CN115440928A - Positive electrode material, positive plate comprising positive electrode material and battery - Google Patents
Positive electrode material, positive plate comprising positive electrode material and battery Download PDFInfo
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- CN115440928A CN115440928A CN202211015095.5A CN202211015095A CN115440928A CN 115440928 A CN115440928 A CN 115440928A CN 202211015095 A CN202211015095 A CN 202211015095A CN 115440928 A CN115440928 A CN 115440928A
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- positive electrode
- electrode material
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- niobium
- tungsten oxide
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 55
- 239000010955 niobium Substances 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 35
- 239000011572 manganese Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 29
- QONMOXAMRUZUCK-UHFFFAOYSA-N niobium;oxotungsten Chemical compound [Nb].[W]=O QONMOXAMRUZUCK-UHFFFAOYSA-N 0.000 claims abstract description 28
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010405 anode material Substances 0.000 claims abstract description 25
- 239000011163 secondary particle Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 25
- 239000010406 cathode material Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
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- 229910015118 LiMO Inorganic materials 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 10
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
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- 238000002360 preparation method Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
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- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 3
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- 239000003792 electrolyte Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000004146 energy storage Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZXEGFFDKNSXGQQ-UHFFFAOYSA-I Cl.[Cl-].[Nb+5].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound Cl.[Cl-].[Nb+5].[Cl-].[Cl-].[Cl-].[Cl-] ZXEGFFDKNSXGQQ-UHFFFAOYSA-I 0.000 description 1
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
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- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WIDQNNDDTXUPAN-UHFFFAOYSA-I tungsten(v) chloride Chemical compound Cl[W](Cl)(Cl)(Cl)Cl WIDQNNDDTXUPAN-UHFFFAOYSA-I 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode material, a positive plate and a battery comprising the same, wherein the positive electrode material is formed by coating nano niobium tungsten oxide (Nb) on the surface of secondary particles of a lithium-rich manganese-based positive electrode material 12 WO 33 ) A fast ion conductor; the battery has the characteristics of excellent cycle performance and rate performance. The positive electrode material has simple synthesis process, does not need additional modification operation, and can be directly and synchronously modified and prepared in the precursor lithium mixed sintering processThe prepared modified anode material has high purity and can realize large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a niobium-tungsten oxide coated lithium-rich manganese-based modified positive electrode material, a positive electrode plate comprising the positive electrode material and a battery.
Background
The lithium ion battery has the advantages of excellent electrochemical performance, environmental friendliness and the like, and is widely applied to various aspects of the field of new energy, such as 3C digital, power supply and energy storage system. The positive electrode material, which is the most important energy storage and conversion substance among them, determines the energy density of the lithium ion battery. With the increase of the energy density requirement of the lithium ion battery cathode material in the field of power batteries, the existing commercialized cathode material is difficult to meet the increasing demand. And because the cost of lithium resources is continuously improved, the difficulty of increasing energy and reducing cost of the anode material is increased.
The lithium-rich manganese-based cathode material is widely favored due to the advantages of higher capacity (> 250 mAh/g), higher energy density (> 860 Wh/kg), lower raw material cost and the like. However, there are still some problems to be solved in large-scale application: (1) The first cycle coulomb efficiency is low, resulting in loss of reversible lithium quantity; (2) poor cycle performance, severe voltage and capacity fade; (3) poor rate capability. Therefore, the solution to any one of the problems has high practical significance and application value.
At present, the means for improving the performance of the lithium-rich manganese-based anode material mainly comprises element doping (such as metal elements including Mg, al and Zr and the like and non-metal elements including B, F and the like) and surface coating (such as phosphate, oxide, conductive carbon and the like), and the main purposes are to improve the stability of the crystal structure of the lithium-rich manganese-based anode material and reduce the contact between the surface of the lithium-rich manganese-based anode material and electrolyte.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a positive electrode material, a positive plate and a battery comprising the positive electrode material, wherein the positive electrode material is formed by coating nano niobium tungsten oxide (Nb) on the surface of secondary particles of a lithium-rich manganese-based positive electrode material 12 WO 33 ) (ii) a The battery has the characteristics of excellent cycle performance and rate performance. The synthesis process of the anode material of the invention is simple, no additional modification operation is needed,the method can be directly used for synchronous modification in the mixed sintering process of the lithium-rich manganese-based anode material precursor, the niobium tungsten oxide and the lithium source, the prepared anode material has high purity, and large-scale industrial production can be realized.
The invention aims to realize the following technical scheme:
the cathode material is represented by a plurality of chemical formulas xLi 2 MnO 3 ·(1-x)LiMO 2 The surface of the secondary particles has a chemical formula of Nb 12 WO 33 A cladding region formed of niobium tungsten oxide of (1); wherein 0<x<1,M is a combination of Mn and at least one of the following elements: ni, co, al, mg, zr, ti, nb, W, P, B.
