CN113044890A - Cathode material, preparation method thereof and lithium ion battery - Google Patents
Cathode material, preparation method thereof and lithium ion battery Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 58
- 239000007774 positive electrode material Substances 0.000 claims abstract description 45
- 239000011572 manganese Substances 0.000 claims abstract description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 transition metal cations Chemical class 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims abstract description 13
- 229910003927 NixMnyMz Inorganic materials 0.000 claims abstract description 10
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229960002799 stannous fluoride Drugs 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000005245 sintering Methods 0.000 claims description 51
- 239000002243 precursor Substances 0.000 claims description 38
- 239000012266 salt solution Substances 0.000 claims description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims description 22
- 159000000002 lithium salts Chemical class 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 150000003624 transition metals Chemical class 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 150000002696 manganese Chemical class 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- NLPMQGKZYAYAFE-UHFFFAOYSA-K titanium(iii) fluoride Chemical compound F[Ti](F)F NLPMQGKZYAYAFE-UHFFFAOYSA-K 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052744 lithium Inorganic materials 0.000 abstract description 22
- 229910052748 manganese Inorganic materials 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 238000003756 stirring Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000012716 precipitator Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 5
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
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- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention particularly relates to a positive electrode material, a preparation method thereof and a lithium ion battery, belonging to the technical field of lithium ion battery electrodes, wherein the positive electrode material has the chemical formula as follows: li1.2NixMnyMzO2FzWherein M is transition metal element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1, z is more than 0 and less than 0.1, the lithium-rich manganese-based anode material body phase contains transition metal cations, the structural stability of the material is improved, and the energy density of the material can be improved by doping fluorine ions in a shallow layer. By synthesizing the lithium-rich manganese-based positive electrode material with fluoride ions, the electrochemical performance is obviously improved. Wherein the lithium-rich manganese-based cathode material doped with stannous fluoride is 0.1C (1C is 200 mAg)‑1) Is/are as followsMultiplying power, the first effect can reach 79.0%, and after 100 circles of circulation, 298.4mAhg is still provided‑1The specific capacity of (A).
Description
Technical Field
The invention belongs to the technical field of lithium ion battery electrodes, and particularly relates to a positive electrode material, a preparation method of the positive electrode material and a lithium ion battery.
Background
The lithium ion battery is widely applied to energy storage equipment such as 3C products and electric vehicles due to the advantages of high energy density, high cost performance, environmental friendliness and the like. With the wider and wider application of lithium battery energy storage equipment, higher requirements are put forward on energy density, safety, cost performance and the like of the energy storage equipment, and the lithium battery performance is urgently needed to be improved.
Compared with the traditional lithium ion battery anode material, the lithium-rich manganese-based anode material can reach 250mAhg in specific capacity and energy density-1And 1000Wh/Kg are of great interest. However, the cycle, rate, stability and other aspects still need to be improved, and the wide application of the lithium-rich manganese-based cathode material is restricted.
Disclosure of Invention
In view of the above problems, the present invention has been made to provide a cathode material, a method of preparing the same, and a lithium ion battery that overcome or at least partially solve the above problems.
The embodiment of the invention provides a positive electrode material, which has a chemical formula as follows: li1.2NixMnyMzO2FzWherein M is a transition metal element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1, and z is more than 0 and less than 0.1.
Optionally, the chemical formula of the cathode material is: li1.2NixMnyMzO2FzWherein M is one element of Sn, Ti and Fe, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1, and z is more than 0 and less than 0.1.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the cathode material, which comprises the following steps:
obtaining a precursor with a chemical formula of NixMny(OH)2Wherein x is more than or equal to 0 and less than 0.5, and y is more than 0.5 and less than 1;
grinding, mixing and sintering the precursor, fluoride of transition metal elements and lithium salt to obtain the anode material, wherein the chemical formula of the anode material is as follows: li1.2NixMnyMzO2FzWherein M is a transition metal element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1, and z is more than 0 and less than 0.1.
