CN114927693A - Positive electrode active material, method for producing same, electrochemical device, and electronic device - Google Patents
Positive electrode active material, method for producing same, electrochemical device, and electronic device Download PDFInfo
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- CN114927693A CN114927693A CN202210605411.8A CN202210605411A CN114927693A CN 114927693 A CN114927693 A CN 114927693A CN 202210605411 A CN202210605411 A CN 202210605411A CN 114927693 A CN114927693 A CN 114927693A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000463 material Substances 0.000 claims abstract description 98
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 56
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 54
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 52
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000010936 titanium Substances 0.000 claims abstract description 44
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 36
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims description 48
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 230000001351 cycling effect Effects 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000006183 anode active material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 229920000515 polycarbonate Polymers 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 229910014031 strontium zirconium oxide Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- -1 titanium oxide) Chemical class 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Classifications
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive active material, a preparation method thereof, an electrochemical device and electronic equipment, wherein the positive active material comprises a ternary material core and a titanium compound coated on the surface of the ternary material core, and the ternary material core comprises zirconium element and strontium element; based on the total mass of metal elements in the positive electrode active material, the total content of zirconium elements in the positive electrode active material is 1400ppm to 2200ppm, the total content of strontium elements in the positive electrode active material is 200ppm to 800ppm, and the content of titanium elements in the titanium compound is 500ppm to 1000 ppm. The positive active material has good crystallinity and interface stability, and has higher gram capacity, coulombic efficiency and cycle stability.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a positive active material, a preparation method thereof, an electrochemical device and electronic equipment.
Background
Ternary layered material LiNi x Co y Mn 1-x-y O 2 The high-capacity lithium ion battery has high theoretical specific capacity (274mAh/g), high reaction platform voltage (3.0V to 4.4V) and excellent reaction kinetics, so that the high-capacity lithium ion battery is widely applied to a power battery system with high energy density. In order to take the safety performance of the material into consideration, the Ni content, namely the x value, in the ternary material is controlled below 0.7. Meanwhile, in consideration of the fact that Co is increasingly scarce as a rare mineral resource in the raw material, the Co content in the raw material, that is, the y value, generally needs to be controlled to 0.2 or less.
In the ternary material, the capacity is mainly determined by the content of Ni, and reduction in Ni causes reduction in the capacity of the material, thereby further reducing the energy density of the entire battery. The reduction of Co content can affect the overall conductivity of the material, and improve the diffusion barrier of lithium ions in crystal lattices, thereby bringing about a serious reaction kinetics retardation problem and finally affecting the capacity exertion of the battery. Therefore, the Ni content and the Co content in the ternary material are reduced, and the energy density, the dynamic performance and the cycle performance of the material are considered at the same time, so that the ternary material is a problem to be solved urgently.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide a positive electrode active material, a method of preparing the same, an electrochemical device, and an electronic apparatus. According to the invention, the ternary material is doped and coated and modified to obtain the anode active material with the ternary material kernel doped with the zirconium element and the strontium element with specific contents, and the titanium compound with proper content is coated outside the kernel, so that the crystallinity and the interface stability of the anode active material are controlled in an optimal range, and thus a product with excellent capacity and cycle performance is obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a positive active material, which comprises a ternary material core and a titanium compound coated on the surface of the ternary material core, wherein the ternary material core comprises zirconium element and strontium element;
based on the total mass of metal elements in the positive electrode active material, the total content of zirconium elements in the positive electrode active material is 1400ppm to 2200ppm, the total content of strontium elements in the positive electrode active material is 200ppm to 800ppm, and the content of titanium elements in the titanium compound is 500ppm to 1000 ppm.
In the present invention, the total content of the zirconium element in the positive electrode active material is 1400ppm to 2200ppm, and may be, for example, 1400ppm, 1500ppm, 1600ppm, 1700ppm, 1800ppm, 1900ppm, 2000ppm, 2100ppm, 2200ppm, or the like; the total content of strontium element in the positive electrode active material is 200ppm to 800ppm, and may be, for example, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm or the like; the content of titanium element in the titanium compound is 500ppm to 1000ppm, and may be, for example, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1000ppm or the like.
The anode active material comprises a ternary material core and a titanium compound coated on the surface of the ternary material core, wherein the ternary material core is doped with strontium elements and zirconium elements with specific contents, the core is coated with the titanium elements with specific contents, and the strontium elements, the zirconium elements and the titanium elements are distributed in the anode active material according to a proper proportion, so that the crystallinity and the interface stability of the material can be improved, and the material has high capacity and good cycle stability.
