CN115385394A - Ternary cathode material, preparation method and lithium ion battery - Google Patents
Ternary cathode material, preparation method and lithium ion battery Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 94
- 239000002184 metal Substances 0.000 claims abstract description 85
- 238000005245 sintering Methods 0.000 claims abstract description 77
- 239000002243 precursor Substances 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 239000007774 positive electrode material Substances 0.000 claims abstract description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 24
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 24
- 150000002739 metals Chemical class 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 71
- 239000011572 manganese Substances 0.000 claims description 37
- 229910052759 nickel Inorganic materials 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 34
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 239000010955 niobium Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 229910052758 niobium Inorganic materials 0.000 claims description 17
- 229910052715 tantalum Inorganic materials 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 9
- 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 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002019 doping agent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- ZIRLXLUNCURZTP-UHFFFAOYSA-I tantalum(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Ta+5] ZIRLXLUNCURZTP-UHFFFAOYSA-I 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011247 coating layer Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 24
- 238000006138 lithiation reaction Methods 0.000 description 21
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 20
- 239000003513 alkali Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 12
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 12
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 239000006258 conductive agent Substances 0.000 description 10
- 239000010405 anode material Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000011812 mixed powder Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application relates to the technical field of lithium ion battery materials, in particular to a ternary cathode material, a preparation method and a lithium ion battery. The preparation method of the ternary cathode material comprises the following steps: mixing a ternary positive electrode material precursor, a lithium salt and a doped metal source to obtain a mixed material; the doped metal source is selected from oxide and/or hydroxide of doped metal, the doped metal source contains at least two doped metals, and the total amount of the doped metals is calculated by the balance after the doped metals are doped in the precursor of the ternary cathode material; and sintering the mixed material to obtain the ternary cathode material. According to the preparation method, the metal element doping and the coating layer preparation of the ternary cathode material are simultaneously realized by adopting a one-step pure solid phase method, the prepared ternary cathode material has a good doping effect, the cycle stability can be remarkably improved, and the preparation method has a good application prospect in a lithium ion battery.
Description
Technical Field
The application belongs to the technical field of lithium ion battery materials, and particularly relates to a ternary cathode material, a preparation method of the ternary cathode material and a lithium ion battery.
Background
The high-nickel ternary positive electrode material has the advantages of ultrahigh specific capacity, higher working voltage, higher compacted density and the like, becomes a preferred choice of high-end lithium ion power batteries, and is applied to long-endurance new energy automobiles. However, the high-nickel ternary cathode material faces two industrial pain points of poor cycle stability and safety, and further popularization of the high-nickel ternary cathode material is hindered, and the important reasons are that the Ni-O chemical bond is weak, so that oxygen is easily separated out, and the material structure is changed from alpha-NaFeO 2 The layered structure is converted into a NiO rock salt structure without electrochemical activity, and the stress generated by the volume anisotropy change in the charging and discharging process can also cause the anode material to be easily crushed. In addition, the high-nickel ternary cathode material has a large amount of Ni with strong oxidizing property in a charging state 4+ Ions are easy to have strong side reactions with the electrolyte, and the circulation stability is influenced. In addition, the surface of a general high-nickel ternary precursor is provided with residual alkali, and the residual alkali is derived from a residual lithium compound after sintering. The residual alkali reacts with moisture and carbon dioxide in the air, so that the gel of the positive electrode slurry is easy to form into jelly, and the high moisture also easily causes the battery to expand, thereby deteriorating the cycle stability and the safety.
At present, the conventional solution is a water washing method, but the water washing can damage the surface chemical structure of the ternary cathode material and seriously deteriorate the cycle life. Therefore, the industry is moving towards the direction of 'no water washing', such as pure coating, single-element or multi-element co-doping, coating combined doping and the like. The coating method is to coat other inorganic substances or organic compounds by a dry method or a wet method, and the coating object wraps the surface of the ternary cathode material and even a crystal boundary so as to prevent side reaction between the electrolyte and the ternary cathode material; element doping is generally to dope elements into a ternary positive electrode material lattice by a wet method or a solid-phase sintering method; however, the single element doping or the single cladding is not enough to completely solve the problems of the attenuation and the safety of the ternary cathode material.
In order to exert a synergistic effect, the ternary cathode material can be coated and element-doped simultaneously, generally, element doping is carried out firstly, and then coating is carried out, but the method has long working procedures, so that not only is the cost high and the product quality uncontrollable, but also the electronic resistance and the ion transmission resistance of the ternary cathode material are increased due to ex-situ coating. It has been reported that element doping and cladding can be simultaneously performed by a one-step method, but element doping and cladding can be realized by a one-step method under a liquid phase or semi-liquid phase condition, such a process is relatively complex and high in cost, and mainly surface doping, but not bulk doping, has limited effect.
