has high equipment cost and is difficult to industrially produce, and the prepared alumina-coated Ni-Co-Mn ternary positive electrode material has higher electrochemical activity and cycling stability compared with the existing similar materials.

Description

Aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material and preparation method and application thereof
Technical Field
The invention relates to a Ni-Co-Mn ternary lithium battery positive electrode material, in particular to a Ni-Co-Mn ternary lithium battery positive electrode material with a uniform and compact alumina coating layer, a preparation method and application thereof, and belongs to the technical field of lithium ion batteries.
Background
The rapid development of the intelligent society cannot avoid the sustainable supply of energy, and as an important energy transfer and storage system, the lithium battery is successfully applied to daily production and life. Currently, there are various cathode materials on the market, mainly including lithium cobaltate (LiCoO)2) Lithium iron phosphate (LiFePO)4) Ni-Co-Mn ternary (LiNi)xCoyMnzO2) And the like. Wherein the lithium cobaltate material is stable in charge and discharge and generates electricityThe production process is simple, but the cycle life of the material is short, and the price of cobalt resources is gradually increased, so that the market share of the material is gradually compressed. The lithium iron phosphate material has the characteristics of high stability, long cycle stability and the like, but the material has lower energy density and can be effectively applied to a large-space system, such as an electric motor coach and the like. However, in the process of new energy automobile development, the small automobiles are the main force in the market, which results in that the lithium iron phosphate battery system with lower specific energy cannot be well developed and used.
In recent years, the market share of ternary positive electrode materials in the field of electric vehicles has been rising year by year, mainly due to the higher specific energy and the relatively low price of ternary positive electrode materials, which meets the urgent need of long endurance for drivers. However, the internal electrochemical reaction of the ternary cathode material at high voltage is not ideal, mainly because the ternary cathode material is dissolved at high voltage. Therefore, the surface of the ternary cathode material is coated, and an effective compounding method is provided. Alumina (Al)2O3) The ternary positive electrode material is an inactive oxide, can capture HF ions when being in the electrolyte, thereby inhibiting the dissolution of the ternary positive electrode material and having an excellent coating effect. Most of the conventional coating methods adopt hydroxyl (OH)-) The precipitation method carries out surface deposition, and inevitably introduces water phase, so that the electrode of the material is damaged. The atomic deposition method can obtain a more uniform alumina coating layer, but the required equipment cost is higher, and the method is not beneficial to large-scale industrial production application. In view of the above, it is very necessary to provide a preparation method of a novel alumina-coated Ni-Co-Mn ternary lithium battery positive electrode material.
Disclosure of Invention
Aiming at the defects of uneven and excessively thick aluminum oxide coating, water phase introduction, unstable interface structure and the like of the aluminum oxide coated Ni-Co-Mn ternary lithium battery anode material in the prior art, the first purpose of the invention is to provide the aluminum oxide coated Ni-Co-Mn ternary lithium battery anode material which has an uniform, compact and nanometer thickness aluminum oxide coating layer and is stable in interface structure.
The second purpose of the invention is to provide a method for preparing the aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material, which is simple, effective, strong in controllability, fast and capable of being produced in a large scale, and overcomes the defects of nonuniform aluminum oxide coating, excessive thickness, water introduction, unstable interface structure and the like of the aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material prepared by the conventional hydroxyl precipitation method, and the defects of high equipment cost and difficulty in industrial production of the conventional atomic deposition method.
The third purpose of the invention is to provide an application of the aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material, wherein the aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material has a uniform and compact aluminum oxide coating layer, has a stable interface structure, shows better electrochemical performance, and has electrochemical performance such as high multiplying power, long cycle and the like compared with the existing aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material.
In order to achieve the technical purpose, the invention provides a preparation method of an aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material, which comprises the steps of dissolving an aluminate coupling agent in a solvent, uniformly mixing the aluminate coupling agent with the Ni-Co-Mn ternary lithium battery positive electrode material, and volatilizing to remove the solvent to obtain a precursor material; and calcining the precursor material in an oxygen-containing atmosphere to obtain the catalyst.
