CN111600023B - Titanium dioxide coated nickel-cobalt-manganese ternary cathode material and preparation method and application thereof - Google Patents

Titanium dioxide coated nickel-cobalt-manganese ternary cathode material and preparation method and application thereof Download PDF

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CN111600023B
CN111600023B CN202010273857.6A CN202010273857A CN111600023B CN 111600023 B CN111600023 B CN 111600023B CN 202010273857 A CN202010273857 A CN 202010273857A CN 111600023 B CN111600023 B CN 111600023B
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cobalt
titanium dioxide
manganese ternary
nickel
titanate
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CN111600023A (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 a titanium dioxide coated nickel-cobalt-manganese ternary positive electrode material and a preparation method and application thereof. The method overcomes the defects that the titanium dioxide coating of the titanium dioxide coating nickel-cobalt-manganese ternary positive electrode material prepared by the existing hydrolysis precipitation method is uneven and too thick, acid medium and water are introduced to damage the surface activity and the interface structure is unstable, and overcomes the defects that the existing atomic deposition method has high equipment cost and is difficult to industrially produce, and the prepared titanium dioxide coating nickel-cobalt-manganese ternary positive electrode material has higher electrochemical activity and circulation stability.

Description

Titanium dioxide coated nickel-cobalt-manganese ternary cathode material and preparation method and application thereof
Technical Field
The invention relates to a nickel-cobalt-manganese ternary cathode material, in particular to a nickel-cobalt-manganese ternary cathode material with a uniform and compact titanium dioxide coating layer, and also relates to a preparation method and application thereof, belonging to the technical field of lithium ion batteries.
Background
In recent years, the lithium battery industry is rapidly and rapidly developed and rapidly popularized to various fields in daily life of people, including portable electronic equipment, new energy electric automobiles and the like. At present, nickel-cobalt-manganese ternary lithium battery positive electrode materials attract extensive attention of people in the industry and are already mature to be applied to the field of partial energy storage, and the reason is that the ternary positive electrode materials have higher energy density and effectively increase the endurance time of energy storage devices. In the process of energy storage application of the material, researchers find that the cycle life of the material is irrational, and the capacity of the battery has a rapid downward sliding trend along with the continuation of the cycle times. The research shows that the surface of the ternary electrode material gradually dissolves in the circulation process, and the battery system is further degraded.
How to prevent the surface of the ternary cathode material from dissolving becomes an important problem which troubles the development of the industry. Titanium dioxide, which is low in cost and stable in chemical properties, has been successfully used as other energy storage materials. Titanium dioxide is uniformly coated on the surface of the ternary cathode material, so that the corrosion of electrolyte and byproducts to the outer surface of the electrode can be effectively prevented, and the cycle life of the material is prolonged. When the traditional titanium salt is coated, the coating needs to be carried out under an acidic condition, so that on one hand, an acidic medium is introduced, and on the other hand, a water phase is introduced, and the damage to the surface activity of the ternary cathode material is large. The methods of atomic deposition and vapor deposition have high requirements on equipment and are difficult to meet the requirements of large-scale production.
Disclosure of Invention
The first purpose of the invention is to provide a titanium dioxide coated nickel-cobalt-manganese ternary cathode material which has a uniform, compact and nanometer thickness titanium dioxide coating layer and a stable interface structure, aiming at the defects of the titanium dioxide coated nickel-cobalt-manganese ternary cathode material in the prior art, such as uneven titanium dioxide coating, excessive thickness, unstable interface structure and the like.
The second purpose of the invention is to provide a simple, effective, strong controllable, fast and large-scale production method for preparing the titanium dioxide coated nickel-cobalt-manganese ternary cathode material, which overcomes the defects of the titanium dioxide coated nickel-cobalt-manganese ternary cathode material prepared by the existing hydrolysis precipitation method, such as uneven titanium dioxide coating, over-thickness, damage to surface activity caused by introduction of acid medium and water, unstable interface structure and the like, and overcomes the defects of the existing atomic deposition method, such as high equipment cost and difficulty in industrial production.
