CN112909237A - Modified lithium-nickel-cobalt-manganese oxide positive electrode material, and preparation method and application thereof - Google Patents
Modified lithium-nickel-cobalt-manganese oxide positive electrode material, and preparation method and application thereof Download PDFInfo
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- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical class [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims abstract description 62
- JVPGYYNQTPWXGE-UHFFFAOYSA-N 2-(4-methylphenyl)-1,3-benzothiazole Chemical compound C1=CC(C)=CC=C1C1=NC2=CC=CC=C2S1 JVPGYYNQTPWXGE-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000010406 cathode material Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 28
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 12
- 150000002642 lithium compounds Chemical class 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910016488 Ni0.4Co0.3Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 1
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 1
- 229910003618 NixCoyMn1-x-y(OH)2 Inorganic materials 0.000 description 1
- 229910003616 NixCoyMn1−x−yCO3 Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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Abstract
A preparation method of a modified lithium nickel cobalt manganese oxide positive electrode material comprises the following steps: providing lithium nickel cobalt manganese oxide; providing aluminum tungstate; and mixing the lithium nickel cobalt manganese oxide and the aluminum tungstate, and then sintering to obtain the modified lithium nickel cobalt manganese oxide cathode material. The application also provides a modified lithium nickel cobalt manganese oxide positive electrode material, a positive electrode comprising the modified lithium nickel cobalt manganese oxide positive electrode material and a lithium ion battery.
Description
Technical Field
The application relates to the field of lithium ion batteries, in particular to a modified lithium nickel cobalt manganese oxide positive electrode material, and a preparation method and application thereof.
Background
The performance of the lithium nickel cobalt manganese oxide cathode material is continuously improved after years of practice in the application fields of electronic products, electric bicycles, electric automobiles and the like. However, the current large-scale commercialized lithium nickel cobalt manganese oxide still cannot well meet the application requirements of high capacity and high energy density, and particularly, the current power battery system is expected to further achieve the aim of prolonging the endurance mileage, so that higher requirements are put forward on the positive electrode material.
The high-nickel low-cobalt type lithium nickel cobalt manganese oxide is a hot spot of a recent positive electrode material, the specific capacity of the material can be increased due to the high nickel content, the material cost can be reduced due to the low cobalt content, and a small amount of manganese plays a role of a supporting structure during charge-discharge cycle of the positive electrode material, so the high-nickel low-cobalt type lithium nickel cobalt manganese oxide becomes one of mainstream materials of future power batteries, large batteries and energy storage batteries. However, higher nickel content and lower cobalt content can reduce the cycling, rate and conductivity properties of the material. Therefore, the lithium nickel cobalt manganese oxide cathode material needs to be modified, and the surface modification method which is commonly used at present is surface modification, which can obviously improve the cycle performance and rate performance of the cathode material, but the conductivity performance of the cathode material is often reduced by the surface-modified substances.
Disclosure of Invention
In view of the above, there is a need for a method for preparing a modified lithium nickel cobalt manganese oxide cathode material with simple process and convenient operation, and the modified cathode material can improve cycle performance, rate capability and conductivity performance of the cathode material at the same time.
One embodiment of the present application provides a method for preparing a modified lithium nickel cobalt manganese oxide positive electrode material, including the following steps: providing lithium nickel cobalt manganese oxide; and mixing the lithium nickel cobalt manganese oxide and aluminum tungstate, and sintering to obtain the modified lithium nickel cobalt manganese oxide cathode material.
In an alternative embodiment, the mass of aluminum tungstate is 0.1% to 0.5% of the total mass of aluminum tungstate and lithium nickel cobalt manganese oxide.
In an alternative embodiment, the step of preparing the lithium nickel cobalt manganese oxide comprises:
providing a lithium compound and a nickel-cobalt-manganese precursor, and mixing the lithium compound and the nickel-cobalt-manganese precursor to obtain a mixed precursor; and
and sintering the mixed precursor to obtain the lithium nickel cobalt manganese oxide.
In an optional embodiment, the molar ratio of lithium in the lithium compound to the nickel-cobalt-manganese precursor is 1.00 to 1.05: 1.
in an optional embodiment, the mixed precursor is sintered at 850-950 ℃ for 10-12 h.