As a preferable scheme, the aluminate coupling agent comprises trimethyl aluminate, triisopropyl aluminate, tribenzyl aluminate, distearoyl isopropyl aluminate, DL-411-A, DL-411-AF, DL-411-D, DL-411-DF, DL-411-B, DL-411-C, DL-A, DL-412-B, DL-812, DL-414, DL-481, DL-881, DL-482, DL-882, DL-429, DL-467, DL-461, DL-491-A, DL-471, DL-472, DL-492, F-1, F-2, F-3, F-4, L-1A, L-1H, L-3A, At least one of H-4A. The aluminate coupling agents simultaneously contain hydrophilic and hydrophobic functional groups, have strong adsorption performance on the surfaces of nickel-cobalt-manganese ternary positive electrode material particles, can form a tightly attached aluminum-containing organic layer by adsorption on the surfaces of powder materials in the liquid phase mixing process, and are directly coupled with trace carboxyl or hydroxyl adsorbed on the surfaces of the nickel-cobalt-manganese ternary positive electrode materials through the alkoxy of the aluminate coupling agents under the chemical action, so that a tight and uniform aluminum-containing organic coating layer can be formed on the surfaces of the Ni-Co-Mn ternary positive electrode materials through chemical bonding, and a uniform and complete aluminum oxide coating layer can be further formed on the surfaces of the ternary positive electrode materials through pyrolysis; and the titanium dioxide and the Ni-Co-Mn ternary cathode material are chemically bonded on the surface and generated in situ, and have a stable interface structure.
As a preferable scheme, the mass ratio of the aluminate coupling agent to the Ni-Co-Mn ternary lithium battery positive electrode material is 1: 1-1: 100; the thickness of the aluminum oxide can be adjusted within the range of 2 nm-200 nm by controlling the mass ratio of the aluminate coupling agent to the Ni-Co-Mn ternary lithium battery positive electrode material; as a preferable scheme, the mass ratio of the aluminate coupling agent to the Ni-Co-Mn ternary lithium battery positive electrode material is 1: 10-1: 50, and the thickness of the aluminum oxide coating layer is adjusted within the range of 3-50 nm.
As a preferred scheme, the solvent comprises at least one of gasoline, ethyl acetate, toluene and turpentine. The preferable solvent has good solubility to the aluminate coupling agent, is easy to remove, and can improve the uniformity of the aluminate coupling agent in the surface coating of the Ni-Co-Mn ternary lithium battery anode material.
As a preferable scheme, the oxygen-containing gas is a mixed gas of oxygen and nitrogen, and the volume percentage of the oxygen is 50-95%; the preferred oxygen volume percentage is 75% to 90%. The oxygen content of the oxygen-containing gas mainly affects the pyrolysis rate of the aluminate coupling agent. When the oxygen concentration is too low, the pyrolysis nucleation rate of the aluminate coupling agent is slow, and the aluminum oxide coating layer has more defects. When the oxygen concentration is too high, the pyrolysis rate is too fast, the organic aluminum source is rapidly decomposed to form aluminum oxide, and the aluminum oxide nanoparticles are gradually agglomerated into spherical microparticles due to large surface energy, so that the aluminum oxide coating layer is difficult to form effectively.
As a preferred embodiment, the calcination conditions are: heating to 300-800 ℃ at a heating rate of 1-15 ℃/min, and preserving heat for 1-24 h. The heating rate is preferably 3-10 ℃/min, and the preferred calcining temperature is 350-750 ℃; the preferable calcination time is 1-15 h. As a further preferred embodiment, the calcination conditions are: heating to 400-700 ℃ at a heating rate of 3-10 ℃/min, and preserving heat for 3-8 h. The choice of calcination conditions is critical to the formation of the alumina coating. When the calcining temperature is too high and the calcining time is too long, the crystal structure of the Ni-Co-Mn ternary lithium battery positive electrode material is influenced, the electrochemical activity of the bulk material is damaged, and the electrochemical performance of the material is reduced. When the calcination temperature is too low and the calcination time is too short, the aluminate coupling agent is difficult to be effectively pyrolyzed, or the formed coating layer has low crystallinity and is difficult to form an effective coating layer.
The invention provides an aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material which is prepared by the method.
The invention also provides an application of the aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material as a lithium ion battery positive electrode material.
The proportion of nickel, cobalt and manganese in the Ni-Co-Mn ternary lithium battery positive electrode material is mainly 1/1/1, 8/1/1, 4/2/4, 3/3/3, 5/2/3, 70/15/15 and other Ni-Co-Mn ternary lithium battery positive electrode materials common in the field, and the materials are all suitable for coating modification by adopting aluminum oxide in the technical scheme of the invention.
The solvent volatilization and removal process of the invention comprises the steps of distilling at low temperature under reduced pressure to remove toluene, and then carrying out freeze drying treatment.