The third purpose of the invention is to provide an application of the titanium dioxide coated nickel-cobalt-manganese ternary cathode material, wherein the titanium dioxide coated nickel-cobalt-manganese ternary cathode material has a uniform titanium dioxide coating layer, has a stable interface structure, shows good electrochemical performance, and has good electrochemical performance such as high multiplying power and long cycle compared with the existing titanium dioxide coated nickel-cobalt-manganese ternary cathode material.
In order to achieve the technical purpose, the invention provides a preparation method of a titanium dioxide coated nickel-cobalt-manganese ternary cathode material, which comprises the steps of dissolving a titanate coupling agent in a solvent, uniformly mixing the titanate coupling agent with the nickel-cobalt-manganese ternary cathode 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 preferred embodiment, the titanate-based coupling agent includes at least one of monoalkoxy titanate, NDZ-401 tetraisopropyl bis (dioctyl phosphite) titanate, GR311W bis (dioctyloxypyrophosphate) ethylene titanate, NDZ311 bis (dioctylpyrophosphate) ethylene titanate, NDZ101, NDZ102, NDZ105, NDZ311W, SG-AL 822. The titanate coupling agents simultaneously contain hydrophilic and hydrophobic functional groups and have strong adsorption performance on the surfaces of nickel-cobalt-manganese ternary positive electrode material particles, and in the liquid phase mixing process, the titanate coupling agents can form a tightly attached titanium-containing organic layer on the surface of a powder material in an adsorption mode, and are directly coupled with trace carboxyl or hydroxyl adsorbed on the surface of a nickel-cobalt-manganese ternary positive electrode material through the alkoxy of the titanate coupling agents under the chemical action, so that a tight and uniform titanium-containing organic coating layer can be formed on the surface of the nickel-cobalt-manganese ternary positive electrode material through chemical bonding, and a uniform and complete titanium dioxide coating layer can be further formed on the surface of the ternary material through pyrolysis; and the titanium dioxide and the nickel-cobalt-manganese ternary positive electrode 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 titanate coupling agent to the nickel-cobalt-manganese ternary positive electrode material is 1: 1-1: 60, and the thickness of the titanium dioxide can be adjusted within the range of 5 nm-300 nm by controlling the mass ratio of the titanate coupling agent to the nickel-cobalt-manganese ternary lithium battery positive electrode material. As a further preferable scheme, the mass ratio of the titanate coupling agent to the nickel-cobalt-manganese ternary positive electrode material is 1: 10-1: 30. More preferably, the thickness of the titanium dioxide is adjusted within the range of 10 to 150 nm.
As a preferred scheme, the solvent comprises at least one of solvent naphtha, petroleum ether, benzene alcohol, liquid paraffin and isopropanol. The preferable solvent has good solubility on the titanate coupling agent, is easy to remove, and can improve the coating uniformity of the titanate coupling agent on the surface of the nickel-cobalt-manganese ternary lithium battery anode material, thereby obtaining a more uniform titanium dioxide coating layer.
As a preferable scheme, the oxygen-containing gas is a mixed gas of oxygen and nitrogen, and the volume percentage of the oxygen is 60-90%; the preferred oxygen volume percentage is 80% to 90%. The concentration of oxygen mainly influences the thermal de-nucleation rate of the titanate coupling agent, when the concentration of the oxygen is too high, the titanium oxide is rapidly condensed, and the uniformity of the formed coating layer is poor. When the oxygen concentration is too low, the organic titanium source is difficult to be effectively pyrolyzed on the surface of the powder material, and the formed titanium dioxide coating layer is incomplete and can fall off.
As a preferred embodiment, the calcination conditions are: heating to 300-900 ℃ at a heating rate of 1-12 ℃/min, and preserving heat for 1-18 h. The heating rate is preferably 5-10 ℃/min, and the preferred calcining temperature is 300-800 ℃; the preferable calcination time is 1-12 h. As a further preferred embodiment, the calcination conditions are: heating to 400-700 ℃ at a heating rate of 5-10 ℃/min, and preserving heat for 4-7 h. The selection of the calcining condition is crucial to the formation of the titanium dioxide coating layer, when the calcining temperature is too high and the calcining time is too long, the crystal structure of the nickel-cobalt-manganese ternary lithium battery anode material is influenced, the electrochemical activity of the body material is damaged, and the electrochemical performance of the ternary anode material is reduced.