In an alternative embodiment, the lithium nickel cobalt manganese oxide is mixed with aluminum tungstate by ball milling.
In an optional embodiment, the sintering temperature of the sintering treatment after the lithium nickel cobalt manganese oxide and the aluminum tungstate are mixed is 400-600 ℃, and the sintering time is 4-6 h.
An embodiment of the present application further provides a modified lithium nickel cobalt manganese oxide cathode material, including a lithium nickel cobalt manganese oxide and aluminum tungstate coated on the lithium nickel cobalt manganese oxide.
An embodiment of the present application also provides a positive electrode including the modified lithium nickel cobalt manganese oxide positive electrode material.
An embodiment of the present application also provides a lithium ion battery including the positive electrode.
The preparation method of the modified lithium nickel cobalt manganese oxide cathode material provided by the application is simple in process flow, and the cycle performance, the rate performance and the conductivity performance of the cathode material can be improved by coating aluminum tungstate on the lithium nickel cobalt manganese oxide.
Drawings
Fig. 1 is a flowchart of a method for preparing a modified lithium nickel cobalt manganese oxide cathode material according to an embodiment of the present disclosure.
Fig. 2 is a charge and discharge performance test chart of the button cell of the embodiment 3 and the comparative examples 1-3.
Fig. 3 is a graph showing the cycle performance test of the button cell of example 3 and comparative examples 1-3.
The following detailed description will further illustrate the present application in conjunction with the above-described figures.
Detailed Description
In order that the above objects, features and advantages of the present application can be more clearly understood, a detailed description of the present application will be given below with reference to the accompanying drawings and detailed description. In addition, the embodiments and features of the embodiments of the present application may be combined with each other without conflict. In the following description, numerous specific details are set forth to provide a thorough understanding of the present application, and the described embodiments are merely a subset of the embodiments of the present application, rather than all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive work based on the embodiments in the present application are within the scope of protection of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the present application provides a method for preparing a modified lithium nickel cobalt manganese oxide cathode material, including the following steps:
step S1: providing a lithium compound and a nickel-cobalt-manganese precursor, and mixing the lithium compound and the nickel-cobalt-manganese precursor to obtain a mixed precursor.
The lithium compound includes at least one of lithium carbonate or lithium hydroxide. The chemical formula of the nickel-cobalt-manganese precursor conforms to NixCoyMn1-x-y(OH)2And NixCoyMn1-x-yCO3At least one of (1), wherein 0<x<1、0<y<1、0<x+y<1。
The molar ratio of lithium in the lithium compound to the nickel-cobalt-manganese precursor is 1.00-1.05: 1.
step S2: and sintering the mixed precursor to obtain the lithium nickel cobalt manganese oxide.
Specifically, the mixed precursor is sintered in a high-temperature roller furnace and then crushed to obtain the powdery lithium nickel cobalt manganese oxide. Wherein the sintering temperature is 850-950 ℃, and the heat preservation time is 10-12 h; the sintering atmosphere is an oxygen-containing atmosphere, and the oxygen content is 21% to 100%, for example, an air atmosphere, an oxygen atmosphere, and a mixed atmosphere of air and oxygen.
Step S3: mixing the lithium nickel cobalt manganese oxide with aluminum tungstate (Al)2O12W3) And sintering after mixing to obtain the modified lithium nickel cobalt manganese oxide cathode material.
In this embodiment, the mass of the aluminum tungstate is 0.1% to 0.5% of the total mass of the aluminum tungstate and the lithium nickel cobalt manganese oxide.
And mixing the lithium nickel cobalt manganese oxide and the aluminum tungstate in a ball milling mode.
In step S3, the sintering temperature is 400-600 ℃, the heat preservation time is 4-6 h, and the sintering atmosphere is oxygen-containing atmosphere, such as air atmosphere, oxygen atmosphere, etc.
An embodiment of the present application further provides a modified lithium nickel cobalt manganese oxide positive electrode material prepared by the above preparation method, where the modified lithium nickel cobalt manganese oxide positive electrode material includes a lithium nickel cobalt manganese oxide and aluminum tungstate coated on the lithium nickel cobalt manganese oxide.