The aluminum oxide coated Ni-Co-Mn ternary lithium battery anode material is used as an electrode anode material and is assembled into an electrochemical energy storage device by adopting the prior art.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material provided by the invention has an aluminum oxide coating layer with complete, uniform, compact and nanometer thickness and stable interface chemical bonds, can effectively inhibit the surface dissolution of the positive electrode material, improves the interface structure stability of the positive electrode material, prevents the electrode material from being corroded by electrolyte and the like, shows excellent electrochemical activity, and can obtain a lithium battery device with high cycle stability.
The preparation method of the aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material provided by the invention is simple, effective, strong in controllability, fast and capable of realizing large-scale production. The aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material prepared by the method has an aluminum oxide coating layer with uniform, compact and complete thickness of nanometer, and the interface structure is stable, so that the defects of nonuniform aluminum oxide coating, excessive thickness, water introduction, unstable interface structure and the like of the aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material prepared by the conventional hydroxyl precipitation method and the defects of high equipment cost and difficulty in industrial production of the conventional atomic deposition method are overcome.
Drawings
FIG. 1 is a transmission electron microscope picture of the Ni-Co-Mn ternary material @ alumina composite material prepared in example 1;
FIG. 2 is a graph of the cycle performance of the Ni-Co-Mn ternary material @ alumina composite made in example 1;
FIG. 3 is a graph of the cycle performance of the Ni-Co-Mn ternary material @ alumina composite made in example 2;
FIG. 4 is a plot of the coulombic efficiency of the Ni-Co-Mn ternary material @ alumina composite made in example 3;
FIG. 5 is a graph showing the rate of formation of Ni-Co-Mn ternary material @ alumina composite obtained in example 4.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
Dissolving 0.2g of commercial trimethyl aluminate in 100ml of toluene, magnetically stirring for 30min to obtain a clear solution, adding 10g of 1/1/1 type ternary material into the solution, stirring for 1h, distilling the material at low temperature under reduced pressure to remove toluene, placing the obtained material in a freeze dryer for freeze drying, and finally obtaining the mixed material of the dried trimethyl aluminate and the ternary material. At 90% oxygenCalcining at 500 deg.C for 2h in a concentration atmosphere, and heating at 3 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the ternary material @ aluminum oxide composite material. As shown in FIG. 1, in a transmission electron microscope image of the surface coating of the prepared composite material, it can be seen that the thickness of the alumina coating is uniform and dense, and the thickness of the coating is about 6 nm.
The obtained ternary material @ aluminum oxide composite material, conductive carbon black and PTFE are proportioned according to the mass ratio of 7/1.5/1.5, placed in deionized water and stirred to be in a uniform slurry shape, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at the temperature of 80 ℃ after the contained moisture is blown and dried, and then the lithium foil loaded with the electrode active material is uniformly cut into wafers with the diameter of 11 mm. And (3) assembling the CR2016 type button cell in a glove box filled with high-purity argon by using the cut electrode copper foil as a working electrode, using metal lithium as a counter electrode and using glass fiber as a diaphragm. The performance of the lithium ion battery thus produced was examined. As shown in FIG. 2, at 0.1Ag-1After 100 cycles, the lithium capacity of the material is kept to 174mAh g-1. The relatively high capacity residue indicates that the prepared ternary material @ alumina composite material has excellent electrochemical performance.
Example 2
Dissolving 1.0g of commercial trimethyl aluminate in 100ml of toluene, magnetically stirring for 30min to obtain a clear solution, adding 10g of 1/1/1 type ternary material into the solution, stirring for 1h, distilling the material at low temperature under reduced pressure to remove toluene, and freeze-drying the obtained material in a freeze dryer to obtain the final dried mixed material of trimethyl aluminate and ternary material. Calcining at 500 deg.C for 2h in 90% oxygen atmosphere at a heating rate of 3 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the ternary material @ aluminum oxide composite material. The alumina cladding layer of the composite material has uniform and compact thickness, and the thickness of the alumina cladding layer is about 40 nm.