According to embodiments of the present invention, 0-and x-layers are woven, for example, x is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9.
According to an implementation of the invention, said number is more than one.
According to an embodiment of the present invention, the cathode material is of the formula xLi 2 MnO 3 ·(1-x)LiMO 2 The lithium-rich manganese-based primary particles are agglomerated to form spherical or ellipsoidal secondary particles, and the surface of the secondary particles has a chemical formula of Nb 12 WO 33 A clad region formed of niobium tungsten oxide.
According to embodiments of the present invention, the several chemical formulas are xLi 2 MnO 3 ·(1-x)LiMO 2 The lithium-rich manganese-based primary particles of (2) form secondary particles having a median particle diameter of 6 to 15 μm, for example, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 μm.
According to an embodiment of the invention, the chemical formula is Nb 12 WO 33 The mass of the niobium tungsten oxide in (b) is 0.1 to 5wt.%, for example, 0.1wt.%, 0.2wt.%, 0.3wt.%, 0.4wt.%, 0.5wt.%, 0.6wt.%, 0.7wt.%, 0.8wt.%, 0.9wt.%, 1.0wt.%, 1.1wt.%, 1.2wt.%, 1.3wt.%, 1.4wt.%, 1.5wt.%, 1.6wt.%, 1.7wt.%, 1.8wt.%, 1.9wt.%, 2.0wt.%, 2.2wt.%, 2.3wt.% of the total mass of the positive electrode material2.5wt.%, 2.6wt.%, 2.8wt.%, 3wt.%, 3.2wt.%, 3.5wt.%, 3.6wt.%, 3.8wt.%, 4wt.%, 4.2wt.%, 4.5wt.%, 4.8wt.%, 5wt.%. The research finds that when the chemical formula is Nb 12 WO 33 The larger coating amount of the niobium tungsten oxide can hinder the contact of the anode material and the conductive agent, increase the resistance of the anode plate and is not beneficial to the performance of the battery. The chemical formula of the invention is Nb 12 WO 33 The coating amount (0.1-5 wt.%) and the coating structure of the niobium-tungsten oxide do not reduce the conductivity of the positive plate, and can improve certain rate performance.
According to an embodiment of the invention, the chemical formula is Nb 12 WO 33 The niobium tungsten oxide of (b) has a median particle diameter of 5 to 50nm, for example, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50nm.
According to an embodiment of the invention, the median particle size of the positive electrode material is 6 μm to 15 μm, for example 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm.
According to the embodiment of the invention, the cathode material is a lithium-rich manganese-based cathode material with a surface coated with niobium tungsten oxide.
According to the embodiment of the invention, the niobium-tungsten oxide has high ionic conductivity, good structural stability and high lithium ion diffusion rate, and lithium ions can pass through the niobium-tungsten oxide in a three-dimensional manner due to a larger atomic gap between Nb and W and O, so that the rate capability of the anode material is improved, and the polarization of a battery during large-rate charge and discharge is reduced; when the material is used as a coating of a positive electrode material, the cycling stability and rate capability of the positive electrode material can be remarkably improved. In addition, the niobium-tungsten oxide has a hard and open structure, does not capture lithium ions in the de-intercalation process, can enhance the structural stability of the surface of the lithium-manganese-rich-base anode material after being coated on the surface of the lithium-manganese-rich-base anode material, reduces cracks on the surface of secondary particles caused by internal stress in the long-cycle process, and prevents electrolyte from immersing into the secondary particles and generating side reaction, thereby improving the cycle performance and safety performance of the anode material.
The invention also provides a preparation method of the cathode material, which comprises the following steps:
(1) Mixing soluble salt of the element M with water, adding a precipitator and a complexing agent, and carrying out coprecipitation reaction to prepare a precursor of the lithium-rich manganese-based positive electrode material;
(2) Mixing a complexing agent, a niobium-containing compound and a tungsten-containing compound, preparing sol and gel, drying, sintering and ball-milling to prepare niobium-tungsten oxide;
(3) Mixing the precursor of the lithium-rich manganese-based positive electrode material in the step (1), the niobium tungsten oxide in the step (2) and a lithium source to obtain a mixed material;
(4) And (4) sintering the mixed material obtained in the step (3) to prepare the anode material.