Optionally, the obtaining a precursor, specifically including,
mixing an ammonia water solution and a sodium hydroxide solution to obtain a precipitant solution;
putting nickel salt and manganese salt solution into water to obtain transition metal salt solution;
adding the precipitant solution into the transition metal salt solution for reaction to obtain a precipitate;
and filtering, washing and drying the precipitate to obtain a precursor.
Optionally, in the precipitant solution obtained by mixing an ammonia water solution and a sodium hydroxide solution, the mass fraction of the ammonia water solution is 5% to 10%, the molar concentration of the sodium hydroxide solution is 0.5mol/L to 1mol/L, and the ratio of the sodium hydroxide solution to the ammonia water solution is 0.5 to 1: 10-20.
Optionally, the nickel salt solution and the manganese salt solution are put in water to obtain a transition metal salt solution, and the ratio of nickel element in the nickel salt to manganese element in the manganese salt is 0-0.25 by mass.
Optionally, in the step of grinding, mixing and sintering the precursor, the fluoride of the transition metal element and the lithium salt to obtain the cathode material, the fluoride of the transition metal element includes at least one of stannous fluoride, ferric trifluoride and titanium trifluoride, and the lithium salt is at least one of lithium hydroxide and lithium carbonate.
Optionally, the precursor, the fluoride of the transition metal element and the lithium salt are ground, mixed and sintered to obtain the positive electrode material, wherein the mixing time is 30-50 min, and the ratio of the Mn ions in the precursor to the F ions in the fluoride of the transition metal element to the lithium salt is 0.5-1: 0.01-0.1: 1.17-1.25 in terms of the amount of the material.
Optionally, the precursor, the fluoride of the transition metal element and the lithium salt are ground, mixed and sintered to obtain the anode material, wherein the sintering comprises a first-stage sintering and a second-stage sintering, in the first-stage sintering, the sintering temperature is 400-500 ℃, the heating rate is 4-6 ℃/min, and the heat preservation time is 180-300 min; in the second stage of sintering, the sintering temperature is 800-1000 ℃, the heating rate is 4-6 ℃/min, and the heat preservation time is 600-720 min; and the first-stage sintering and the second-stage sintering are carried out under the protection of pure oxygen.
Based on the same inventive concept, the embodiment of the invention also provides a lithium ion battery, wherein the lithium ion battery comprises a positive electrode, and the positive electrode is made of the positive electrode material.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
according to the cathode material provided by the embodiment of the invention, the chemical formula of the cathode material is as follows: li1.2NixMnyMzO2FzWherein M is transition metal element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1, z is more than 0 and less than 0.1, the lithium-rich manganese-based anode material body phase contains transition metal cations, the structural stability of the material is improved, and the energy density of the material can be improved by doping fluorine ions in a shallow layer. By synthesizing the lithium-rich manganese-based positive electrode material with fluoride ions, the electrochemical performance is obviously improved. Wherein the lithium-rich manganese-based cathode material doped with stannous fluoride is 0.1C (1C is 200 mAg)-1) The first effect can reach 79.0%, and 298.4mAhg is still available after 100 cycles of circulation-1The specific capacity of (A).
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a flow chart of a method provided by an embodiment of the present invention;
fig. 2 is an SEM image of the positive electrode material provided in example 1 of the present invention;
fig. 3 is an SEM image of the positive electrode material provided in example 2 of the present invention;
fig. 4 is an SEM image of the positive electrode material provided in example 3 of the present invention;
fig. 5 is an SEM image of the positive electrode material provided in example 4 of the present invention;
fig. 6 is an SEM image of the positive electrode material provided in comparative example 1 of the present invention;
FIG. 7 is a graph of first cycle voltage capacity of the positive electrode materials provided in examples 1 to 4 of the present invention and comparative example 1;
fig. 8 is a 100-cycle chart of the positive electrode materials provided in examples 1 to 4 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to an exemplary embodiment of the present invention, there is provided a positive electrode material having a chemical formula of: li1.2NixMnyMzO2FzWherein M is a transition metal element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1, and z is more than 0 and less than 0.1. Specifically, M may be one element selected from Sn, Ti, and Fe, in other words, the chemical formula of the positive electrode material may be: li1.2NixMnySnzO2Fz、Li1.2NixMnyTizO2Fz、Li1.2NixMnyFezO2FzAnd the like.