An embodiment of the present application also provides a positive electrode including a current collector and a coating material disposed on a surface of the current collector. The coating material comprises the modified lithium nickel cobalt manganese oxide cathode material, a conductive material and a binder. And dispersing the modified lithium nickel cobalt manganese oxide positive electrode material, the conductive material and the binder in a solvent according to a certain proportion, uniformly mixing to obtain a dispersion solution, coating the dispersion solution on the current collector, drying and slicing to obtain the positive electrode.
The present application further provides a lithium ion battery including the positive electrode, the negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte.
The present application will be described below with reference to specific examples.
Example 1
Lithium carbonate and Ni0.4Co0.3Mn0.3(OH)2And mixing the nickel-cobalt-manganese precursor by a ball milling blender mixer to obtain a mixed precursor. Wherein lithium and Ni in the lithium carbonate0.4Co0.3Mn0.3(OH)2In a molar ratio of 1.04: 1.
and sintering the mixed precursor in a high-temperature roller way sintering furnace, and preserving heat for 12 hours at 910 ℃ in an air atmosphere. And crushing the sintered lump material by using a jaw crusher, and then crushing by using a machine to obtain the lithium nickel cobalt manganese oxide.
And mixing the lithium nickel cobalt manganese oxide and aluminum tungstate according to a mass ratio of 99.7:0.3, and keeping the temperature at 450 ℃ for 6 hours in an air atmosphere to obtain the lithium nickel cobalt manganese oxide with the surface coated with the aluminum tungstate.
Example 2
Lithium hydroxide is mixed with Ni0.8Co0.1Mn0.1(OH)2And mixing the nickel-cobalt-manganese precursor by a ball milling blender mixer to obtain a mixed precursor. Wherein lithium and Ni in the lithium carbonate0.8Co0.1Mn0.1(OH)2In a molar ratio of 1.02: 1.
and (3) placing the mixed precursor into a high-temperature roller sintering furnace for sintering, and preserving heat for 12 hours at 870 ℃ in an oxygen atmosphere. And crushing the sintered lump material by using a double-roller machine, and then crushing mechanically to obtain the lithium nickel cobalt manganese oxide.
And mixing the lithium nickel cobalt manganese oxide and aluminum tungstate according to a mass ratio of 99.7:0.3, and then keeping the temperature at 450 ℃ for 6 hours in an oxygen atmosphere to obtain the lithium nickel cobalt manganese oxide with the surface coated with the aluminum tungstate.
Example 3
Lithium hydroxide is mixed with Ni0.6Co0.2Mn0.2(OH)2And mixing the nickel-cobalt-manganese precursor by a ball milling blender mixer to obtain a mixed precursor. Wherein lithium and Ni in the lithium carbonate0.6Co0.2Mn0.2(OH)2Is 1.03: 1.
and (3) sintering the mixed precursor in a high-temperature roller sintering furnace, and keeping the temperature for 12 hours at 870 ℃ in an air-oxygen mixed atmosphere (with the oxygen content of 60%). And crushing the sintered lump material by using a double-roller machine, and then crushing mechanically to obtain the lithium nickel cobalt manganese oxide.
And mixing the lithium nickel cobalt manganese oxide and aluminum tungstate according to a mass ratio of 99.7:0.3, and keeping the temperature at 450 ℃ for 6 hours in an air atmosphere to obtain the lithium nickel cobalt manganese oxide with the surface coated with the aluminum tungstate.
Example 4
The difference from example 3 is: and (3) performing ball milling and mixing on the lithium nickel cobalt manganese oxide prepared in the example 3 and aluminum tungstate according to the mass ratio of 99.9:0.1, and then keeping the temperature at 400 ℃ for 6 hours in an air atmosphere to obtain the lithium nickel cobalt manganese oxide with the surface coated with the aluminum tungstate.
The rest is the same as embodiment 3, and is not described herein.