The principle of the invention is as follows: firstly, strontium has strong oxygen bonding force, the sintering temperature in the material preparation process can be reduced, 200ppm to 800ppm of strontium and 1400ppm to 2200ppm of zirconium are doped into a ternary material core in a bonding manner, and the crystallinity and the interface stability of the material can be improved and the capacity, the thermal property and the long-term cycling stability of the material can be improved by the mutual matching of the strontium and the zirconium with specific contents; secondly, coating the titanium compound with specific content on the surface of the material, wherein the content of titanium element is 500ppm to 1000ppm, so that the dynamics of the surface of the material can be further improved, the material is prevented from being corroded by electrolyte, and the material is protected; thirdly, the zirconium, strontium and titanium with specific contents act synergistically to obtain a material with the best crystallinity and interface stability, and the gram volume, the coulombic efficiency and the cycling stability of the positive active material are improved.
Preferably, the depth of the titanium element distributed inward along the surface of the positive electrode active material is 140nm to 560nm, and may be 140nm, 180nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 560nm, or the like, for example.
It should be noted that, in the present invention, the titanium element is distributed inward along the surface of the positive electrode active material, and the depth thereof includes the thickness of the titanium compound, and when the titanium element penetrates into the core of the ternary material, the thickness thereof also includes the penetration depth of the titanium element into the core of the ternary material.
Preferably, the D50 particle size of the positive electrode active material is 2 μm to 6 μm, and may be, for example, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, or 6 μm, etc.; the positive active material prepared by the method has a proper particle size, and meanwhile, the titanium element has a proper penetration depth (140 nm-560 nm) in the positive active material, and the crystallinity and the interface stability of the material can be improved by matching the proper penetration depth of the titanium element in the particle size range.
Preferably, the titanium compound comprises titanium oxide.
Preferably, the ternary material core also comprises titanium element.
Preferably, zirconia and/or strontium oxide is/are further included between the ternary material core and the titanium compound.
In the anode active material, the strontium element and the zirconium element are doped in the ternary material core, and can be partially present between the ternary material core and the titanium compound in the form of strontium oxide and zirconium oxide; besides being coated on the surface of the ternary material core in the form of a titanium compound, the titanium element can also partially permeate into crystal lattices of the ternary material core, so that the capacity and the cycling stability of the battery are further improved.
Preferably, the surface of the positive electrode active material includes free lithium, and the content of the free lithium is 350ppm to 1150ppm, for example, 350ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1100ppm, 1150ppm, or the like, based on the total mass of the metal elements in the positive electrode active material.
In a second aspect, the present invention provides a method for producing the positive electrode active material according to the first aspect, the method comprising the steps of:
(1) mixing a ternary material precursor, a lithium source, a zirconium source and a strontium source, and sintering at 920-975 ℃ for one time to obtain a first product;
(2) mixing the first product with a titanium source, and performing secondary sintering at 150-400 ℃ to obtain the positive electrode active material;
based on the total mass of metal elements in the ternary material precursor, the lithium source, the zirconium source, the strontium source and the titanium source, the content of the zirconium element in the zirconium source is 2000ppm to 3000ppm, the content of the strontium element in the strontium source is 300ppm to 1000ppm, and the content of the titanium element in the titanium source is 800ppm to 1500 ppm.
The temperature of the primary sintering in the invention is 920-975 ℃, such as 920 ℃, 925 ℃, 930 ℃, 935 ℃, 940 ℃, 945 ℃, 950 ℃, 955 ℃, 960 ℃, 965 ℃, 970 ℃ or 975 ℃; the temperature of the secondary sintering is 150 ℃ to 400 ℃, and may be, for example, 150 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃ or 400 ℃.
In the present invention, the content of the zirconium element in the zirconium source is 2000ppm to 3000ppm, for example, 2000ppm, 2100ppm, 2200ppm, 2300ppm, 2400ppm, 2500ppm, 2600ppm, 2700ppm, 2800ppm, 2900ppm, 3000ppm, or the like, based on the total mass of the metal elements in the ternary material precursor, the lithium source, the zirconium source, the strontium source, and the titanium source; the strontium element in the strontium source is 300ppm to 1000ppm, for example, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm or 1000 ppm; the titanium source may contain titanium in an amount of 800ppm to 1500ppm, for example, 800ppm, 900ppm, 1000ppm, 1100ppm, 1200ppm, 1300ppm, 1400ppm, 1500ppm, or the like.