The invention also provides a titanium dioxide coated nickel-cobalt-manganese ternary cathode material which is prepared by the method.
The invention also provides a preparation method of the titanium dioxide coated nickel-cobalt-manganese ternary cathode material, which is applied as a lithium ion battery cathode material.
The proportion of nickel, cobalt and manganese in the nickel, cobalt and manganese ternary cathode material is mainly 1/1/1, 8/1/1, 4/2/4, 3/3/3, 5/2/3, 70/15/15 and other common nickel, cobalt and manganese ternary cathode materials in the field, and the materials are all suitable for coating and modifying by adopting titanium dioxide in the technical scheme of the invention.
The solvent volatilization and removal process of the invention is low-temperature reduced pressure distillation and then freeze drying treatment.
The titanium dioxide coated nickel-cobalt-manganese ternary cathode material is used as an electrode cathode 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 titanium dioxide coated nickel-cobalt-manganese ternary cathode material provided by the invention has a complete and uniform titanium dioxide coating layer and stable interface chemical bonds, can effectively inhibit the surface dissolution of the nickel-cobalt-manganese ternary cathode material, improves the interface structure stability of the nickel-cobalt-manganese ternary cathode material, prevents the nickel-cobalt-manganese ternary cathode 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 titanium dioxide coated nickel-cobalt-manganese ternary cathode material provided by the invention is simple, effective, strong in controllability, fast and capable of realizing large-scale production. The titanium dioxide coated nickel-cobalt-manganese ternary cathode material prepared by the method has a uniform and complete titanium dioxide coating layer with a nanometer thickness, and has a stable interface structure, so that the defects that the titanium dioxide coated nickel-cobalt-manganese ternary cathode material prepared by the conventional hydrolytic precipitation method has nonuniform titanium dioxide coating, excessive thickness, damage to the surface activity of the material due to introduction of acid media and water, unstable interface structure and the like are overcome, and the defects that the conventional atomic deposition method has high equipment cost and is difficult to industrially produce are overcome.
Drawings
FIG. 1 is a transmission electron microscope picture of a Ni-Co-Mn ternary material @ titanium dioxide composite material prepared in example 1;
FIG. 2 is a graph of the cycle performance of the Ni-Co-Mn ternary material @ titanium dioxide composite material prepared in example 1;
FIG. 3 is a graph of the cycle performance of the Ni-Co-Mn ternary material @ titanium dioxide composite material prepared in example 2;
FIG. 4 is a graph of the cycle performance of the Ni-Co-Mn ternary material @ titanium dioxide composite material prepared in example 3;
fig. 5 is a rate plot of the nickel-cobalt-manganese ternary material @ titanium dioxide composite material prepared 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 0.4g of commercial monoalkoxy titanate in 100ml of petroleum ether, obtaining a clear solution after 1 hour of magnetic stirring, adding 10g of 8/1/1 type ternary material into the solution, performing ultrasonic treatment for 1 hour after 2 hours of stirring, distilling the material at low temperature under reduced pressure to remove the petroleum ether, placing the obtained material in a freeze dryer for freeze drying, and obtaining the final dried monoalkoxy titanate and ternary material mixed material. Calcining at 600 deg.C for 5h in 85% oxygen atmosphere at a heating rate of 5 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the nickel-cobalt-manganese ternary material @ titanium oxide composite material. Referring to fig. 1, in a transmission electron microscope image of the surface titanium dioxide coating layer of the prepared composite material, it can be seen that the thickness of the titanium dioxide coating layer is uniform and dense, and the thickness of the titanium dioxide coating layer is about 13 nm.