The obtained ternary material @ aluminum oxide composite material and the conductive materialThe preparation method comprises the following steps of proportioning the electrical carbon black and the PTFE according to the mass ratio of 7/1.5/1.5, placing the mixture into deionized water, stirring the mixture until the mixture is in a uniform slurry state, coating the mixture on a current collector aluminum foil, drying the current collector aluminum foil for 6 hours at 80 ℃ after the contained moisture is blown dry, and uniformly cutting the lithium foil loaded with the electrode active material into a wafer with the diameter of 11 mm. And (3) assembling the CR2016 type button cell in a glove box filled with high-purity argon by using the cut electrode copper foil as a working electrode, using metal lithium as a counter electrode and using glass fiber as a diaphragm. The performance of the lithium ion battery thus produced was examined. As shown in fig. 3, at 0.1A g-1After 100 cycles, the lithium capacity of the material is kept to be 160mAh g-1The capacity retention rate is about 94.7%, and the relatively high capacity retention rate indicates that the prepared ternary material @ alumina composite material has excellent electrochemical performance.
Example 3
Dissolving 1.0g of commercial triisopropyl aluminate in 100ml of toluene, magnetically stirring for 30min to obtain a clear solution, adding 10g of 1/1/1 type ternary material into the solution, stirring for 1h, distilling the material at low temperature under reduced pressure to remove toluene, and freeze-drying the obtained material in a freeze dryer to obtain the final dried triisopropyl aluminate and ternary material mixed material. Calcining at 700 deg.C for 2h under 85% oxygen atmosphere, and heating at 3 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the ternary material @ aluminum oxide composite material. The alumina cladding layer of the composite material has uniform and compact thickness, and the thickness of the alumina cladding layer is about 27 nm.
The obtained ternary material @ aluminum oxide composite material, conductive carbon black and PTFE are proportioned according to the mass ratio of 7/1.5/1.5, placed in deionized water and stirred to be in a uniform slurry shape, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at the temperature of 80 ℃ after the contained moisture is blown and dried, and then the lithium foil loaded with the electrode active material is uniformly cut into wafers with the diameter of 11 mm. In a glove box filled with high-purity argon, the cut electrode copper foil is used as a working electrode, and the metal lithium is used as a counter currentAnd the glass fiber is used as a diaphragm, and the CR2016 type button cell battery is assembled. The performance of the lithium ion battery thus produced was examined. As shown in fig. 4, at 0.1A g-1After 100 cycles of cycling, the first cycle efficiency of the lithium battery of the material is about 82%, and the cycle efficiency from 10 th cycle to 100 th cycle is over 99.5%, which indicates that the material has good cycle reversibility.
Example 4
Dissolving 1.0g of commercial triisopropyl aluminate in 100ml of toluene, magnetically stirring for 30min to obtain a clear solution, adding 10g of 1/1/1 type ternary material into the solution, stirring for 1h, distilling the material at low temperature under reduced pressure to remove toluene, and freeze-drying the obtained material in a freeze dryer to obtain the final dried triisopropyl aluminate and ternary material mixed material. Calcining at 700 deg.C for 5h in 80% oxygen atmosphere at a heating rate of 3 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the ternary material @ aluminum oxide composite material. The alumina cladding layer of the composite material has uniform and compact thickness, and the thickness of the alumina cladding layer is about 32 nm.
The obtained ternary material @ aluminum oxide composite material, conductive carbon black and PTFE are proportioned according to the mass ratio of 7/1.5/1.5, placed in deionized water and stirred to be in a uniform slurry shape, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at the temperature of 80 ℃ after the contained moisture is blown and dried, and then the lithium foil loaded with the electrode active material is uniformly cut into wafers with the diameter of 11 mm. And (3) assembling the CR2016 type button cell in a glove box filled with high-purity argon by using the cut electrode copper foil as a working electrode, using metal lithium as a counter electrode and using glass fiber as a diaphragm. The performance of the lithium ion battery thus produced was examined. As shown in FIG. 5, at 0.5Ag-1The capacity of the material can still reach 158.5mAh g after 100 cycles under the current density-1The material has good rate capability.
Example 5
Commercial triisopropyl aluminate 1.0g was dissolved in 100ml toluene and subjected to magnetic force for 30minStirring to obtain a clear solution, adding 10g of 1/1/1 type ternary material into the solution, stirring for 1h, distilling the material at low temperature under reduced pressure to remove toluene, placing the obtained material in a freeze dryer for freeze drying, and obtaining the final dried mixed material of the triisopropyl aluminate and the ternary material. Calcining at 700 deg.C for 5h in 90% oxygen atmosphere at a heating rate of 10 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the ternary material @ aluminum oxide composite material. The alumina cladding layer of the composite material has uniform and compact thickness, and the thickness of the alumina cladding layer is about 20 nm.