The invention adopts a two-step sintering mode, firstly, a zirconium source and a strontium source are mixed and sintered with a ternary material precursor and a lithium source at a specific temperature, most of zirconium and strontium in the zirconium source and the strontium source enter crystal lattices of the ternary material precursor, and a small amount of zirconium and strontium are remained on the surface of the precursor in the form of compounds (such as zirconium oxide and strontium oxide); then adding a titanium source to perform secondary sintering at a specific temperature, reacting the more active titanium with residual lithium on the surface of the material, coating the most part of the titanium on the surface of the material in the form of a titanium compound (such as titanium oxide), and infiltrating a small part of the titanium into crystal lattices of the material to obtain the anode active material.
According to the invention, when sintering is carried out at 920-975 ℃ for one time, a zirconium source and a strontium source with specific contents are added into the ternary material precursor, strontium has strong oxygen bonding force, the sintering temperature can be reduced, and the combination of zirconium and strontium can improve the capacity, thermal performance and long-term circulation stability of the material; meanwhile, a strontium source and a zirconium source are added at the temperature for sintering, so that zirconium element can permeate into the crystal lattice, and the cooperation of strontium and zirconium source can reduce the sintering temperature, improve the crystallinity of the crystal lattice and prevent the disorder of the crystal lattice. And a titanium source is added during secondary sintering at the temperature of between 150 and 400 ℃, so that a titanium compound is coated on the surface of the material, the dynamics of the surface of the material can be further improved, the material is prevented from being corroded by electrolyte, and the material is protected. According to the invention, zirconium, strontium and titanium are cooperated according to a certain proportion, and sintering conditions are controlled, so that a material with the best crystallinity and interface stability can be obtained, and the gram volume, the coulombic efficiency and the cycling stability of the positive active material are improved.
As a preferred technical scheme of the preparation method, the temperature of the primary sintering is 930-975 ℃.
Preferably, the time of the primary sintering is 12h to 24h, and for example, 12h, 14h, 16h, 18h, 20h, 22h or 24h and the like can be provided.
Preferably, the atmosphere of the primary sintering includes oxygen, and the content of the oxygen is greater than or equal to 80% by volume based on the total volume of the atmosphere, for example, 80%, 82%, 84%, 96%, 88%, 90%, 92%, 94%, 96%, 98%, 100%, or the like.
Preferably, the temperature of the secondary sintering is 200 ℃ to 400 ℃.
Preferably, the time of the secondary sintering is 4h to 10h, for example, 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc.
Preferably, the atmosphere of the secondary sintering includes oxygen, and the content of the oxygen is greater than or equal to 80% by volume based on the total volume of the atmosphere, for example, 80%, 82%, 84%, 96%, 88%, 90%, 92%, 94%, 96%, 98%, 100%, or the like.
According to the invention, the material with the best crystallinity and interface stability is obtained by further optimizing the primary sintering temperature and the secondary sintering temperature and matching with a certain content of a zirconium source, a strontium source and a titanium source, and the gram volume, the coulombic efficiency and the cycling stability of the positive active material are further improved.
Preferably, the ternary material precursor has a chemical formula of Ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.56 and less than or equal to 0.60, such as 0.56, 0.57, 0.58, 0.59 or 0.6, etc., and y is more than or equal to 0.09 and less than or equal to 0.13, such as 0.09, 0.1, 0.11, 0.12 or 0.13, etc., the invention adopts a low-cobalt ternary material, and within the element proportion range, the safety of the finished battery can be improved, the use of a rare element Co element can be reduced, and the capacity and the cycling stability of the prepared positive active material can be improved by the synergistic effect of the low-cobalt ternary material and a zirconium source, a strontium source and a titanium source.
Preferably, the lithium source comprises lithium carbonate and/or lithium hydroxide.
Preferably, the zirconium source comprises zirconium oxide.
Preferably, the strontium source comprises strontium oxide.
Preferably, the titanium source comprises titanic acid.
The zirconium oxide, strontium oxide and titanic acid in the present invention may also be replaced by other zirconium-, strontium-or titanium-containing compounds, respectively, such as zirconium hydroxide, lithium zirconate (Li) 2 ZrO 3 ) Zirconium carbonate, strontium hydroxide, strontium carbonate, lithium titanate (Li) 4 Ti 5 O 12 ) Titanium dioxide or titanium sesquioxide, and the like.
The zirconia and the strontium oxide in the invention can adopt nano zirconia and nano strontium oxide, and the D50 particle size is in the range of 50nm to 500 nm.
In a third aspect, the present invention provides an electrochemical device comprising the positive electrode active material according to the first aspect in a positive electrode thereof.
The anode active material has good crystallinity and stable interface structure, and the electrochemical device prepared by the anode active material has higher capacity and better cycle performance.