Disclosure of Invention
The application aims to provide a ternary cathode material, a preparation method and a lithium ion battery, and aims to solve the technical problem of how to realize bulk phase doping of doped metal elements or reduce surface alkalinity while coating the ternary cathode material.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a ternary cathode material, comprising:
mixing a ternary positive electrode material precursor, a lithium salt and a doped metal source to obtain a mixed material; the doped metal source is selected from oxide and/or hydroxide of doped metal, the doped metal source contains at least two doped metals, and the total amount of the doped metals is calculated by the residual amount after the doped metals are doped in the precursor of the ternary cathode material;
and sintering the mixed material to obtain the ternary cathode material.
In one embodiment, the precursor of the ternary cathode material has a general formula of Ni x Co y Mn 1-x-y (OH) z (ii) a Wherein x is more than or equal to 0.85 and less than or equal to 0.90,0 and less than or equal to 0.15, x + y is more than or equal to 1.0,1.8 and less than or equal to 2.2;
the ratio of the total molar weight of the nickel, the cobalt and the manganese in the obtained ternary cathode material to the total molar weight of the doped metal elements is n: m, and 0 & lt 1-n & lt m & lt 0.05.
In one embodiment, the molar ratio of the total molar amount of the three elements, i.e., nickel, cobalt, and manganese, in the ternary positive electrode material precursor to the lithium element in the lithium salt is (1.
In one embodiment, the dopant metal of the dopant metal source is selected from at least two of aluminum, niobium, and tantalum.
In one embodiment, when the doping metal includes aluminum element, the source of the doping metal corresponding to the aluminum element is selected from at least one of aluminum oxide and aluminum hydroxide;
when the doped metal comprises niobium, the doped metal source corresponding to the niobium is at least one selected from niobium oxide and niobium hydroxide;
when the doped metal comprises tantalum, the doped metal source corresponding to the tantalum is selected from at least one of tantalum oxide and tantalum hydroxide.
In one embodiment, the lithium salt is selected from at least one of lithium hydroxide and lithium carbonate.
In one embodiment, the step of sintering the mixture comprises: placing the mixed material in a sintering furnace, firstly preserving heat for 3-5 h at 490-600 ℃, then raising the temperature to 700-800 ℃ and preserving heat for 8-20 h; and/or the presence of a gas in the gas,
the method for mixing the ternary positive electrode material precursor, the lithium salt and the doped metal source comprises the following steps: mechanically mixing the precursor of the ternary positive electrode material, lithium salt and a doped metal source.
In one embodiment, the mixed material is placed in a sintering furnace, and sintering is carried out after oxygen atmosphere is introduced into the sintering furnace; and/or the presence of a gas in the gas,
the heating rate of heating to 700-800 ℃ is 2-5 ℃/min.
In a second aspect, the present application provides a ternary cathode material prepared by the preparation method of the ternary cathode material of the present application.
In a third aspect, the present application provides a lithium ion battery, wherein a ternary cathode material prepared by the preparation method of the present application is used for a cathode of the lithium ion battery.
In the preparation method of the ternary cathode material provided by the first aspect of the application, metal element doping and coating layer preparation of the ternary cathode material are simultaneously realized by adopting a one-step pure solid phase method, and specifically, a ternary cathode material precursor, a lithium salt and a doped metal source (selected from doped metal oxides and/or hydroxides, containing at least two doped metals, and the total amount of the doped metals is calculated by the balance after being doped in the ternary cathode material precursor) are mixed and sintered to obtain the ternary cathode material. Therefore, the ternary cathode material obtained by the preparation method has a good doping effect, can remarkably improve the cycle stability, and has a good application prospect in lithium ion batteries.
The ternary cathode material provided by the second aspect of the application is prepared by the preparation method of the ternary cathode material, and based on the preparation method, the metal element doping and the coating layer preparation of the ternary cathode material can be simultaneously realized in a pure solid phase manner in one step, so that the ternary cathode material provided by the application has a good doping effect, can remarkably improve the cycle stability, and has a good application prospect in a lithium ion battery.