According to an embodiment of the present invention, step (1) specifically comprises the steps of:
dissolving soluble salt of an element M in water according to a required molar ratio, respectively preparing a precipitator solution and a complexing agent solution or a mixed solution of the precipitator solution and the complexing agent solution, introducing all prepared solutions into a reaction kettle, controlling the temperature, the pH value and the stirring speed in the reaction kettle by using deionized water as a base solution (the amount of the base solution is 25-35% of the volume of the reaction kettle), and carrying out coprecipitation reaction; and after the reaction is finished, washing and drying the precipitate to obtain the precursor of the lithium-rich manganese-based positive electrode material.
According to an embodiment of the invention, the soluble salt is selected from a mixture of one or more of the sulfates, nitrates, phosphates, oxalates, acetates, citrates of the element M.
According to an embodiment of the present invention, in the mixed solution of step (1), the concentration of the soluble salt of the element M is 0.5 to 4mol/L.
According to an embodiment of the present invention, in the step (1), the precipitant is at least one selected from the group consisting of sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, ammonium carbonate, and ammonium bicarbonate.
According to an embodiment of the present invention, in the mixed solution of step (1), the concentration of the precipitant is 0.5 to 8mol/L.
According to an embodiment of the present invention, in step (1), theThe complexing agent is selected from ammonia water (aqueous solution of ammonia gas, chemical formula is NH) 3 ·H 2 O)。
According to an embodiment of the present invention, in the mixed solution of step (1), the concentration of the complexing agent is 0.01 to 8mol/L.
According to an embodiment of the present invention, in step (1), the temperature of the coprecipitation reaction is maintained between 45 and 65 ℃.
According to an embodiment of the present invention, in the step (1), the pH of the coprecipitation reaction is 7.0 to 12.0.
According to an embodiment of the present invention, in the step (1), the coprecipitation reaction is performed under stirring at a speed of 50 to 1500rpm.
According to an embodiment of the present invention, in the step (1), the coprecipitation reaction is performed under air or nitrogen. Preferably under nitrogen, to prevent Mn 2+ Is oxidized.
According to the embodiment of the invention, in the step (1), the reaction time of the coprecipitation reaction is 5 to 50 hours.
According to an embodiment of the present invention, in the step (2), the niobium-containing compound is selected from niobium-containing organic and inorganic substances such as niobium oxalate hydrate, niobium pentachloride, ammonium niobate oxalate hydrate, niobium amyl alcohol, niobium N-propyl alcohol, niobium N-butyl alcohol, and the like.
According to the embodiment of the present invention, in the step (2), the tungsten-containing compound is selected from tungsten hexachloride, tungsten pentachloride, ammonium paratungstate, ammonium metatungstate and other tungsten-containing organic and inorganic substances.
According to an embodiment of the present invention, in the step (2), the molar ratio of Nb and W in the niobium-containing compound and the tungsten-containing compound is 12.
According to an embodiment of the present invention, in the step (2), the method for preparing the sol and the gel comprises the steps of: mixing the complexing agent, the niobium-containing compound and the tungsten-containing compound, fully dissolving to form molten gel, heating and evaporating, and continuously stirring until gel is formed.
According to an embodiment of the invention, in step (2), the complexing agent is selected from one or more of citric acid, EDTA, PVP and sucrose.
According to the embodiment of the invention, in the step (2), the drying temperature is 100-150 ℃, and the drying time is 5-10 h.
According to the embodiment of the invention, in the step (2), the sintering is two-stage sintering, the first-stage sintering temperature is 300-500 ℃ (such as 300 ℃, 350 ℃, 400 ℃, 450 ℃ or 500 ℃), the sintering time is 5-8 h (such as 5h, 6h, 7h or 8 h), and the heating rate is 3-5 ℃/min; the second stage sintering temperature is 1000-1300 ℃ (such as 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ or 1300 ℃), the sintering time is 8-15 h (such as 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15 h), and the heating rate is 3-5 ℃/min.
According to the embodiment of the invention, in the step (2), the ball milling time is 1-4 h, and the ball mass ratio is 3-5:1.
According to an embodiment of the present invention, in the step (2), the niobium tungsten oxide has a median particle diameter of 5nm to 50nm.
According to an embodiment of the present invention, in the step (3), the lithium source is at least one selected from lithium carbonate and lithium hydroxide.
According to an embodiment of the present invention, in the step (3), the niobium tungsten oxide is added in an amount of 0.1 to 2wt.% based on the total mass of the mixture of the lithium-rich manganese-based positive electrode material precursor and the lithium source of the step (1).
According to an embodiment of the present invention, in step (3), the molar ratio of Li to TM is 1.2 to 1.6 (e.g., 1.2, 1.3, 1.4, 1.5, or 1.6), and TM is a transition metal in the precursor of the lithium-rich manganese-based positive electrode material, i.e., including Li 2 MnO 3 Medium Mn and LiMO 2 M in (1) and M are as defined above.