In an alternative embodiment, the present invention provides a method for detecting whether a positive active material according to the present invention is contained in an electrochemical device, comprising:
the electrochemical device sample is split to obtain a positive electrode, the positive electrode is washed by a solvent and dried, the surface of the positive electrode is coated by blade coating to obtain active substance powder, the active substance powder is subjected to ICP test, and the content of Ti, Sr and Zr elements is observed to be in a limited range (Ti: 500ppm to 1000ppm, Sr: 200ppm to 800ppm, Zr: 1400ppm to 2200ppm), so that the positive electrode of the electrochemical device sample can be confirmed to contain the positive electrode active material. And a time-of-flight secondary ion mass spectrometer is used for testing the distribution depth of the Ti element, and the penetration depth of the Ti element is observed and found to be in a limited range (140nm to 560nm), so that the positive electrode of the electrochemical device sample is further confirmed to contain the positive electrode active material.
In an alternative embodiment, the present invention provides a method for preparing the positive electrode, including:
and mixing the positive active material, the conductive agent, the binder and the solvent to obtain positive slurry, coating the positive slurry on an aluminum foil, and rolling to obtain the positive electrode.
Preferably, the conductive agent comprises conductive carbon black (SP) and/or Carbon Nanotubes (CNT).
Preferably, the binder comprises polyvinylidene fluoride (PVDF).
Preferably, the mass ratio of the positive electrode active material, the SP, the CNT and the PVDF is (90 to 99):1:0.5:1, and may be, for example, 90:1:0.5:1, 92:1:0.5:1, 94:1:0.5:1, 96:1:0.5:1, 98:1:0.5:1 or 99:1:0.5:1, etc.
In an alternative embodiment, the electrochemical device is a lithium ion battery.
In an alternative embodiment, the negative electrode of the electrochemical device comprises graphite, SP, carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR) in a mass ratio (90 to 99) of 1:1.5:2, which may be, for example, 90:1:1.5:2, 92:1:1.5:2, 94:1:1.5:2, 96:1:1.5:2, 98:1:1.5:2, or 99:1:1.5:2, etc.
In an alternative embodiment, the electrolyte of the electrochemical device includes a lithium salt and a solvent.
In an alternative embodiment, the lithium salt comprises LiPF 6 。
In an alternative embodiment, the lithium salt is present in an amount of 4 wt% to 24 wt%, for example, 4 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 24 wt%, or the like, based on 100 wt% of the mass of the electrolyte.
In an alternative embodiment, the solvent comprises at least one of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC) and Polycarbonate (PC) or a combination of any two thereof, for example, a combination of EC and EMC, a combination of DMC and PC, a combination of EC, EMC and DMC, or a combination of EC, EMC, DMC and PC, or the like.
In an alternative embodiment, the mass ratio of EC, EMC, DMC and PC in the solvent is (2 to 4): (3 to 5): (2 to 4): (0 to 1), the selection range of EC (2 to 4) may be, for example, 2, 2.5, 3, 3.5, or 4, etc., the selection range of EMC (3 to 5) may be, for example, 3, 3.5, 4, 4.5, or 5, etc., the selection range of DMC (2 to 4) may be, for example, 2, 2.5, 3, 3.5, or 4, etc., the selection range of PC (0 to 1) may be, for example, 0, 0.1, 0.2, 0.3, 0.5, 0.7, or 1, etc., and when PC is 0, it means that PC is not contained in the solvent.
In an alternative embodiment, the separator of the electrochemical device has a thickness of 9 μm to 18 μm, and may be, for example, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, or the like.
In an alternative embodiment, the separator of the electrochemical device has an air permeability of 180s/100mL to 380s/100mL, and may be, for example, 180s/100mL, 200s/100mL, 240s/100mL, 250s/100mL, 280s/100mL, 300s/100mL, 250s/100mL, or 380s/100mL, or the like.
In an alternative embodiment, the porosity of the separator of the electrochemical device is 30% to 50%, and may be, for example, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, or 50%, etc.
The diaphragm with appropriate parameters is selected to be matched with the anode and the cathode to prepare the electrochemical device, so that the capacity and the cycling stability of the electrochemical device are improved.
In a fourth aspect, the invention provides an electronic device comprising an electrochemical device according to the third aspect.
The electronic device according to the present invention may be, for example, a mobile computer, a portable phone, a memory card, a liquid crystal television, an automobile, a motorcycle, a motor, a timepiece, a camera, or the like.