According to another exemplary embodiment of the present invention, there is provided a method of preparing a positive electrode material, the method including:
s1, obtaining a precursor with a chemical formula of NixMny(OH)2Wherein x is more than or equal to 0 and less than 0.5, and y is more than 0.5 and less than 1;
as an alternative embodiment, the obtaining of the precursor, in particular comprising,
s1.1, mixing an ammonia water solution and a sodium hydroxide solution to obtain a precipitant solution;
specifically, an ammonia water solution and a sodium hydroxide solution are mixed to obtain a precipitant solution, wherein the mass fraction of the ammonia water solution is 5% -10%, the molar concentration of the sodium hydroxide solution is 0.5-1 mol/L, and the ratio of the sodium hydroxide solution to the ammonia water solution is 0.5-1: 10-20.
S1.2, putting a nickel salt solution and a manganese salt solution into water to obtain a transition metal salt solution;
specifically, a nickel salt solution and a manganese salt solution are put into water to obtain a transition metal salt solution, wherein the nickel salt and the manganese salt can be selected from one or more than two of sulfate, nitrate, carbonate and acetate; the proportion of the nickel element in the nickel salt and the manganese element in the manganese salt is 0-0.25 by mass.
S1.3, adding the precipitant solution into the transition metal salt solution for reaction to obtain a precipitate;
specifically, a peristaltic pump is adopted to uniformly add the precipitant solution at a certain flow rate of 1mL/min for 2-3h, the reaction temperature required for adding the precipitant solution into the metal salt solution is 60-90 ℃, and the stirring speed is controlled at 300-500 rpm.
And S1.4, filtering, washing and drying the precipitate to obtain a precursor.
Specifically, washing needs to be performed for 3-5 times by using deionized water, and the drying temperature of the precipitate is 100-200 ℃.
S2, grinding, mixing and sintering the precursor, the fluoride of the transition metal element and the lithium salt to obtain the anode material, wherein the chemical formula of the anode material is as follows: li1.2NixMnyMzO2FzWherein M is a transition metal element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1, and z is more than 0 and less than 0.1.
As an alternative embodiment, in the step of grinding, mixing and sintering the precursor, the fluoride of the transition metal element and the lithium salt to obtain the cathode material, the fluoride of the transition metal element includes one of stannous fluoride, ferric trifluoride and titanium trifluoride, and the lithium salt is at least one of lithium hydroxide and lithium carbonate.
As an optional embodiment, in the step of grinding, mixing and sintering the precursor, the fluoride of the transition metal element and the lithium salt to obtain the cathode material, the grinding and mixing are carried out in a mortar, the mixing time is 30min to 50min, and the ratio of the Mn ions in the precursor, the F ions in the fluoride of the transition metal element and the lithium salt is 0.5-1: 0.01-0.1: 1.17-1.25 by mass.
The reason for controlling the material mixing time to be 30-50 min is that the precursor is more fully and uniformly contacted with the fluoride and lithium salt of the transition metal element, so that the active substance can be more uniform in the subsequent sintering process, the adverse effect of overlarge value of the time is to increase the cost and reduce the efficiency, and the adverse effect of undersize is to make the distribution of the fluoride and lithium salt of the precursor and the transition metal element uneven, so that the performance of the product is poor;
the reason for controlling the ratio of Mn ions in the precursor, F ions in the fluoride of the transition metal element and lithium salt to be 0.5-1: 0.01-0.1: 1.17-1.25 is to synthesize the layered manganese-based anode material and reduce the cost, the reason for controlling the ratio of F ions is to increase the number of inactive transition metal elements and reduce the capacity of the material due to the addition of excessive fluorine ions, and the lithium salt is selected in proportion to form a polycrystalline phase of the lithium-rich material and has uniform appearance.