The obtained ternary material @ aluminum oxide composite material, conductive carbon black and PTFE are proportioned according to the mass ratio of 7/1.5/1.5, placed in deionized water and stirred to be in a uniform slurry shape, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at the temperature of 80 ℃ after the contained moisture is blown and dried, and then the lithium foil loaded with the electrode active material is uniformly cut into wafers with the diameter of 11 mm. And (3) assembling the CR2016 type button cell in a glove box filled with high-purity argon by using the cut electrode copper foil as a working electrode, using metal lithium as a counter electrode and using glass fiber as a diaphragm. The performance of the lithium ion battery thus produced was examined. As shown in fig. 5, at 0.5A g-1The capacity of the material can still reach 171mAh g after 100 cycles under the current density-1The material has good rate capability.
Example 6
1.0g of commercial DL-411-AF and DL-411-D (1:1) are dissolved in 100ml of toluene, magnetic stirring is carried out for 30min to obtain clear solution, 10g of 1/1/1 type ternary material is added into the solution, stirring is carried out for 1h, the material is distilled at low temperature under reduced pressure to remove toluene, the obtained material is placed in a freeze dryer for freeze drying, and finally the dry mixed material of DL-411-AF and DL-411-D and ternary material is obtained. Calcining at 700 deg.C for 5h in 90% oxygen atmosphere at a heating rate of 3 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the ternary material @ aluminum oxide composite material. Of the composite materialThe thickness of the alumina coating is uniform and compact, and the thickness of the alumina coating is about 30 nm.
The obtained ternary material @ aluminum oxide composite material, conductive carbon black and PTFE are proportioned according to the mass ratio of 7/1.5/1.5, placed in deionized water and stirred to be in a uniform slurry shape, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at the temperature of 80 ℃ after the contained moisture is blown and dried, and then the lithium foil loaded with the electrode active material is uniformly cut into wafers with the diameter of 11 mm. And (3) assembling the CR2016 type button cell in a glove box filled with high-purity argon by using the cut electrode copper foil as a working electrode, using metal lithium as a counter electrode and using glass fiber as a diaphragm. The performance of the lithium ion battery thus produced was examined. At 0.1A g-1Under the current density of (1), after the material is circulated for 200 circles, the capacity can still reach 157mAh g-1The material has good rate capability.
Comparative example 1
1.0g of commercial aluminum isopropoxide is dissolved in 100ml of toluene, a clear solution is obtained after 30min of magnetic stirring, 10g of 1/1/1 type ternary material is added into the solution, the toluene is removed by distilling the material at low temperature under reduced pressure after 1h of stirring, the obtained material is placed in a freeze dryer for freeze drying, and finally the dried mixed material of the triisopropyl aluminate and the ternary material is obtained. Calcining at 700 deg.C for 5h in 90% oxygen atmosphere at a heating rate of 3 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the ternary material @ aluminum oxide composite material. The thickness of the alumina coating layer of the composite material is uneven, and the thickness of the alumina coating layer is about 20-90 nm.
The obtained ternary material @ aluminum oxide composite material, conductive carbon black and PTFE are proportioned according to the mass ratio of 7/1.5/1.5, placed in deionized water and stirred to be in a uniform slurry shape, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at the temperature of 80 ℃ after the contained moisture is blown and dried, and then the lithium foil loaded with the electrode active material is uniformly cut into wafers with the diameter of 11 mm. In a glove box filled with high-purity argon, cutting electrodesAnd (3) assembling a CR2016 type button cell by using copper foil as a working electrode, metal lithium as a counter electrode and glass fiber as a diaphragm. The performance of the lithium ion battery thus produced was examined. At 0.1A g-1The capacity of the material can still reach 106mAh g after 200 cycles under the current density-1. Compared with the coupling agent as an aluminum source, the electrochemical performance of the example is obviously reduced, and the advantages of the coupling agent as an organic aluminum source are fully proved.
Comparative example 2
1.0g of commercial DL-411-AF and DL-411-D (1:1) are dissolved in 100ml of toluene, magnetic stirring is carried out for 30min to obtain clear solution, 10g of 1/1/1 type ternary material is added into the solution, stirring is carried out for 1h, the material is distilled at low temperature under reduced pressure to remove toluene, the obtained material is placed in a freeze dryer for freeze drying, and finally the dry mixed material of DL-411-AF and DL-411-D and ternary material is obtained. Calcining at 700 deg.C for 5h in 30% oxygen atmosphere at a heating rate of 3 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the ternary material @ aluminum oxide composite material. The alumina cladding layer of the composite material has uniform and compact thickness, and the thickness of the alumina cladding layer is about 30 nm.