Compared with the prior art, the invention has the beneficial effects that:
the cathode active material comprises a ternary material core doped with strontium element and zirconium element and a titanium compound coated on the surface of the ternary material core, wherein strontium has strong oxygen bonding force, the sintering temperature in the material preparation process can be reduced, and the strontium element and the zirconium element with specific contents are combined and doped into the ternary material core, so that the crystallinity and the interface stability of the material can be improved, and the capacity, the thermal property and the long-term circulation stability of the material can be improved. The titanium compound with specific content is coated outside the inner core of the ternary material, so that the dynamics of the surface of the material can be further improved, the material is prevented from being corroded by electrolyte, and the material is protected. The strontium element, the zirconium element and the titanium element are distributed in the positive active material in a proper proportion and are cooperated to obtain a material with the best crystallinity and the best interface stability, and the gram volume, the coulomb efficiency and the cycling stability of the positive active material are improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a positive active material, which comprises a ternary material core LiNi 0.58 Co 0.11 Mn 0.31 O 2 And titanium oxide coated on the surface of the ternary material core, wherein the ternary material core is doped with zirconium element, strontium element and titanium element, and the surface of the positive active material also comprises free lithium; based on the total mass of metal elements (Li, Ni, Co, Mn, Zr, Sr and Ti) in the positive electrode active material, the total content of zirconium element in the positive electrode active material is 1892ppm, the total content of strontium element in the positive electrode active material is 544ppm, the content of titanium element in titanium oxide is 665ppm, the depth of the inward distribution of the titanium element along the surface of the positive electrode active material is 243nm, and the content of free lithium on the surface of the positive electrode active material is 670 ppm.
The embodiment also provides a preparation method of the positive active material, which comprises the following steps:
(1) precursor Ni of ternary material 0.58 Co 0.11 Mn 0.31 (OH) 2 Mixing lithium carbonate, nano zirconia and nano strontium oxide, and sintering for 17 hours in an oxygen atmosphere at the temperature of 950 ℃ to obtain a first product;
(2) mixing the first product with titanic acid, and sintering for the second time for 6 hours in an oxygen atmosphere, wherein the temperature of the second sintering is 300 ℃, so as to obtain the anode active material;
wherein, with said Ni 0.58 Co 0.11 Mn 0.31 (OH) 2 Based on the total mass of metal elements (Li, Ni, Co, Mn, Zr, Sr and Ti) in lithium carbonate, nano-zirconia, nano-strontium oxide and titanic acid, the content of zirconium element in the nano-zirconia is 2000ppm, the content of strontium element in the nano-strontium oxide is 600ppm, the content of titanium element in the titanic acid is 1000ppm, and lithium carbonate and Ni are added 0.58 Co 0.11 Mn 0.31 (OH) 2 In a molar ratio of 1.02: 1.
Assembling of lithium ion battery
(1) Preparation of the positive electrode: mixing the positive electrode active material, SP, CNT and PVDF which are prepared in the embodiment and the comparative example of the invention with N-methyl pyrrolidone (NMP) according to the mass ratio of 97.5:1:0.5:1 to prepare positive electrode slurry, then coating the positive electrode slurry on aluminum foil, and rolling to obtain a positive electrode;
(2) preparation of a negative electrode: mixing graphite, SP, CMC and SBR according to a mass ratio of 95.5:1:1.5:2 to prepare slurry, coating the slurry on a copper foil, and rolling to obtain a negative electrode;
(3) preparing a lithium ion battery: adhering an aluminum positive electrode tab to a positive electrode, adhering a copper negative electrode tab to a negative electrode, selecting a diaphragm with the thickness of 10 μm, the air permeability of 200s/100mL and the porosity of 40%, sequentially and tightly overlapping the positive electrode, the diaphragm and the negative electrode, and injecting 5 wt% LiPF solute into two sides of the diaphragm 6 And the solvent is an electrolyte of EC, EMC, DMC and PC with the mass ratio of 3:4:3:0.5 to obtain a battery cell, and the battery cell is stacked to the required number of layers to obtain the lithium ion battery.
Second, performance test
(1) Testing of positive electrode active material:
the contents of Zr, Sr and Ti elements were measured by Inductively Coupled Plasma (ICP).
A depth test method in which Ti element is distributed inward along the surface of the positive electrode active material: the powder particles of the positive active material were cut by a focused ion beam method, and then the distribution depth of Ti element was tested by a time-of-flight secondary ion mass spectrometer.
Testing of the content of free lithium on the surface of the positive electrode active material: 1g of positive electrode active material powder was placed inStirring with a glass rod for 5min in deionized water, standing for 4h, collecting supernatant, and testing LiOH and Li with a potentiometric titrator 2 CO 3 The content of (a), wherein the amount of lithium element, is the content of surface-coated free lithium.