The obtained nickel-cobalt-manganese ternary material @ titanium 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 uniform slurry, coated on a current collector aluminum foil, and the mixture is subjected toThe moisture content was blow-dried and then dried in a drying oven at 80 ℃ for 6 hours, and then the lithium foil loaded with the electrode active material was uniformly cut into a circular piece having a 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 0.2Ag-1After 200 cycles of the cycle, the lithium capacity of the material is maintained to be 192mAh g-1. The relatively high capacity residue indicates that the prepared ternary material @ titanium oxide composite material has excellent electrochemical performance.
Example 2
Dissolving 1g of commercial monoalkoxy titanate in 100ml of petroleum ether, magnetically stirring for 1h to obtain a clear solution, adding 10g of 8/1/1 type ternary material into the solution, stirring for 2h, performing ultrasonic treatment for 1h, distilling the material at low temperature under reduced pressure to remove the petroleum ether, placing the obtained material in a freeze dryer for freeze drying, and finally obtaining the final dry monoalkoxy titanate and ternary material mixed material. Calcining at 600 deg.C for 5h in 85% oxygen atmosphere at a heating rate of 5 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the nickel-cobalt-manganese ternary material @ titanium oxide composite material, wherein the titanium dioxide coating layer of the composite material is uniform and compact in thickness, and the thickness of the titanium dioxide coating layer is about 75 nm.
The obtained nickel-cobalt-manganese ternary material @ titanium 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 state, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at 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. 3, at 0.2Ag-1After 200 cycles of cycle, the lithium capacity of the material is kept to 152mAh g-1. The relatively high capacity residue indicates that the prepared ternary material @ titanium oxide composite material has excellent electrochemical performance.
Example 3
Dissolving 0.4g of commercial NDZ-401 tetraisopropylbis (dioctyl phosphite) titanate in 100ml of petroleum ether, magnetically stirring for 1h to obtain a clear solution, adding 10g of 8/1/1 type ternary material into the solution, stirring for 2h, performing ultrasound for 1h, distilling the material at low temperature under reduced pressure to remove the petroleum ether, placing the obtained material in a freeze dryer, and performing freeze drying to obtain the final dried mixed material of the NDZ-401 and the ternary material. Calcining at 600 deg.C for 10h in 85% oxygen atmosphere at a heating rate of 5 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the nickel-cobalt-manganese ternary material @ titanium oxide composite material. The titanium dioxide coating layer of the composite material is uniform and compact in thickness, and the thickness of the titanium dioxide coating layer is about 15 nm.
The obtained nickel-cobalt-manganese ternary material @ titanium 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 state, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at 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. 4, at 0.2Ag-1After 200 cycles of circulation, the lithium capacity of the material is kept at 189mAh g-1. The relatively high capacity residue indicates that the prepared ternary material @ titanium oxide composite material has excellent electrochemical performance.
Example 4
Commercial NDZ-401 tetraisopropylbis (A)0.4g of dioctyl phosphite) titanate is dissolved in 100ml of petroleum ether, a clear solution is obtained after 1h of magnetic stirring, 10g of 8/1/1 type ternary material is added into the solution, after 2h of stirring, ultrasound is carried out for 1h, the petroleum ether is removed by low-temperature reduced pressure distillation of the material, the obtained material is placed in a freeze dryer for freeze drying, and finally the dry mixed material of the NDZ-401 and the ternary material is obtained. Calcining at 500 deg.C for 5h in 85% oxygen atmosphere at a heating rate of 5 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the nickel-cobalt-manganese ternary material @ titanium oxide composite material. The titanium dioxide coating layer of the composite material is uniform and compact in thickness, and the thickness of the titanium dioxide coating layer is about 31 nm.
The obtained nickel-cobalt-manganese ternary material @ titanium 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 state, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at 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. 4, at 2.0Ag-1After 200 cycles of the cycle, the lithium capacity of the material is kept to be 113mAh g-1. The relatively high capacity residue indicates that the prepared ternary material @ titanium oxide composite material has excellent rate capability.