The lithium ion battery anode provided by the third aspect of the application uses the ternary anode material prepared by the preparation method of the ternary anode material, and based on the preparation method, the metal element doping and coating layer preparation of the ternary anode material can be simultaneously realized in a pure solid phase manner by one step, so that the ternary anode material used in the lithium ion battery provided by the third aspect of the application has a good doping effect, and the cycle stability of the lithium ion battery can be remarkably improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, 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 only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is an X-ray diffraction pattern of a ternary cathode material prepared in example 1 of the present application;
FIG. 2 is a mapping diagram of aluminum element in EDX test of scanning electron microscope after ion milling and slicing of ternary cathode material prepared in example 1 of the present application;
fig. 3 is a performance graph of a button cell assembled by the ternary cathode material prepared in example 1 of the present application, wherein a is a charge-discharge curve of the 2 nd, 40 th and 210 th circles of a 0.5C cycle, and b is a discharge curve corresponding to each circle of the cycle;
fig. 4 is a performance graph of a button cell assembled by the ternary cathode material prepared in example 2 of the present application, where a is a charge-discharge curve at the 2 nd, 74 th and 200 th circles of the 0.5C cycle, and b is a discharge curve corresponding to each circle of the cycle;
fig. 5 is a performance graph of a button cell assembled by the ternary cathode material prepared in example 3 of the present application, wherein a is a charge-discharge curve of the 2 nd, 100 th and 180 th circles of a 0.5C cycle, and b is a discharge curve corresponding to each circle of the cycle;
fig. 6 is a discharge curve corresponding to each cycle of 0.5C cycle of a button cell assembled by the ternary cathode material prepared in example 4 of the present application;
fig. 7 is a discharge curve corresponding to each cycle of 0.5C cycle of a button cell assembled by the ternary cathode material prepared in example 5 of the present application;
fig. 8 is a discharge curve corresponding to each cycle of 0.5C cycle of a button cell assembled from the ternary cathode material prepared in example 6 of the present application;
fig. 9 is a performance graph of a button cell assembled by the ternary cathode material prepared in comparative example 1 of the present application, wherein a is a charge-discharge curve of the 2 nd, 100 th and 180 th circles of a 0.5C cycle, and b is a discharge curve corresponding to each circle of the cycle;
fig. 10 is a performance graph of a button cell assembled by the ternary cathode material prepared in comparative example 2 of the present application, wherein a is a charge-discharge curve of the 2 nd, 100 th and 180 th circles of a 0.5C cycle, and b is a discharge curve corresponding to each circle of the cycle;
fig. 11 is a discharge curve for each cycle of 0.5C cycle of a button cell assembled from the ternary cathode material prepared in comparative example 3 of the present application;
fig. 12 is a performance chart of button cell assembled by ternary positive electrode material prepared in comparative example 4 of the present application, wherein a is a charge and discharge curve of cycle 2, 100 and 180 at 0.5C, and b is a discharge curve corresponding to each cycle.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a alone, A and B together, and B alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "plural" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
A first aspect of an embodiment of the present application provides a method for preparing a ternary cathode material, including the following steps:
s01: mixing a ternary positive electrode material precursor, a lithium salt and a doped metal source to obtain a mixed material; the doped metal source is selected from oxide and/or hydroxide of doped metal, the doped metal source contains at least two doped metals, and the total amount of the doped metals is calculated by the balance after the doped metals are doped in the precursor of the ternary cathode material;
s02: and sintering the mixed material to obtain the ternary cathode material.
The preparation method of the ternary cathode material comprises the steps of mixing a ternary cathode material precursor, lithium salt and the specially selected doped metal source, and then sintering to obtain the ternary cathode material, wherein no solvent exists in the process, and multiple metal elements can be simultaneously doped into the ternary cathode material precursor body and the surface, so that the bonding force of transition metal ions and oxygen atoms is greatly enhanced, the cycle stability is improved, and in addition, the redundant doped metal elements and the surface residual alkali are subjected to neutralization reaction to form a compact coating layer, so that the surface residual lithium salt can be converted to reduce the alkalinity, and the coating layer can effectively prevent electrolyte from contacting with the ternary cathode material to reduce the side reaction. Therefore, the ternary cathode material obtained by the preparation method has a good doping effect, can remarkably improve the cycle stability, and has a good application prospect in lithium ion batteries.
In an embodiment, the precursor of the ternary cathode material is a precursor of a nickel-cobalt-manganese ternary cathode material, and the prepared ternary cathode material is the nickel-cobalt-manganese ternary cathode material.