As an optional embodiment, the precursor, fluoride of transition metal element and lithium salt are ground, mixed and sintered to obtain the anode material, wherein the sintering comprises a first-stage sintering and a second-stage sintering, in the first-stage sintering, the sintering temperature is 400-500 ℃, the heating rate is 4-6 ℃/min, and the heat preservation time is 180-300 min; in the second stage of sintering, the sintering temperature is 800-1000 ℃, the heating rate is 4-6 ℃/min, and the heat preservation time is 600-720 min; and the first-stage sintering and the second-stage sintering are carried out under the protection of pure oxygen.
The reason for adopting two-stage sintering is that the materials can be mixed and heated more uniformly and stably, and the stability and consistency of the product are better.
According to another exemplary embodiment of the present invention, a lithium ion battery is provided, which includes a positive electrode, and the material of the positive electrode adopts the positive electrode material provided above.
The positive electrode material, the method for preparing the same, and the lithium ion battery according to the present application will be described in detail with reference to examples, comparative examples, and experimental data.
Example 1
(1) Adding 200mL of 5% ammonia water solution into 10mL of prepared sodium hydroxide solution with the molar concentration of 0.5mol/L, and continuously stirring to obtain a precipitant solution;
(2) 2.6285g of nickel sulfate hexahydrate and 6.7604g of manganese sulfate monohydrate are dissolved in 100mL of deionized water to prepare a mixed solution, and a transition metal salt solution is obtained;
(3) adding the precipitator solution prepared in the step one into the metal salt solution in the step two according to the flow rate of 1mL/min, keeping the reaction temperature of 80 ℃ in the adding process, continuously stirring, filtering, washing and drying the precipitate after the reaction is completed, and obtaining the transition metal hydroxide precursor TM prepared by the coprecipitation method0.2Mn0.8(OH)2(TM is Ni element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1);
(4) weighing 1.757g of dried precursor, 0.063g of stannous fluoride and 1.031g of lithium hydroxide monohydrate according to the molar ratio of the transition metal element to the lithium element of 1: 1.2 grinding, mixing, high-temperature sectional sintering and oxygen protection are carried out, the first-stage sintering temperature is 400 ℃, the heat preservation time is 4 hours, the second-stage sintering temperature is 1000 ℃, the heat preservation time is 10 hours, the heating rate is 5 ℃/min, and the temperature is naturally reduced to the room temperature, so that the fluorine ion-containing lithium-rich manganese-based cathode material is prepared.
Example 2
(1) Adding 200mL of 5% ammonia water solution into 10mL of prepared sodium hydroxide solution with the molar concentration of 0.5mol/L, and continuously stirring to obtain a precipitant solution;
(2) 2.6285g of nickel sulfate hexahydrate and 6.7604g of manganese sulfate monohydrate are dissolved in 100mL of deionized water to prepare a mixed solution, and a transition metal salt solution is obtained;
(3) adding the precipitator solution prepared in the step one into the metal salt solution in the step two according to the flow rate of 1mL/min, keeping the reaction temperature of 80 ℃ in the adding process, continuously stirring, filtering, washing and drying the precipitate after the reaction is completed, and obtaining the transition metal hydroxide precursor TM prepared by the coprecipitation method0.2Mn0.8(OH)2(TM is Ni element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1);
(4) 1.757g of dried precursor, 0.045g of ferric trifluoride and 1.031g of lithium hydroxide monohydrate were weighed out in such a manner that the molar ratio of transition metal element to lithium element was 1: 1.2 grinding, mixing, high-temperature sectional sintering and oxygen protection are carried out, the first-stage sintering temperature is 400 ℃, the heat preservation time is 4 hours, the second-stage sintering temperature is 1000 ℃, the heat preservation time is 10 hours, the heating rate is 5 ℃/min, and the temperature is naturally reduced to the room temperature, so that the fluorine ion-containing lithium-rich manganese-based cathode material is prepared.