Example 5
Dissolving GR311W0.4 g of commercialized material in 100ml of petroleum ether, obtaining a clear solution after 1 hour of magnetic stirring, adding 8/1/1 g of ternary material into the solution, stirring for 2 hours, then performing ultrasonic treatment for 1 hour, distilling the material at low temperature under reduced pressure to remove the petroleum ether, placing the obtained material in a freeze dryer for freeze drying, and obtaining the final dried mixed material of GR311W and the ternary material. Under 80% oxygen atmosphere, 500 deg.CCalcining for 5h at a temperature rise rate of 5 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the nickel-cobalt-manganese ternary material @ titanium oxide composite material. The titanium dioxide coating layer of the composite material is uniform and compact in thickness, and the thickness of the titanium dioxide coating layer is about 32 nm.
The obtained nickel-cobalt-manganese ternary material @ titanium 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 state, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at 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 2.0Ag-1After 200 cycles of cycle under the current density of (1), the lithium capacity of the material is kept to be 110mAh g-1. The relatively high capacity residue indicates that the prepared ternary material @ titanium oxide composite material has excellent electrochemical performance.
Example 6
Dissolving 0.4g of commercial NDZ-401 tetraisopropylbis (dioctyl phosphite) titanate in 100ml of petroleum ether, magnetically stirring for 1h to obtain a clear solution, adding 10g of 8/1/1 type ternary material into the solution, stirring for 2h, performing ultrasound for 1h, distilling the material at low temperature under reduced pressure to remove the petroleum ether, placing the obtained material in a freeze dryer, and performing freeze drying to obtain the final dried mixed material of the NDZ-401 and the ternary material. Calcining at 500 deg.C for 5h in 85% 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 nickel-cobalt-manganese ternary material @ titanium oxide composite material. The titanium dioxide coating layer of the composite material is uniform and compact in thickness, and the thickness of the titanium dioxide coating layer is about 37 nm.
The nickel-cobalt-manganese ternary material @ titanium oxide composite material is prepared,The conductive carbon black and the PTFE are proportioned according to the mass ratio of 7/1.5/1.5, are placed in deionized water and stirred to be uniform slurry, are coated on a current collector aluminum foil, are placed in a drying box for drying for 6 hours at the temperature of 80 ℃ after the contained moisture is blown dry, 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 2.0Ag-1After 200 cycles of the cycle, the lithium capacity of the material is kept to be 121mAh g-1. The relatively high capacity residue indicates that the prepared ternary material @ titanium oxide composite material has excellent electrochemical performance.
Example 7
Dissolving 0.4g of commercial NDZ-401 tetraisopropylbis (dioctyl phosphite) titanate in 100ml of petroleum ether, magnetically stirring for 1h to obtain a clear solution, adding 10g of 5/3/2 type ternary material into the solution, stirring for 2h, performing ultrasound for 1h, distilling the material at low temperature under reduced pressure to remove the petroleum ether, placing the obtained material in a freeze dryer, and performing freeze drying to obtain the final dried mixed material of the NDZ-401 and the ternary material. Calcining at 500 deg.C for 5h in 85% 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 nickel-cobalt-manganese ternary material @ titanium oxide composite material. The titanium dioxide coating layer of the composite material is uniform and compact in thickness, and the thickness of the titanium dioxide coating layer is about 40 nm.
The obtained nickel-cobalt-manganese ternary material @ titanium 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 state, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at 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 taken as a working electrode,and assembling the CR2016 type button cell by using metal lithium as a counter electrode and glass fiber as a diaphragm. The performance of the lithium ion battery thus produced was examined. At 1.0Ag-1After 100 cycles of the cycle, the lithium capacity of the material is kept to be 150mAh g-1. The relatively high capacity residue indicates that the prepared ternary material @ titanium oxide composite material has excellent electrochemical performance.