Example 5
The difference from example 3 is: and (3) performing ball milling and mixing on the lithium nickel cobalt manganese oxide prepared in the example 3 and aluminum tungstate according to the mass ratio of 99.5:0.5, and then keeping the temperature at 550 ℃ for 6 hours in an air atmosphere to obtain the lithium nickel cobalt manganese oxide with the surface coated with the aluminum tungstate.
The rest is the same as embodiment 3, and is not described herein.
Example 6
The difference from example 3 is: and (3) performing ball milling and mixing on the lithium nickel cobalt manganese oxide prepared in the example 3 and aluminum tungstate according to the mass ratio of 99.5:0.5, and then keeping the temperature at 450 ℃ for 6 hours in an air atmosphere to obtain the lithium nickel cobalt manganese oxide with the surface coated with the aluminum tungstate.
The rest is the same as embodiment 3, and is not described herein.
Example 7
The difference from example 3 is: and (3) performing ball milling and mixing on the lithium nickel cobalt manganese oxide prepared in the example 3 and aluminum tungstate according to the mass ratio of 99.5:0.5, and then keeping the temperature at 600 ℃ for 6 hours in an air atmosphere to obtain the lithium nickel cobalt manganese oxide with the surface coated with the aluminum tungstate.
The rest is the same as embodiment 3, and is not described herein.
Comparative example 1
The lithium nickel cobalt manganese oxide prepared in example 3 was used as a positive electrode material without modification.
Comparative example 2
Example 3 differs in that: the lithium nickel cobalt manganese oxide prepared in example 3 was mixed with alumina (Al)2O3) Ball-milling and mixing according to the mass ratio of 99.7:0.3, and then keeping the temperature for 6 hours at 450 ℃ in the air atmosphere to obtain the lithium-nickel-cobalt-manganese oxide with the surface coated with the alumina.
Comparative example 3
The difference from example 3 is: the lithium nickel cobalt manganese oxide prepared in example 3 was mixed with tungsten oxide (WO)3) Ball-milling and mixing according to the mass ratio of 99.7:0.3, and then keeping the temperature for 6 hours at 450 ℃ in the air atmosphere to obtain the lithium-nickel-cobalt-manganese oxide with the surface coated with the tungsten oxide.
Some preparation parameters of examples 1 to 7 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1
The powder conductivities of the positive electrode materials prepared in examples 1 to 7 and comparative examples 1 to 3 were measured on a Four-probe conductivity tester type Four Dimensions 208SI with the results detailed in table 2.
The positive electrode materials prepared in examples 1 to 7 and comparative examples 1 to 3 were mixed with conductive carbon and a binder polyvinylidene fluoride (PVDF) at a mass ratio of 90: 5: 5, mixing the mixture in an N-methylpyrrolidone (NMP) solvent, stirring the mixture for 12 hours at normal temperature, coating the mixture on an Al foil current collector with the thickness of 16 mu m by a scraper, drying the mixture for 12 hours in vacuum at 120 ℃, and punching the mixture into a wafer positive electrode with the diameter of 14.0mm after cold pressing; the negative electrode adopts a metal lithium sheet with the diameter of 15.0 mm; the electrolyte adopts 1mol/L LiPF6, and EC/EMC is 3:7 (V/V); a polypropylene (PP) isolation film is adopted and assembled in a glove box to obtain a CR2430 button cell, and relevant electrochemical performances are tested on a LAND button cell tester. The test results are shown in table 2.
Testing the specific discharge capacity for the first time: at 25 ℃ and normal pressure (0.1MPa), charging to 4.2V by using a 0.1C constant current, further charging to 0.05C by using a 4.2V constant voltage, and then discharging to 2.8V by using a 0.1C constant current to obtain the initial discharge specific capacity M (mAh/g) of the button cell.
And D, direct current resistance testing: the Direct Current Resistance (DCR) was measured by a discharge method, and for a 3.85V button cell, a 0.1C discharge (current I1) was performed to record the voltage V1 for 10s, followed by a 1C discharge (current I2) and a 0.2s recording of the voltage V2, DCR ═ V1-V2)/(I2-I1.