According to the embodiment of the invention, in the step (4), the sintering is two-stage sintering, the first stage sintering temperature is 450-500 ℃ (such as 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃ or 500 ℃), and the sintering time is 4-5 h (such as 4h, 4.5h or 5 h); the second stage sintering temperature is 870-890 ℃ (such as 870 ℃, 880 ℃ or 890 ℃), and the sintering time is 12 h-18 h (such as 12h, 13h, 14h, 15h, 16h, 17h or 18 h).
According to an embodiment of the present invention, in the step (4), the atmosphere for sintering is air or oxygen.
The invention provides a positive electrode material, which is prepared by the method.
The invention provides a positive plate, which comprises the positive electrode material.
According to the embodiment of the invention, the compacted density of the positive plate is 1.5-4.5 g/cm 3 。
According to an embodiment of the present invention, the uncoated formula in the same chemical ratio as Nb 12 WO 33 The niobium tungsten oxide of (A) has a chemical formula of xLi 2 MnO 3 ·(1-x)LiMO 2 Compared with the positive plate with the same formula, the positive plate of the invention can improve the secondary particles formed by the lithium-rich manganese-based primary particles by 0.1-0.3 g/cm 3 The compacted density of (a).
According to an embodiment of the present invention, the positive electrode sheet includes a current collector and a positive electrode active material layer on at least one side surface of the current collector, and the positive electrode active material layer includes the above-described positive electrode material.
According to an embodiment of the present invention, the current collector is a single-optical-surface aluminum foil, a double-optical-surface aluminum foil, or a porous aluminum foil.
According to an embodiment of the present invention, the mass of the cathode material accounts for 80 to 95wt%, such as 80 to 90wt%, for example, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90wt%, 91wt%, 92wt%, 93wt%, 94wt%, or 95wt% of the total mass of the cathode active material layer.
According to an embodiment of the present invention, the positive electrode active material layer further includes a binder and a conductive agent.
According to an embodiment of the invention, the binder is selected from at least one of PVDF, PTFE, polyacrylate and polyacrylic acid.
According to an embodiment of the present invention, the conductive agent is selected from at least one of graphite, carbon black, acetylene black, graphene, and carbon nanotubes.
The invention provides a battery, which comprises the positive electrode material, or comprises the positive electrode sheet.
According to an embodiment of the invention, the mass energy density of the battery is 300 to 420Wh/kg.
The invention has the beneficial effects that:
the invention provides a positive electrode material, a positive plate and a battery comprising the same, wherein the positive electrode material is formed by coating nano niobium tungsten oxide (Nb) on the surface of secondary particles of a lithium-rich manganese-based positive electrode material 12 WO 33 ) A fast ion conductor; the battery has the characteristics of excellent cycle performance and rate performance. The synthesis process of the cathode material is simple, additional modification operation is not needed, the cathode material can be directly and synchronously modified in the precursor lithium-mixed sintering process, the influence of multiple times of sintering on the two-phase layered structure of the lithium-manganese-rich base material is avoided, the prepared cathode material is high in purity, the time period is short, the cost is low, and large-scale industrial production can be realized.
Drawings
FIG. 1 is a scanning electron micrograph of a positive electrode material synthesized in example 1 of the present invention.
Fig. 2 an XRD pattern of the cathode material synthesized in example 1 of the present invention.
FIG. 3A half-cell made of the positive electrode material synthesized in example 1 of the present invention at 20mA g -1 The first charge-discharge curve at the charge-discharge current density of (1).
FIG. 4A half cell prepared from the positive electrode materials synthesized in example 1 of the present invention and comparative example 1 was operated at 100mA · g -1 The discharge specific capacity map of 100 cycles at the charge/discharge current density of (1).
Fig. 5 is a graph of specific discharge capacity at different rates for half-cells prepared from the positive electrode materials synthesized in example 1 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
(1) Preparation of NiSO 4 、CoSO 4 、MnSO 4 Mixed salt solution of (2) and NaCO 3 、NH 3 ·H 2 Mixed alkali solution of O, wherein the total concentration of metal ions in the salt solution is 2mol/L, ni 2+ :Co 2+ :Mn 2+ 0.13, naCO 3 Has a molar concentration of 2mol/L, NH 3 ·H 2 The molar concentration of O is 0.2mol/L; adding a certain amount of deionized water into a reaction kettle, pumping the salt solution into the reaction kettle at a feeding speed of 175ml/h by using a peristaltic pump, controlling the stirring speed to be 1000rpm, controlling the circulating water temperature to be 55 ℃, adjusting the alkali liquor feeding speed by using a three-stage speed, controlling the pH of a solution system to be 7.5, and keeping the feeding time for 30 hours; and after solid-liquid separation is carried out on the slurry after the reaction is finished, centrifugal cleaning is carried out by using deionized water, and then drying is carried out for 24 hours at 120 ℃ to obtain a carbonate precursor of the cathode material.