Example 8
Dissolving 0.4g of commercial NDZ-401 tetraisopropylbis (dioctyl phosphite) titanate in 100ml of petroleum ether, magnetically stirring for 1h to obtain a clear solution, adding 10g of 5/3/2 type ternary material into the solution, stirring for 2h, performing ultrasound for 1h, distilling the material at low temperature under reduced pressure to remove the petroleum ether, placing the obtained material in a freeze dryer, and performing freeze drying to obtain the final dried mixed material of the NDZ-401 and the ternary material. Calcining at 500 deg.C for 5h in the atmosphere of oxygen-nitrogen mixture (nitrogen gas 10%), and heating at 10 deg.C for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the nickel-cobalt-manganese ternary material @ titanium oxide composite material. The prepared material has uniform coating layer. The titanium dioxide coating layer of the composite material is uniform and compact in thickness, and the thickness of the titanium dioxide coating layer is about 33 nm.
The obtained nickel-cobalt-manganese ternary material @ titanium 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 state, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at 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 1.0Ag-1After 100 cycles of the cycle, the lithium capacity of the material is kept to be 147mAh g-1. The relatively high capacity residue indicates that the prepared ternary material @ titanium oxideThe composite material has excellent electrochemical performance.
Example 9
Dissolving commercial NDZ-401 tetraisopropylbis (dioctyl phosphite) titanate and NDZ311 bis (dioctyl pyrophosphate acyloxy) ethylene titanate (the mass ratio is (1:1)0.4g in 100ml of petroleum ether, obtaining a clear solution after 1h of magnetic stirring, adding 10g of 5/3/2 type ternary material into the solution, stirring for 2h, performing ultrasonic treatment for 1h, distilling the material at low temperature under reduced pressure to remove the petroleum ether, placing the obtained material in a freeze drier for freeze drying, obtaining the finally dried mixed material of tetraisopropylbis (dioctyl phosphite) titanate-based NDZ311 bis (dioctyl pyrophosphate acyloxy) ethylene titanate and the ternary material, calcining for 5h at 500 ℃ in 85% oxygen atmosphere, and increasing the temperature at the rate of 10 ℃ for min-1And naturally cooling. And grinding the calcined black product into powder to obtain the nickel-cobalt-manganese ternary material @ titanium oxide composite material. The titanium dioxide coating layer of the composite material is uniform and compact in thickness, and the thickness of the titanium dioxide coating layer is about 59 nm.
The obtained nickel-cobalt-manganese ternary material @ titanium 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 state, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at 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 1.0Ag-1After 100 cycles, the lithium capacity of the material is maintained at 154mAh g-1. The relatively high capacity residue indicates that the prepared ternary material @ titanium oxide composite material has excellent rate capability.
Comparative example 1
Dissolving commercial butyl titanate 0.4g in petroleum ether 100ml, and magnetically stirring for 1 hrAnd (3) obtaining a clear solution after stirring, adding 10g of 5/3/2 type ternary material into the solution, stirring for 2h, performing ultrasonic treatment for 1h, distilling the material at low temperature under reduced pressure to remove petroleum ether, and freeze-drying the obtained material in a freeze dryer to obtain the final dried mixed material of the butyl titanate and the ternary material. Calcining at 500 deg.C for 5h in 85% 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 nickel-cobalt-manganese ternary material @ titanium oxide composite material. The titanium dioxide coating layer of the composite material is uneven, and the thickness of the titanium dioxide coating layer is about 5-60 nm.
The obtained nickel-cobalt-manganese ternary material @ titanium 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 state, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at 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 1.0A g-1After 100 cycles of the cycle, the lithium capacity of the material is kept to be 127mAh g-1. Compared with example 9, the organic titanium source adopted in the example is a non-coupling agent, so that the generated coating layer falls off, and the electrochemical performance of the material is influenced, thereby fully demonstrating that the coupling agent titanium source as the coating agent has excellent performance improvement effect on the ternary powder material.