Example 3
(1) Adding 200mL of 5% ammonia water solution into 10mL of prepared sodium hydroxide solution with the molar concentration of 0.5mol/L, and continuously stirring to obtain a precipitant solution;
(2) 2.6285g of nickel sulfate hexahydrate and 6.7604g of manganese sulfate monohydrate are dissolved in 100mL of deionized water to prepare a mixed solution, and a transition metal salt solution is obtained;
(3) adding the precipitator solution prepared in the step one into the metal salt solution in the step two according to the flow rate of 1mL/min, keeping the reaction temperature of 80 ℃ in the adding process, continuously stirring, filtering, washing and drying the precipitate after the reaction is completed, and obtaining the transition metal hydroxide precursor TM prepared by the coprecipitation method0.2Mn0.8(OH)2(TM is Ni element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1);
(4) weighing 1.757g of dried precursor, 0.042g of titanium trifluoride and 1.031g of lithium hydroxide monohydrate according to the molar ratio of the transition metal element to the lithium element of 1: 1.2 grinding, mixing, high-temperature sectional sintering and oxygen protection are carried out, the first-stage sintering temperature is 400 ℃, the heat preservation time is 4 hours, the second-stage sintering temperature is 1000 ℃, the heat preservation time is 10 hours, the heating rate is 5 ℃/min, and the temperature is naturally reduced to the room temperature, so that the fluorine ion-containing lithium-rich manganese-based cathode material is prepared.
Comparative example 1
(1) Adding 200mL of 5% ammonia water solution into 10mL of prepared sodium hydroxide solution with the molar concentration of 0.5mol/L, and continuously stirring to obtain a precipitant solution;
(2) 2.6285g of nickel sulfate hexahydrate and 6.7604g of manganese sulfate monohydrate are dissolved in 100mL of deionized water to prepare a mixed solution, and a transition metal salt solution is obtained;
(3) adding the precipitator solution prepared in the step one into the metal salt solution in the step two according to the flow rate of 1mL/min, and adding the precipitator solution in the processKeeping the reaction temperature of 80 ℃, continuously stirring, filtering, washing and drying a precipitate after the reaction is finished completely to obtain a precursor TM of the transition metal hydroxide prepared by a coprecipitation method0.2Mn0.8(OH)2(TM is Ni element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1);
(4) weighing 1.795g of dried precursor and 0.887g of lithium carbonate according to the molar ratio of the transition metal element to the lithium element of 1: 1.2 grinding, mixing, high-temperature sectional sintering and oxygen protection are carried out, the first-stage sintering temperature is 400 ℃, the heat preservation time is 4 hours, the second-stage sintering temperature is 1000 ℃, the heat preservation time is 10 hours, the heating rate is 5 ℃/min, and the temperature is naturally reduced to the room temperature, so that the lithium-rich manganese-based cathode material without fluoride ions is prepared.
Comparative example 2
(1) Adding 200mL of 5% ammonia water solution into 10mL of prepared sodium hydroxide solution with the molar concentration of 0.5mol/L, and continuously stirring to obtain a precipitant solution;
(2) 2.6285g of nickel sulfate hexahydrate and 6.7604g of manganese sulfate monohydrate are dissolved in 100mL of deionized water to prepare a mixed solution, and a transition metal salt solution is obtained;
(3) adding the precipitator solution prepared in the step one into the metal salt solution in the step two according to the flow rate of 1mL/min, keeping the reaction temperature of 80 ℃ in the adding process, continuously stirring, filtering, washing and drying the precipitate after the reaction is completed, and obtaining the transition metal hydroxide precursor TM prepared by the coprecipitation method0.2Mn0.8(OH)2(TM is Ni element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1);
(4) weighing 1.795g of dried precursor and 1.031g of lithium hydroxide monohydrate according to the molar ratio of the transition metal element to the lithium element of 1: 1.2 grinding, mixing, high-temperature sectional sintering and oxygen protection are carried out, the first-stage sintering temperature is 400 ℃, the heat preservation time is 4 hours, the second-stage sintering temperature is 1000 ℃, the heat preservation time is 10 hours, the heating rate is 5 ℃/min, and the temperature is naturally reduced to the room temperature, so that the fluorine ion-containing lithium-rich manganese-based cathode material is prepared.