(2) Dissolving niobium oxalate hydrate, ammonium paratungstate, citric acid and ethylene glycol in deionized water, wherein the molar ratio of Nb to W is 12. Drying the gel in a blast oven at 120 ℃ for 8h, taking out the gel, grinding the gel, heating the gel to 400 ℃ in a muffle furnace, preserving the heat for 5h to remove the organic matrix in the material, then continuously heating the gel to 1200 ℃, sintering the gel for 10h, cooling the gel, and then mechanically ball-milling the gel for 2h to obtain Nb with the median particle size of 5-50 nm 12 WO 33 A compound is provided.
(3) Mixing the carbonate precursor of the positive electrode material with Nb 12 WO 33 Compound and Li 2 CO 3 Mixing fully, wherein the molar ratio of Li to TM =12, TM is Ni, co and Mn; nb 12 WO 33 The compound is added before the carbonatePrecursors and Li 2 CO 3 The anode material is prepared by fully and uniformly mixing 1.2 wt% of the total mass of the mixture in a mixer, placing the mixture in a muffle furnace, pre-sintering the mixture at 500 ℃ for 5 hours, heating the mixture to 880 ℃, and preserving the heat for 15 hours. The anode material has a plurality of chemical formulas of xLi 2 MnO 3 ·(1-x)LiMO 2 The secondary particles are formed by the lithium-rich manganese-based primary particles, and the surface of the secondary particles has a chemical formula of Nb 12 WO 33 The niobium tungsten oxide of (1).
(4) Mixing a positive electrode material with conductive carbon black and PVDF according to a mass ratio of 8. Transferring the positive pole piece into a glove box, taking the lithium piece as a negative pole, the clegard-2400 as a diaphragm, and the electrolyte is 1mol/L LiPF 6 DEC: DEC = 1.
(5) The test temperature of the half cell is 25 ℃, the voltage range of gram capacity test is 2.0-4.8V, and the current density is 20 mA.g -1 The specific discharge capacity at first time is 280.4 mAh.g -1 The test results are shown in fig. 3; the cyclic test voltage range is 2.0-4.6V, and the current density is 100 mA-g -1 The capacity retention rate is 94.37% after 100 cycles, and the test result is shown in fig. 4; at 0.1C (20 mA · g) -1 )、0.5C(100mA·g -1 )、1C(200mA·g -1 )、2C(400mA·g -1 )、5C(1000mA·g -1 ) The current density of (A) is respectively circulated for 5 times, the voltage range is 0.1C and is 2.0-4.8V, the other current densities are 2.0-4.6V, the test results are shown in figure 5, and the average specific discharge capacities under 0.1C, 0.5C, 1C, 2C and 5C are respectively 279.5mAh g -1 、239.8mAh·g -1 、212.3mAh·g -1 、188.5mAh·g -1 、165.6mAh·g -1 。
Example 2
(1) Preparation method of carbonate precursor reference is made to example 1.
(2) Dissolving niobium pentachloride, tungsten hexachloride, citric acid and ethylene glycol in deionized water, wherein the molar ratio of Nb to W is 12. Drying the gel in a blast oven at 120 ℃ for 8h, taking out the gel, grinding the gel, heating the gel to 400 ℃ in a muffle furnace, keeping the temperature for 5h to remove organic matrixes in the material, then continuously heating the gel to 1200 ℃, sintering the gel for 10h, cooling the gel, and carrying out mechanical ball milling for 2h to obtain Nb with the median particle size of 5-50 nm 12 WO 33 A compound is provided.
(3) Mixing the carbonate precursor of the positive electrode material with Nb 12 WO 33 Compound and Li 2 CO 3 And (2) fully mixing, wherein the molar ratio of Li to TM =12 12 WO 33 The addition amount of the compound is carbonate precursor and Li 2 CO 3 The anode material is prepared by fully and uniformly mixing 1.8 wt% of the total mass of the mixture in a mixer, placing the mixture in a muffle furnace, pre-sintering the mixture at 500 ℃ for 5 hours, heating the mixture to 870 ℃ and preserving the heat for 15 hours.
(4) Assembly procedure of button cell reference was made to example 1.