The obtained ternary material @ aluminum oxide composite material, conductive carbon black and PTFE are proportioned according to the mass ratio of 7/1.5/1.5, placed in deionized water and stirred to be in a uniform slurry shape, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at the temperature of 80 ℃ after the contained moisture is blown and dried, and then the lithium foil loaded with the electrode active material is uniformly cut into wafers with the diameter of 11 mm. And (3) assembling the CR2016 type button cell in a glove box filled with high-purity argon by using the cut electrode copper foil as a working electrode, using metal lithium as a counter electrode and using glass fiber as a diaphragm. The performance of the lithium ion battery thus produced was examined. At 0.1Ag-1The capacity of the material can still reach 107mAh g after 200 cycles under the current density-1The proper oxygen concentration is critical to the uniformity and electrochemical performance of the coating.
Comparative example 3
Dissolving 0.2g of commercial trimethyl aluminate in 100ml of toluene, magnetically stirring for 30min to obtain a clear solution, adding 10g of 1/1/1 type ternary material into the solution, stirring for 1h, distilling the material at low temperature under reduced pressure to remove toluene, placing the obtained material in a freeze dryer for freeze drying, and finally obtaining the mixed material of the dried trimethyl aluminate and the ternary material. Calcining at 1000 deg.C for 2h under 90% oxygen concentration atmosphere, and heating at 3 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the ternary material @ aluminum oxide composite material. On the test surface, the aluminum oxide on the surface of the material is in granular aggregation, and obvious gaps exist among granules.
The obtained ternary material @ aluminum oxide composite material, conductive carbon black and PTFE are proportioned according to the mass ratio of 7/1.5/1.5, placed in deionized water and stirred to be in a uniform slurry shape, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at the temperature of 80 ℃ after the contained moisture is blown and dried, and then the lithium foil loaded with the electrode active material is uniformly cut into wafers with the diameter of 11 mm. And (3) assembling the CR2016 type button cell in a glove box filled with high-purity argon by using the cut electrode copper foil as a working electrode, using metal lithium as a counter electrode and using glass fiber as a diaphragm. The performance of the lithium ion battery thus produced was examined. At 0.1A g-1After 100 cycles of the cycle, the lithium capacity of the material is kept to 95mAh g-1. The fact that the proper calcination temperature has an important influence on the surface coating of the material and the lithium electrochemical performance of the material is also shown.

Claims (4)

1. The preparation method of the aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material is characterized by comprising the following steps of: dissolving an aluminate coupling agent in a solvent, uniformly mixing the aluminate coupling agent with the Ni-Co-Mn ternary lithium battery positive electrode material, and volatilizing to remove the solvent to obtain a precursor material; calcining the precursor material in an oxygen-containing atmosphere to obtain the precursor material; the aluminate coupling agent comprises trimethyl aluminate, triisopropyl aluminate, tribenzyl aluminate, distearoyl isopropyl aluminate, DL-411-A, DL-411-AF, DL-411-D, DL-411-DF, DL-411-B, DL-411-C, DL-412-A, DL-412-B, DL-812, DL-414, DL-481, DL-881 and DL-482, at least one of DL-882, DL-429, DL-467, DL-461, DL-491-A, DL-471, DL-472, DL-492, F-1, F-2, F-3, F-4, L-1A, L-1H, L-3A, H-4A; the mass ratio of the aluminate coupling agent to the Ni-Co-Mn ternary lithium battery positive electrode material is 1: 10-1: 50; the oxygen-containing atmosphere is mixed gas of oxygen and nitrogen, and the volume percentage of the oxygen is 50-95%; the calcining conditions are as follows: heating to 400-700 ℃ at a heating rate of 3-10 ℃/min, and preserving heat for 3-8 h.
2. The preparation method of the aluminum oxide-coated Ni-Co-Mn ternary lithium battery positive electrode material according to claim 1, characterized in that: the solvent comprises at least one of gasoline, ethyl acetate, toluene and turpentine.
3. An alumina-coated Ni-Co-Mn ternary lithium battery positive electrode material is characterized in that: prepared by the method of any one of claims 1 to 2.
4. The application of the aluminum oxide coated Ni-Co-Mn ternary lithium battery positive electrode material as claimed in claim 3 is characterized in that: the lithium ion battery anode material is applied as a lithium ion battery anode material.
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