(2) Testing of the lithium ion battery:
adopting a battery performance test system (equipment model: BTS05/10C8D-HP) of the Shenghong electric appliance component electric company Limited to carry out a first discharge capacity test and a 800-week circulation capacity retention rate test;
the first discharge gram capacity test method comprises the following steps: under the condition of 25 ℃, charging and discharging for one week in a charging and discharging mode of 0.063A/g, wherein the voltage interval is 2.8V to 4.35V, and the obtained charging and discharging capacity is divided by the usage amount of the positive electrode, namely the first charging/discharging gram capacity. The first coulombic efficiency is obtained by dividing the first discharge capacity by the first charge capacity.
800-week cycle capacity retention rate test method: under the condition of 25, the cycle is carried out according to the charge-discharge standard of 0.19A/g (calculated by the mass of the anode material), and the voltage interval is 2.8V to 4.35V. After the cycle is performed for 800 weeks, the discharge capacity of the battery at the moment is divided by the discharge capacity of the first cycle, and the cycle capacity retention rate of the battery at 800 cycles is obtained.
Examples 2 to 5 and comparative examples 1 to 6 were modified based on the procedure of example 1, and the specific modified parameters and test results are shown in tables 1 to 6.
TABLE 1
TABLE 2
| First discharge gram capacity (mAh/g) | First coulombic efficiency (%) | Retention ratio of 800-week-cycle Capacity (%) | |
| Example 1 | 187.2 | 87.3 | 95 |
| Example 2 | 189.1 | 88.2 | 94 |
| Example 3 | 186.4 | 87.7 | 96 |
TABLE 3
TABLE 4
As can be seen from the comparison between example 1 and examples 4 to 5 and comparative examples 1 to 2 in tables 3 and 4, the temperature of the primary sintering and the secondary sintering in the present invention affects the content and distribution of elements in the positive electrode active material, the crystallinity and the interfacial stability of the material, and further the gram capacity, the coulombic efficiency and the capacity retention ratio of the material.
In comparative example 1 and example 4, when the secondary sintering temperature is lower, the titanic acid can not fully react with the free lithium on the surface of the material and can not further penetrate into the material, and most of the titanic acid is coated on the surface of the material in the form of a titanium compound, so that the contents of Ti in the titanium compound and the free lithium on the surface of the material in the comparative example 1 are too high, and the first discharge gram capacity, the coulombic efficiency and the 800-week cycle capacity retention rate of the material are lower than those in example 1; compared with the embodiment 1 and the comparative example 1, when the secondary sintering temperature is too high, most of titanium elements enter the interior of the crystal lattice of the material, the Ti elements deeply penetrate inwards along the surface of the positive electrode active material, the titanium element content on the surface of the material is low, and the contact between the material and the electrolyte is influenced, so that the first discharge gram capacity, the coulombic efficiency and the 800-cycle capacity retention rate of the comparative example 1 are all lower than those of the embodiment 1.
Comparing example 1 with example 5, when the primary sintering temperature is lower, the surface free lithium is higher, meanwhile, the primary sintering temperature influences the distribution of titanium element during secondary sintering, the penetration depth of the titanium element is shallower in example 5, and the gram capacity and the cycling stability of the material are not good; comparing example 1 and comparative example 2, when the primary sintering temperature is too high, the surface free lithium is too little, and meanwhile, in comparative example 2, the titanium element has a deeper penetration depth and the content of the coated titanium oxide is less, which affects the gram capacity exertion of the material and has poor cycle stability.
TABLE 5
As can be seen from comparison between example 1 and comparative examples 3 to 5 in table 5, in the present invention, the three elements have appropriate contents, and when sintering is performed under the same conditions, the charging amounts of the three elements of zirconium, strontium, and titanium are changed, so that the contents of the three elements in the positive electrode active material are changed, which affects the discharge capacity and the cycle stability of the finally prepared lithium ion battery. When the addition amount of a certain element is changed to be out of the optimum range singly, the gram-discharge capacity and the first efficiency are reduced, and the cycle stability is also deteriorated, so that the three elements of zirconium, strontium and titanium in example 1 are in the most suitable content range, and the gram-discharge capacity and the cycle stability of the lithium ion battery prepared therefrom are optimum.
Comparative example 6
This comparative example was identical to example 1 except that the secondary sintering was not carried out and titanic acid was added directly at 950 ℃ for the primary sintering.