(5) The test temperature of the half cell is 25 ℃, the voltage range of gram capacity test is 2.0-4.8V, and the current density is 20 mA.g -1 The specific discharge capacity at the first time is 281.2 mAh.g -1 (ii) a The cyclic test voltage range is 2.0-4.6V, and the current density is 100 mA-g -1 The capacity retention rate is 94.45 percent after 100 times of circulation; at 0.1C (20 mA · g) -1 )、0.5C(100mA·g -1 )、1C(200mA·g -1 )、2C(400mA·g -1 )、5C(1000mA·g -1 ) The current densities of the two-phase current transformer are respectively cycled for 5 times, the voltage range is 0.1C and is 2.0-4.8V, the other current densities are 2.0-4.6V, the average specific discharge capacities under 0.1C, 0.5C, 1C, 2C and 5C are 278.8mAh g -1 、239.2mAh·g -1 、212.6mAh·g -1 、187.8mAh·g -1 、165.2mAh·g -1 。
Example 3
(1) Preparation method of carbonate precursor reference is made to example 1.
(2) Dissolving ammonium niobate oxalate hydrate, ammonium paratungstate, citric acid and ethylene glycol in deionized water, wherein the molar ratio of Nb to W is 12. Drying the gel in a blast oven at 120 ℃ for 8h, taking out the gel, grinding the gel, heating the gel to 400 ℃ in a muffle furnace, preserving the heat for 5h to remove the organic matrix in the material, then continuously heating the gel to 1200 ℃, sintering the gel for 10h, cooling the gel, and then mechanically ball-milling the gel for 2h to obtain Nb with the median particle size of 5-50 nm 12 WO 33 A compound is provided.
(3) Mixing the carbonate precursor of the positive electrode material with Nb 12 WO 33 Compound and Li 2 CO 3 And (2) fully mixing, wherein the molar ratio of Li to TM =12, TM is Ni, co and Mn, and Nb is 12 WO 33 The addition amount of the compound is carbonate precursor and Li 2 CO 3 The anode material is prepared by fully mixing 3.0wt.% of the total mass of the mixture in a mixer, placing the mixture in a muffle furnace, pre-sintering at 500 ℃ for 5 hours, heating to 890 ℃ and preserving the temperature for 15 hours.
(4) Assembly procedure of button cell reference was made to example 1.
(5) The test temperature of the half cell is 25 ℃, the voltage range of gram capacity test is 2.0-4.8V, and the current density is 20 mA.g -1 The specific discharge capacity at first time is 280.9 mAh.g -1 (ii) a The cyclic test voltage range is 2.0-4.6V, and the current density is 100 mA-g -1 The capacity retention rate is 95.56% after 100 times of circulation; at 0.1C (20 mA · g) -1 )、0.5C(100mA·g -1 )、1C(200mA·g -1 )、2C(400mA·g -1 )、5C(1000mA·g -1 ) The current densities of the two-phase current transformer are respectively cycled for 5 times, the voltage range is 0.1C and is 2.0-4.8V, the other current densities are 2.0-4.6V, the average specific discharge capacities under 0.1C, 0.5C, 1C, 2C and 5C are 280.6mAh g -1 、240.2mAh·g -1 、211.8mAh·g -1 、188.2mAh·g -1 、166.5mAh·g -1 。
Example 4
(1) Preparation method of carbonate precursor reference example 1 was made.
(2) Dissolving niobium oxalate hydrate, ammonium metatungstate, citric acid and ethylene glycol in deionized water, wherein the molar ratio of Nb to W is 12. Drying the gel in a blast oven at 120 ℃ for 8h, taking out the gel, grinding the gel, heating the gel to 400 ℃ in a muffle furnace, preserving the heat for 5h to remove the organic matrix in the material, then continuously heating the gel to 1200 ℃, sintering the gel for 10h, cooling the gel, and then mechanically ball-milling the gel for 2h to obtain Nb with the median particle size of 5-50 nm 12 WO 33 A compound is provided.
(3) Mixing the carbonate precursor of the positive electrode material with Nb 12 WO 33 Compound and Li 2 CO 3 And (2) fully mixing, wherein the molar ratio of Li to TM =12 12 WO 33 The addition amount of the compound is carbonate precursor and Li 2 CO 3 The anode material is prepared by fully and uniformly mixing 0.5 wt% of the total mass of the mixture in a mixer, placing the mixture in a muffle furnace, pre-sintering the mixture at 500 ℃ for 5 hours, heating the mixture to 870 ℃ and preserving the heat for 15 hours.
(4) Assembly procedure of button cell reference was made to example 1.