Examples of the experiments
The positive electrode materials obtained in examples 1 to 3 and comparative examples 1 to 2 were assembled to form a battery by the following method:
uniformly mixing a positive electrode material, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVdF) in a Nitrogen Methyl Pyrrolidone (NMP) solvent, wherein the mass ratio of the positive electrode material to the conductive agent to the binder is 80: 10: 10, coating the uniformly mixed slurry on an aluminum foil, and performing vacuum drying at 120 ℃ for 12 hours to obtain a lithium ion battery positive plate;
uniformly mixing a graphite negative electrode material, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVdF) in a Nitrogen Methyl Pyrrolidone (NMP) solvent, wherein the mass ratio of the graphite negative electrode material to the conductive agent to the binder is 80: 10: and 10, coating the uniformly mixed slurry on a copper foil, and performing vacuum drying at 120 ℃ for 12 hours to obtain the lithium ion battery negative plate.
And testing the performance of the battery, wherein the testing method comprises the following steps:
the anode plate and the cathode plate are used, the electrolyte adopts 1mol/L solution of ethylene carbonate, dimethyl carbonate and fluoroethylene carbonate of lithium hexafluorophosphate, and the diaphragm adopts a polyethylene and polypropylene composite material with the thickness of 20 microns to assemble the CR2032 type button lithium ion battery. And performing charge and discharge tests on the assembled button battery, wherein the voltage range is 2.0-4.8 volts.
The test results are shown in the following table.
| First week effect/%) | Specific capacity/mAh/g after 100 weeks | |
| Comparative example 1 | 67.1 | 154.5 |
| Comparative example 2 | 61.3 | 141.8 |
| Example 1 | 79.0 | 298.4 |
| Example 2 | 74.5 | 242.8 |
| Example 3 | 71.7 | 213.7 |
As can be seen from the table, the lithium ion battery assembled by the lithium-rich manganese-based positive electrode material obtained by sintering the precursor prepared by the method provided by the embodiment of the present invention, stannous fluoride and lithium carbonate together is superior to the lithium ion battery assembled by the lithium-rich manganese-based positive electrode materials of the comparative example and other embodiments in terms of first cycle/%, and 100 cycles. Wherein, the lithium-rich manganese-based cathode material doped with stannous fluoride is 0.1C (1C is 200 mAg)-1) The first effect can reach 79.0%, and 298.4mAhg is still available after 100 cycles of circulation-1The specific capacity of (A).
Detailed description of the drawings 2-8:
as shown in fig. 2 to 6, fig. 2 to 4 are SEM images of the cathode materials of examples 1 to 3, respectively, and fig. 5 to 6 are SEM images of the cathode materials of comparative examples 1 and 2, respectively, from which it can be obtained that the cathode material in the comparative examples has more uniform morphology, and particularly, the lithium-rich manganese-based cathode material particles added with stannous fluoride in example 1 are more uniform and have less fragmentation;
as shown in fig. 7, a graph of the first cycle voltage capacity of the positive electrode materials provided in examples 1 to 3 and comparative examples 1 to 2 is shown, wherein the line of example 1 is a curve plotted by the data measured by the positive electrode material of example 1, the line of example 2 is a curve plotted by the data measured by the positive electrode material of example 2, and by analogy, the electrochemical performance of the lithium-rich manganese-based positive electrode material added with fluoride ions is improved greatly compared with the original sample of the comparative example, wherein the improvement is the maximum by the sample added with stannous fluoride.