Specifically, the general formula of the precursor of the nickel-cobalt-manganese ternary cathode material is Ni x Co y Mn 1-x-y (OH) z (ii) a Wherein x is more than or equal to 0.85 and less than or equal to 0.90,0 and less than or equal to 0.15, x + y is more than or equal to 1.0,1.8 and less than or equal to 2.2; where x can be 0.86, 0.87, 0.89, etc., x can be 0.1, 0.12, 0.13, 0.14, etc., and z can be 1.9, 2.0, 2.1, 2.2, etc. According to the embodiment of the application, the high-nickel ternary cathode material can be prepared by taking the ternary cathode material precursor as a raw material, so that the high-nickel ternary cathode material with high specific capacity, high working voltage and compacted density can be further improved in cycle stability and safety. Wherein, the ratio of the total molar weight of the nickel (Ni), the cobalt (Co) and the manganese (Mn) in the obtained ternary cathode material to the total molar weight of the doped metal elements is n: m, and 0 < 1-n < m < 0.05, and under the condition of the ratio range, the doped metal elements are doped on the body and the surface of the ternary cathode material, and the rest and the residual alkali (OH) on the surface of the ternary cathode material are remained - 、CO 3 2- ) And reacted, thereby having an effect of reducing the residual alkali content. For example, taking 0.96 of the total molar amount of the three elements of nickel, cobalt and manganese in the ternary cathode material and 0.043 of the total molar amount of the doped metal element as an example, the doped metal is doped on the bulk and surface of the ternary cathode material with 0.96 parts of the total molar amount of the three elements of nickel, cobalt and manganese, and 0.04 part of the rest (0.043-0.04 = 0.003) of the doped metal element and the rest of the alkali (OH) on the surface of the ternary cathode material is doped (0.04 parts by mole) - 、CO 3 2- ) And (4) reacting.
In one embodiment, the molar ratio of the total molar amount of the three elements, i.e., nickel, cobalt, and manganese, in the ternary positive electrode material precursor to the molar amount of the lithium element in the lithium salt is (1. The nickel cobalt lithium manganate ternary positive electrode material can be prepared under the condition of the proportion and used in a lithium ion battery. Further, the lithium salt may be at least one selected from lithium hydroxide and lithium carbonate.
In one embodiment, the dopant metal in the dopant metal source is selected from at least two of aluminum (Al), niobium (Nb), and tantalum (Ta). Specifically, when the doping metal includes aluminum element, the doping metal source corresponding to the aluminum element is selected from at least one of aluminum oxide and aluminum hydroxide; when the doped metal comprises niobium, the doped metal source corresponding to the niobium is at least one selected from niobium oxide and niobium hydroxide; when the doped metal comprises tantalum element, the doped metal source corresponding to the tantalum element is selected from at least one of tantalum oxide and tantalum hydroxide. Two or more doping metal sources are selected, so that two or more metal doping of aluminum, niobium and tantalum elements can be realized.
According to the embodiment of the application, by doping Al, nb and Ta, the bonding force between the transition metal layer and the O layer can be better stabilized, and the phase change in the circulation process is reduced, so that the fragmentation and oxygen evolution are reduced. Calculation proves that the change of the formation energy of the molecules of the ternary cathode material after 10000ppm of metal element is doped, so that LiNi is used 0.89 Co 0.04 Mn 0.07 O 2 For example, when 10000ppm of a metal element is doped with Al, ta, nb, W, and Mg, liNi is obtained 0.89 Co 0.04 Mn 0.07 O 2 The formation energy of the molecules of the ternary cathode material can be varied as shown in table 1 below. According to the thermodynamic principle, the more the formation energy is reduced, the more stable the structure is after the element doping, therefore, the more the formation energy is reduced after the aluminum, tantalum and niobium element doping than the magnesium and tungsten doping, the more stable the structure is.
TABLE 1 LiNi 0.89 Co 0.04 Mn 0.07 O 2 Change of formation energy after molecular doping with metal element
| Doping element | Amount of doping (ppm) | Variation of formation energy (eV) |
| Aluminum (Al) | 10000 | -3.01 |
| Tantalum (Ta) | 10000 | -4.52 |
| Niobium (Nb) | 10000 | -3.32 |
| Tungsten (W) | 10000 | 0.02 |
| Magnesium (Mg) | 10000 | -0.30 |
Further, the doping metal source of Al, nb, ta is selected from the oxides and/or hydroxides of the doping metals. The ternary cathode material in a full-current state contains a large amount of Ni 4+ Has strong oxidizability and can generate side reaction when directly contacting with the electrolyte. In the embodiment of the application, the doped metal oxide reacts with the residual lithium salt on the surface under the high-temperature sintering condition to form aCoating a layer to prevent the electrolyte from directly contacting with the ternary cathode material, thereby reducing side reactions; and the metal oxide doped with metal can reduce residual alkali after reacting with residual lithium salt on the surface, and the reduction of the residual alkali can not only improve the processability of the material, but also improve the cycle life and the safety of a subsequent battery.