(5) The test temperature of the half cell is 25 ℃, the voltage range of gram capacity test is 2.0-4.8V, and the current density is 20 mA.g -1 The specific discharge capacity at first time is 279.6 mAh.g -1 (ii) a The cyclic test voltage range is 2.0-4.6V, and the current density is 100 mA-g -1 The capacity retention rate is 90.06% after 100 times of circulation; at 0.1C (20 mA. G) -1 )、0.5C(100mA·g -1 )、1C(200mA·g -1 )、2C(400mA·g -1 )、5C(1000mA·g -1 ) The current densities of the two-phase current transformer are respectively cycled for 5 times, the voltage range is 0.1C and is 2.0-4.8V, the other current densities are 2.0-4.6V, the average specific discharge capacities under 0.1C, 0.5C, 1C, 2C and 5C are 278.2mAh g -1 、238.5mAh·g -1 、210.1mAh·g -1 、182.6mAh·g -1 、153.4mAh·g -1 。
Example 5
(1) Preparation method of carbonate precursor reference is made to example 1.
(2) Dissolving niobium hexachloride, ammonium metatungstate, citric acid and ethylene glycol in deionized water, wherein the molar ratio of Nb to W is 12. Drying the gel in a blast oven at 120 ℃ for 8h, taking out the gel, grinding the gel, heating the gel to 400 ℃ in a muffle furnace, preserving the heat for 5h to remove the organic matrix in the material, then continuously heating the gel to 1200 ℃, sintering the gel for 10h, cooling the gel, and then mechanically ball-milling the gel for 2h to obtain Nb with the median particle size of 5-50 nm 12 WO 33 A compound is provided.
(3) Mixing the carbonate precursor of the cathode material with Nb 12 WO 33 Compound and Li 2 CO 3 And (2) fully mixing, wherein the molar ratio of Li to TM =12 12 WO 33 The addition amount of the compound is carbonate precursor and Li 2 CO 3 The lithium-rich manganese-based anode material is prepared by the following steps of mixing the materials in a mixer in an amount which is 1.2 wt% of the total mass of the mixture, placing the mixture in a muffle furnace after fully mixing, pre-burning the mixture at 500 ℃ for 5 hours, heating the mixture to 880 ℃ and preserving the heat for 15 hours to obtain the lithium-rich manganese-based anode material.
(4) Assembly procedure of button cell reference was made to example 1.
(5) The test temperature of the half cell is 25 ℃, the voltage range of gram capacity test is 2.0-4.8V, and the current density is 20 mA.g -1 The specific discharge capacity at first time is 279.6 mAh.g -1 (ii) a The cycle test voltage range is 2.0-4.6V, and the current density is 100 mA.g -1 The capacity retention rate is 94.37% after 100 times of circulation; at 0.1C (20 mA · g) -1 )、0.5C(100mA·g -1 )、1C(200mA·g -1 )、2C(400mA·g -1 )、5C(1000mA·g -1 ) The current densities of the two-phase current transformer are respectively cycled for 5 times, the voltage range is 0.1C and is 2.0-4.8V, the other current densities are 2.0-4.6V, the average specific discharge capacities under 0.1C, 0.5C, 1C, 2C and 5C are 279.2mAh g -1 、239.7mAh·g -1 、212.9mAh·g -1 、188.1mAh·g -1 、165.2mAh·g -1 。
Comparative example 1
(1) Preparation method of carbonate precursor reference is made to example 1.
(2) Mixing the carbonate precursor of the cathode material with Li 2 CO 3 And (2) fully mixing, wherein the molar ratio of Li to TM =12, the TM is Ni, co and Mn, fully mixing in a mixer, placing in a muffle furnace, pre-sintering at 500 ℃ for 5h, heating to 880 ℃ and preserving heat for 15h to obtain the cathode material.
(3) Assembly procedure of button cell reference was made to example 1.
(4) The test temperature of the half cell is 25 ℃, the voltage range of gram capacity test is 2.0-4.8V, and the current density is 20 mA.g -1 The specific discharge capacity at first time is 277.8 mAh.g -1 (ii) a The cyclic test voltage range is 2.0-4.6V, and the current density is 100 mA-g -1 The capacity retention rate is 89.57% after 100 times of circulation; at 0.1C (20 mA. G) -1 )、0.5C(100mA·g -1 )、1C(200mA·g -1 )、2C(400mA·g -1 )、5C(1000mA·g -1 ) The current densities of the two-phase current transformer are respectively cycled for 5 times, the voltage range is 0.1C and is 2.0-4.8V, the other current densities are 2.0-4.6V, the average specific discharge capacities under 0.1C, 0.5C, 1C, 2C and 5C are 276.5mAh g -1 、233.2mAh·g -1 、202.4mAh·g -1 、172.6mAh·g -1 、139.8mAh·g -1 。
Comparative example 2
(1) Preparation method of carbonate precursor reference is made to example 1.
(2) Fully and uniformly mixing niobium pentoxide and tungsten trioxide according to the molar ratio of niobium to tungsten being 12 12 WO 33 A compound is provided.