As shown in fig. 8, which is a 100-cycle graph of the positive electrode materials provided in examples 1 to 3 and comparative examples 1 to 2, wherein lines 1 to 3 are curves plotted from data measured by the positive electrode materials of examples 1 to 3, respectively, and lines 4 to 5 are curves plotted from data measured by the positive electrode materials of comparative examples 1 to 2, it can be seen from the graph that, when the positive electrode material containing fluoride of transition metal ions is added, fluorine ions can increase the specific capacity of the material itself, and transition metals can stabilize the structure of the material, and the combination of the two can significantly improve the electrochemical performance of the material compared with the comparative example.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) the positive electrode material provided by the embodiment of the invention contains transition metal cations, so that the structural stability of the material is improved, and the energy density of the material can be improved by doping fluorine ions in a shallow layer;
(2) the lithium-rich manganese-based cathode material with fluoride ions is synthesized, so that the electrochemical performance is obviously improved.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A positive electrode material is characterized in that the chemical formula of the positive electrode material is as follows: li1.2NixMnyMzO2FzWherein M is a transition metal element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1, and z is more than 0 and less than 0.1.
2. The positive electrode material according to claim 1, wherein the positive electrode material has a chemical formula of: li1.2NixMnyMzO2FzWherein M is one element of Sn, Ti and Fe, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1, and z is more than 0 and less than 0.1.
3. A method for producing a positive electrode material, characterized by comprising:
obtaining a precursor with a chemical formula of NixMny(OH)2Wherein x is more than or equal to 0 and less than 0.5, and y is more than 0.5 and less than 1;
grinding, mixing and sintering the precursor, fluoride of transition metal elements and lithium salt to obtain the anode material, wherein the chemical formula of the anode material is as follows: li1.2NixMnyMzO2FzWherein M is a transition metal element, x is more than or equal to 0 and less than 0.5, y is more than 0.5 and less than 1, and z is more than 0 and less than 0.1.
4. The method for preparing a positive electrode material according to claim 3, wherein the obtaining of the precursor comprises,
mixing an ammonia water solution and a sodium hydroxide solution to obtain a precipitant solution;
putting nickel salt and manganese salt solution into water to obtain transition metal salt solution;
adding the precipitant solution into the transition metal salt solution for reaction to obtain a precipitate;
and filtering, washing and drying the precipitate to obtain a precursor.
5. The preparation method of the cathode material according to claim 4, wherein an ammonia solution and a sodium hydroxide solution are mixed to obtain a precipitant solution, the mass fraction of the ammonia solution is 5% -10%, the molar concentration of the sodium hydroxide solution is 0.5-1 mol/L, and the ratio of the sodium hydroxide solution to the ammonia solution is 0.5-1: 10-20.
6. The method for preparing a positive electrode material according to claim 4, wherein the solution of the nickel salt and the manganese salt is dissolved in water to obtain the solution of the transition metal salt, and the ratio of the nickel element in the nickel salt to the manganese element in the manganese salt is 0 to 0.25 by mass.
7. The method for preparing a cathode material according to claim 3, wherein the precursor, the fluoride of the transition metal element and the lithium salt are ground, mixed and sintered to obtain the cathode material, wherein the fluoride of the transition metal element comprises at least one of stannous fluoride, ferric trifluoride and titanium trifluoride, and the lithium salt is at least one of lithium hydroxide and lithium carbonate.
8. The method for preparing the positive electrode material according to claim 3, wherein the precursor, the fluoride of the transition metal element and the lithium salt are ground, mixed and sintered to obtain the positive electrode material, wherein the mixing time is 30-50 min, and the ratio of Mn ions in the precursor, F ions in the fluoride of the transition metal element and the lithium salt is 0.5-1: 0.01-0.1: 1.17-1.25 in terms of the amount of the substance.
9. The preparation method of the cathode material according to claim 3, wherein the precursor, the fluoride of the transition metal element and the lithium salt are ground, mixed and sintered to obtain the cathode material, wherein the sintering comprises a first-stage sintering and a second-stage sintering, and in the first-stage sintering, the sintering temperature is 400-500 ℃, the heating rate is 4-6 ℃/min, and the heat preservation time is 180-300 min; in the second stage of sintering, the sintering temperature is 800-1000 ℃, the heating rate is 4-6 ℃/min, and the heat preservation time is 600-720 min; and the first-stage sintering and the second-stage sintering are carried out under the protection of pure oxygen.
10. A lithium ion battery, which comprises a positive electrode, and is characterized in that the material of the positive electrode adopts the positive electrode material as claimed in any one of claims 1-2.
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