TABLE 6
| First discharge gram capacity (mAh/g) | First coulombic efficiency (%) | Retention ratio of 800-week cycle capacity (%) | |
| Example 1 | 187.2 | 87.3 | 95 |
| Comparative example 6 | 182.7 | 86.8 | 36 |
It can be known from the comparison between the embodiment 1 and the comparative example 6 that the sintering is carried out twice at a specific temperature, the zirconium source and the strontium source are added for doping, and then the titanium source is added for coating, so that most of titanium elements are combined with the ternary material kernel in the form of a coating layer, the crystallinity and the interface stability of the positive active material can be improved, the synergistic effect among the three elements is fully exerted, and the gram capacity, the coulombic efficiency and the cycling stability of the positive active material are improved; in the comparative example 6, titanic acid is directly added during primary sintering, most of titanium element is doped into the core, the content of titanium element in the coating layer is too low, so that the doping and coating effects are poor, and the prepared material has poor circulation stability.
In summary, in examples 1 to 5, it can be seen that, in the present invention, a ternary material is doped and coated and modified to obtain a positive electrode active material in which a core is doped with a specific content of zirconium element and strontium element and is coated with a suitable content of titanium compound, and crystallinity and interface stability of the positive electrode active material can be controlled within an optimal range, so as to obtain a product with excellent capacity and cycle performance.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The positive active material is characterized by comprising a ternary material core and a titanium compound coated on the surface of the ternary material core, wherein the ternary material core comprises zirconium element and strontium element;
based on the total mass of metal elements in the positive electrode active material, the total content of zirconium elements in the positive electrode active material is 1400ppm to 2200ppm, the total content of strontium elements in the positive electrode active material is 200ppm to 800ppm, and the content of titanium elements in the titanium compound is 500ppm to 1000 ppm.
2. The positive electrode active material according to claim 1, wherein the titanium element is distributed inward along the surface of the positive electrode active material to a depth of 140nm to 560 nm.
3. The positive electrode active material according to claim 1, wherein the particle diameter D50 of the positive electrode active material is 2 to 6 μm.
4. The positive electrode active material according to claim 1, wherein the positive electrode active material satisfies any one of the following conditions (a) to (d):
(a) the titanium compound comprises titanium oxide;
(b) the ternary material inner core also comprises titanium element;
(c) zirconium oxide and/or strontium oxide are/is further included between the ternary material inner core and the titanium compound;
(d) the surface of the positive electrode active material includes free lithium, and the content of the free lithium is 350ppm to 1150ppm based on the total mass of the metal elements in the positive electrode active material.
5. A method for producing the positive electrode active material according to any one of claims 1 to 4, characterized by comprising the steps of:
(1) mixing a ternary material precursor, a lithium source, a zirconium source and a strontium source, and sintering at 920-975 ℃ for one time to obtain a first product;
(2) mixing the first product with a titanium source, and performing secondary sintering at 150-400 ℃ to obtain the positive electrode active material;
based on the total mass of metal elements in the ternary material precursor, the lithium source, the zirconium source, the strontium source and the titanium source, the content of the zirconium element in the zirconium source is 2000ppm to 3000ppm, the content of the strontium element in the strontium source is 300ppm to 1000ppm, and the content of the titanium element in the titanium source is 800ppm to 1500 ppm.
6. The production method according to claim 5, wherein the primary sintering satisfies any one of the following conditions (e) to (g):
(e) the temperature of the primary sintering is 930 ℃ to 975 ℃;
(f) the time of the primary sintering is 12-24 h;
(g) the atmosphere of the primary sintering comprises oxygen, and the volume content of the oxygen is greater than or equal to 80% based on the total volume of the atmosphere.
7. The production method according to claim 5, wherein the secondary sintering satisfies any one of the following conditions (h) to (j):
(h) the temperature of the secondary sintering is 200-400 ℃;
(i) the secondary sintering time is 4-10 h;
(j) the atmosphere of the secondary sintering comprises oxygen, and the volume content of the oxygen is greater than or equal to 80% by taking the total volume of the atmosphere as a reference.
8. The production method according to claim 5, wherein the ternary material precursor, the zirconium source, the strontium source, and the titanium source satisfy any one of the following conditions (k) to (n):
(k) the chemical formula of the ternary material precursor is Ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.56 and less than or equal to 0.60, and y is more than or equal to 0.09 and less than or equal to 0.13;
(l) The zirconium source comprises zirconium oxide;
(m) the strontium source comprises strontium oxide;
(n) the titanium source comprises titanic acid.
9. An electrochemical device comprising the positive electrode active material according to any one of claims 1 to 4 in a positive electrode thereof.