(3) Mixing the carbonate precursor of the positive electrode material with Nb 12 WO 33 Compound and Li 2 CO 3 And (2) fully mixing, wherein the molar ratio of Li to TM =12, TM is Ni, co, and,Mn；Nb 12 WO 33 The addition amount of the compound is carbonate precursor and Li 2 CO 3 The anode material is prepared by fully and uniformly mixing 1.2 wt% of the total mass of the mixture in a mixer, placing the mixture in a muffle furnace, pre-sintering the mixture at 500 ℃ for 5 hours, heating the mixture to 880 ℃, and preserving the heat for 15 hours. The anode material has a plurality of chemical formulas of xLi 2 MnO 3 ·(1-x)LiMO 2 The secondary particles are formed by the lithium-rich manganese-based primary particles, and the surface of the secondary particles has a chemical formula of Nb 12 WO 33 The niobium tungsten oxide of (1).
(4) Assembly procedure of button cell reference was made to example 1.
(5) The test temperature of the half cell is 25 ℃, the voltage range of gram capacity test is 2.0-4.8V, and the current density is 20 mA.g -1 The specific discharge capacity at first time is 277.2 mAh.g -1 (ii) a The cyclic test voltage range is 2.0-4.6V, and the current density is 100 mA-g -1 When the capacity is maintained, the capacity retention rate is 87.25 percent after 100 times of circulation; at 0.1C (20 mA. G) -1 )、0.5C(100mA·g -1 )、1C(200mA·g -1 )、2C(400mA·g -1 )、5C(1000mA·g -1 ) The current densities of the two-phase current transformer are respectively cycled for 5 times, the voltage range is 0.1C and is 2.0-4.8V, the other current densities are 2.0-4.6V, the average specific discharge capacities under 0.1C, 0.5C, 1C, 2C and 5C are 276.4mAh g -1 、234.9mAh·g -1 、205.5mAh·g -1 、178.8mAh·g -1 、144.9mAh·g -1 。
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The cathode material is characterized in that the cathode material has a plurality of chemical formulas of xLi 2 MnO 3 ·(1-x)LiMO 2 The surface of the secondary particles has a chemical formula of Nb 12 WO 33 Niobium tungsten oxide ofA cladding region formed of the compound; wherein, 0<x<1,M is a combination of Mn and at least one of the following elements: ni, co, al, mg, zr, ti, nb, W, P, B.
2. The positive electrode material according to claim 1, wherein the positive electrode material has a chemical formula of xLi 2 MnO 3 ·(1-x)LiMO 2 The lithium-rich manganese-based primary particles are agglomerated to form spherical or ellipsoidal secondary particles, and the surface of the secondary particles has a chemical formula of Nb 12 WO 33 A clad region formed of niobium tungsten oxide.
3. The positive electrode material as claimed in claim 2, wherein the chemical formulae are xLi 2 MnO 3 ·(1-x)LiMO 2 The secondary particles formed by the lithium-rich manganese-based primary particles have a median particle diameter of 6 to 15 mu m.
4. The positive electrode material as claimed in claim 1, wherein the chemical formula is Nb 12 WO 33 The mass of the niobium tungsten oxide accounts for 0.1 to 5wt percent of the total mass of the anode material.
5. The positive electrode material as claimed in claim 1, wherein the chemical formula is Nb 12 WO 33 The median particle diameter of the niobium tungsten oxide is 5nm to 50nm.
6. The positive electrode material according to claim 1, wherein the positive electrode material has a median particle diameter of 6 to 15 μm.
7. The method for producing a positive electrode material according to any one of claims 1 to 6, characterized by comprising the steps of:
(1) Mixing soluble salt of the element M with water, adding a precipitator and a complexing agent, and carrying out coprecipitation reaction to prepare a precursor of the lithium-rich manganese-based positive electrode material;
(2) Mixing a complexing agent, a niobium-containing compound and a tungsten-containing compound, preparing sol and gel, drying, sintering and ball-milling to prepare niobium-tungsten oxide;
(3) Mixing the precursor of the lithium-rich manganese-based positive electrode material in the step (1), the niobium tungsten oxide in the step (2) and a lithium source to obtain a mixed material;
(4) And (4) sintering the mixed material obtained in the step (3) to prepare the anode material.
8. A positive electrode sheet, characterized in that it comprises the positive electrode material according to any one of claims 1 to 6.
9. A battery comprising the positive electrode material according to any one of claims 1 to 6, or the battery comprising the positive electrode sheet according to claim 8.
10. The battery of claim 9, wherein the battery has a mass energy density of 300 to 420Wh/kg.
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