TABLE 2
As can be seen from the test results of comparative examples 1-3 in table 2, the pure alumina or tungsten oxide modification can improve the specific first discharge capacity of the button cell compared to the lithium nickel cobalt manganese oxide without surface modification coating, but has limited effect on the powder conductivity of the positive electrode material and the DCR. As can be seen from the results of comparing examples 1 to 7 and comparative examples 1 to 3, the powder conductivity and DCR of the lithium nickel cobalt manganese oxide cathode material modified by aluminum tungstate were significantly improved as compared to the lithium nickel cobalt manganese oxide cathode material modified or not modified by other modifying substances (aluminum oxide or tungsten oxide), and the powder conductivity of the lithium nickel cobalt manganese oxide cathode material coated by aluminum tungstate modified in examples 1 to 7 was about 2 to 3 times that of the lithium nickel cobalt manganese oxide cathode material modified or not modified by other modifying substances (aluminum oxide or tungsten oxide) in comparative examples 1 to 3, and the DCR was reduced by more than 30%.
The button cell batteries of example 3 and comparative examples 1-3 were tested for charge and discharge performance and cycle stability, respectively, at a charge and discharge voltage of 3.0-4.2V and a current density of 3C (540 mA/g). The charge and discharge performance test results are shown in fig. 2, and the cycle stability test results are shown in fig. 3.
Referring to fig. 2, the first charge-discharge specific capacity of example 3 is significantly improved compared to comparative examples 1 to 3. Referring to fig. 3, the cycling stability of the button cell of example 3 is significantly improved compared to the comparative examples 1-3. Therefore, the aluminum tungstate modified and coated lithium nickel cobalt manganese oxide as the positive electrode material can obviously improve the charge-discharge specific capacity and the cycle performance of the button cell.
The preparation method of the modified lithium nickel cobalt manganese oxide cathode material provided by the application is simple in process flow, and the cycle performance, the rate performance and the conductivity performance of the cathode material can be improved by coating aluminum tungstate on the lithium nickel cobalt manganese oxide.
Although the present application has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the present application.
Claims (10)
1. The preparation method of the modified lithium nickel cobalt manganese oxide cathode material is characterized by comprising the following steps of:
providing lithium nickel cobalt manganese oxide;
and mixing the lithium nickel cobalt manganese oxide and aluminum tungstate, and sintering to obtain the modified lithium nickel cobalt manganese oxide cathode material.
2. The method for preparing a modified lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein the mass of the aluminum tungstate is 0.1% to 0.5% of the total mass of the aluminum tungstate and the lithium nickel cobalt manganese oxide.
3. The method of claim 1, wherein the step of providing the lithium nickel cobalt manganese oxide comprises:
providing a lithium compound and a nickel-cobalt-manganese precursor, and mixing the lithium compound and the nickel-cobalt-manganese precursor to obtain a mixed precursor;
and sintering the mixed precursor to obtain the lithium nickel cobalt manganese oxide.
4. The method for preparing the modified lithium nickel cobalt manganese oxide cathode material according to claim 3, wherein the molar ratio of lithium in the lithium compound to the nickel cobalt manganese precursor is 1.00 to 1.05: 1.
5. the preparation method of the modified lithium nickel cobalt manganese oxide cathode material according to claim 3, wherein the mixed precursor is sintered at 850-950 ℃ for 10-12 h.
6. The method for preparing the modified lithium nickel cobalt manganese oxide cathode material according to claim 1, wherein the lithium nickel cobalt manganese oxide is mixed with aluminum tungstate by a ball milling method.
7. The preparation method of the modified lithium nickel cobalt manganese oxide cathode material according to claim 1, wherein the sintering temperature of the sintering treatment after the lithium nickel cobalt manganese oxide is mixed with aluminum tungstate is 400-600 ℃, and the sintering time is 4-6 h.
8. The modified lithium nickel cobalt manganese oxide positive electrode material is characterized by comprising a lithium nickel cobalt manganese oxide and aluminum tungstate coated on the lithium nickel cobalt manganese oxide.
9. A positive electrode comprising the modified lithium nickel cobalt manganese oxide positive electrode material of claim 8.
10. A lithium ion battery comprising the positive electrode of claim 9.
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