10. An electronic device, characterized in that the electrochemical device according to claim 9 is included in the electronic device.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019027215A2 (en) * | 2017-08-01 | 2019-02-07 | 주식회사 에코프로비엠 | Lithium composite oxide precursor, preparation method therefor, and lithium composite oxide prepared using same |
| WO2019103488A1 (en) * | 2017-11-22 | 2019-05-31 | 주식회사 엘지화학 | Positive electrode active material for lithium secondary battery and manufacturing method therefor |
| CN109888235A (en) * | 2019-03-06 | 2019-06-14 | 广东邦普循环科技有限公司 | A kind of nickelic tertiary cathode material of gradation and its preparation method and application |
| CN110993936A (en) * | 2019-12-02 | 2020-04-10 | 当升科技(常州)新材料有限公司 | High-energy density type nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN111463411A (en) * | 2019-01-18 | 2020-07-28 | 天津国安盟固利新材料科技股份有限公司 | High-nickel ternary cathode material with single crystal morphology and preparation method thereof |
| CN111525118A (en) * | 2020-05-15 | 2020-08-11 | 陕西红马科技有限公司 | Preparation method of mixed nickel-cobalt lithium aluminate anode material |
| CN111646523A (en) * | 2020-06-29 | 2020-09-11 | 蜂巢能源科技有限公司 | High-safety double-doped high-nickel ternary cathode material, preparation method thereof and lithium ion battery |
| CN111902978A (en) * | 2018-04-06 | 2020-11-06 | 株式会社Lg化学 | Positive electrode active material for lithium secondary battery, method for producing same, positive electrode for lithium secondary battery comprising same, and lithium secondary battery |
| CN113161548A (en) * | 2021-03-29 | 2021-07-23 | 广东邦普循环科技有限公司 | Cobalt-free nickel-manganese cathode material and preparation method and application thereof |
| CN113871603A (en) * | 2021-09-29 | 2021-12-31 | 蜂巢能源科技有限公司 | High-nickel ternary cathode material and preparation method thereof |
| CN114243014A (en) * | 2021-10-29 | 2022-03-25 | 广东邦普循环科技有限公司 | Single crystal ternary cathode material and preparation method and application thereof |
| CN114447315A (en) * | 2021-12-29 | 2022-05-06 | 格林美(湖北)新能源材料有限公司 | Ultra-small particle size single crystal nickel-cobalt-manganese ternary cathode material and preparation method thereof |
-
2022
- 2022-05-30 CN CN202210605411.8A patent/CN114927693B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019027215A2 (en) * | 2017-08-01 | 2019-02-07 | 주식회사 에코프로비엠 | Lithium composite oxide precursor, preparation method therefor, and lithium composite oxide prepared using same |
| WO2019103488A1 (en) * | 2017-11-22 | 2019-05-31 | 주식회사 엘지화학 | Positive electrode active material for lithium secondary battery and manufacturing method therefor |
| CN111902978A (en) * | 2018-04-06 | 2020-11-06 | 株式会社Lg化学 | Positive electrode active material for lithium secondary battery, method for producing same, positive electrode for lithium secondary battery comprising same, and lithium secondary battery |
| CN111463411A (en) * | 2019-01-18 | 2020-07-28 | 天津国安盟固利新材料科技股份有限公司 | High-nickel ternary cathode material with single crystal morphology and preparation method thereof |
| CN109888235A (en) * | 2019-03-06 | 2019-06-14 | 广东邦普循环科技有限公司 | A kind of nickelic tertiary cathode material of gradation and its preparation method and application |
| CN110993936A (en) * | 2019-12-02 | 2020-04-10 | 当升科技(常州)新材料有限公司 | High-energy density type nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN111525118A (en) * | 2020-05-15 | 2020-08-11 | 陕西红马科技有限公司 | Preparation method of mixed nickel-cobalt lithium aluminate anode material |
| CN111646523A (en) * | 2020-06-29 | 2020-09-11 | 蜂巢能源科技有限公司 | High-safety double-doped high-nickel ternary cathode material, preparation method thereof and lithium ion battery |
| CN113161548A (en) * | 2021-03-29 | 2021-07-23 | 广东邦普循环科技有限公司 | Cobalt-free nickel-manganese cathode material and preparation method and application thereof |
| CN113871603A (en) * | 2021-09-29 | 2021-12-31 | 蜂巢能源科技有限公司 | High-nickel ternary cathode material and preparation method thereof |
| CN114243014A (en) * | 2021-10-29 | 2022-03-25 | 广东邦普循环科技有限公司 | Single crystal ternary cathode material and preparation method and application thereof |
| CN114447315A (en) * | 2021-12-29 | 2022-05-06 | 格林美(湖北)新能源材料有限公司 | Ultra-small particle size single crystal nickel-cobalt-manganese ternary cathode material and preparation method thereof |
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