Comparative example 2
Dissolving 0.4g of commercial NDZ-401 tetraisopropylbis (dioctyl phosphite) titanate in 100ml of petroleum ether, magnetically stirring for 1h to obtain a clear solution, adding 10g of 5/3/2 type ternary material into the solution, stirring for 2h, performing ultrasound for 1h, distilling the material at low temperature under reduced pressure to remove the petroleum ether, placing the obtained material in a freeze dryer for freeze drying, and obtaining the productThe final dried NDZ-401 is mixed with ternary material. Calcining at 1000 deg.C for 5h in 85% 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 nickel-cobalt-manganese ternary material @ titanium oxide composite material. The titanium dioxide coating of the composite material is uneven, the coating presents granular existence and more gaps exist. At the same time, it was found that the original ternary material particles were broken. Fully shows that the coating layer is not uniform due to overhigh temperature, and the particles of the material are seriously damaged, thereby influencing the appearance structure of the bulk material.
The obtained nickel-cobalt-manganese ternary material @ titanium 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 state, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at 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 1.0Ag-1After 100 cycles of the cycle, the lithium capacity of the material is kept to 97mAh g-1. Based on this, it is demonstrated that after forming a mixture of a coupling agent and a ternary material, the calcination temperature is critical to the coating layer and electrochemical performance of the material.
Comparative example 3
Dissolving 0.4g of commercial NDZ-401 tetraisopropylbis (dioctyl phosphite) titanate in 100ml of petroleum ether, magnetically stirring for 1h to obtain a clear solution, adding 10g of 5/3/2 type ternary material into the solution, stirring for 2h, performing ultrasound for 1h, distilling the material at low temperature under reduced pressure to remove the petroleum ether, placing the obtained material in a freeze dryer, and performing freeze drying to obtain the final dried mixed material of the NDZ-401 and the ternary material. Calcining at 700 deg.C for 5h in 100% oxygen atmosphere at a heating rate of 10 deg.C for min-1Naturally descendAnd (4) warming. And grinding the calcined black product into powder to obtain the nickel-cobalt-manganese ternary material @ titanium oxide composite material. The titanium dioxide coating of the composite material is not uniform, the coating is in the form of particles, and the particle size is large.
The obtained nickel-cobalt-manganese ternary material @ titanium 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 state, coated on a current collector aluminum foil, placed in a drying oven for drying for 6 hours at 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 1.0Ag-1After 100 cycles of the cycle, the lithium capacity of the material is kept to 97mAh g-1. Based on this, it is demonstrated that after forming a mixture of a coupling agent and a ternary material, the calcination temperature is critical to the coating layer and electrochemical performance of the material.

Claims (5)

1. A preparation method of a titanium dioxide coated nickel-cobalt-manganese ternary cathode material is characterized by comprising the following steps: dissolving titanate coupling agent in solvent, mixing with nickel-cobalt-manganese ternary positive electrode material uniformly, and volatilizing to remove solvent to obtain precursor material; calcining the precursor material in an oxygen-containing atmosphere to obtain the precursor material;
the mass ratio of the titanate coupling agent to the nickel-cobalt-manganese ternary positive electrode material is 1: 10-1: 30;
the oxygen-containing gas is a mixed gas of oxygen and nitrogen, and the volume percentage of the oxygen is 60-90%;
the calcining conditions are as follows: 5 to 10 times ofoHeating to 400-700 ℃ at a C/min heating rate oCAnd keeping the temperature for 4-7 h.
2. The preparation method of the titanium dioxide coated nickel-cobalt-manganese ternary cathode material according to claim 1, characterized in that: the titanate coupling agent comprises at least one of monoalkoxy titanate, tetraisopropyl di (dioctyl phosphite) titanate, bis (dioctyloxy pyrophosphate) ethylene titanate, bis (dioctylphosphonate) ethylene titanate, NDZ101, NDZ102, NDZ105, NDZ311W and SG-AL 822.
3. The method for preparing the titanium dioxide coated nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: the solvent comprises at least one of solvent oil, petroleum ether, benzene alcohol, liquid paraffin and isopropanol.
4. The titanium dioxide coated nickel-cobalt-manganese ternary cathode material is characterized in that: prepared by the method of any one of claims 1 to 3.
5. The application of the titanium dioxide coated nickel-cobalt-manganese ternary cathode material as claimed in claim 4, is characterized in that: the lithium ion battery anode material is applied as a lithium ion battery anode material.
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