In one embodiment, the step of sintering the mixture comprises: placing the mixed material in a sintering furnace, firstly preserving heat for 3-5 h at 490-600 ℃, and then heating to 700-800 ℃ and preserving heat for 8-20 h. Specifically, for example, the temperature is kept at 500 ℃, 520 ℃, 540 ℃, 550 ℃, 580 ℃ or 600 ℃ for 3h, 3.5h, 4h or 5h, and then the temperature is kept at 700 ℃, 750 ℃, 760 ℃, 780 ℃ or 800 ℃ for 8h, 9h, 10h, 12h, 14h, 16h, 18h or 20h, etc. The sintering process can better carry out pre-lithiation and crystal growth, and the ternary cathode material product is obtained after sintering, crushing and refining.
Furthermore, oxygen atmosphere is introduced into the sintering furnace, the oxygen flow can be 200-400 sccm, and the heating rate of heating to 700-800 ℃ is 2-5 ℃/min. For example, the temperature rise rate is 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, or the like. Under the above conditions, the oxidation sintering can be performed more stably.
In one embodiment, the step of mixing the ternary positive electrode material precursor, the lithium salt and the doping metal source comprises: mechanically mixing the ternary positive electrode material precursor, the lithium salt and the doped metal source, for example, first mechanically mixing the ternary positive electrode material precursor and the lithium salt, and then adding the doped metal source for second mechanical mixing. Wherein, the first mechanical mixing can be mixing by a stirrer and a ball mill, and the structure of the aggregate is not destroyed by precursors in the mixing process; the second mechanical mixing may be mixing by a blender, ball mill, without destroying the structure of the agglomerates during the mixing process.
In one embodiment, a method for preparing a ternary cathode material comprises the following steps:
the method comprises the following steps:mechanically mixing the ternary positive electrode material precursor and lithium hydroxide monohydrate uniformlyHomogenizing, including but not limited to high speed mixers, ball mills, without damaging the agglomerate structure by the precursor during the mechanical mixing process. Wherein, the molar ratio of the total molar weight of nickel-cobalt-manganese in the ternary cathode material precursor to the molar weight of lithium element in the lithium hydroxide monohydrate is (1.
Adding a certain amount of doping metal source (metal oxide and/or metal hydroxide) into the mixture obtained above, and mechanically mixing uniformly, including but not limited to a high-speed stirrer and a ball mill, wherein the aggregate structure of the precursor is not damaged in the mechanical mixing process. The doping metal elements comprise two or three of Al, nb and Ta, the ratio of the total molar weight of the Ni, co and Mn elements in the finally obtained ternary cathode material to the total molar weight of the Al/Nb/Ta doping metal elements is n: m, and 0 & lt 1-n & lt m & lt 0.05.
Step two:and (3) sintering the mixture obtained in the step one at high temperature step by step, introducing oxygen atmosphere, wherein the sintering furnace comprises one of a tubular furnace and a box furnace. The high-temperature sintering specifically comprises: keeping the temperature at 490-600 ℃ for 3-5 h to pre-lithiate and remove crystal water, and then keeping the temperature at 700-800 ℃ for 8-20 h to grow crystals. Wherein the heating rate is 2-5 ℃/min, and the cooling rate is 2-5 ℃/min.
The second aspect of the embodiments of the present application provides a ternary cathode material, and the ternary cathode material is prepared by the preparation method of the ternary cathode material in the embodiments of the present application.
The ternary cathode material provided by the embodiment of the application is prepared by the preparation method of the ternary cathode material special in the embodiment of the application, and based on the preparation method, the metal element doping and coating layer preparation of the ternary cathode material can be realized simultaneously in a pure solid phase manner in one step, so that the ternary cathode material provided by the embodiment of the application has a good doping effect, can remarkably improve the cycle stability, and has a good application prospect in a lithium ion battery.
The third aspect of the embodiments of the present application also provides a lithium ion battery, where the positive electrode of the lithium ion battery uses the ternary positive electrode material prepared by the above preparation method of the embodiments of the present application.
According to the lithium ion battery anode provided by the embodiment of the application, the ternary anode material prepared by the preparation method of the ternary anode material is used, and based on the preparation method, the metal element doping and coating layer preparation of the ternary anode material can be realized simultaneously in a pure solid phase manner in one step.
The following description will be given with reference to specific examples.
Example 1
A preparation method of a ternary cathode material comprises the following steps:
S11：9.165 grams (Ni) 0.89 Co 0.04 Mn 0.07 )(OH) 2 Uniformly mixing a high-nickel ternary precursor and 4.402 g of lithium hydroxide monohydrate, wherein the molar ratio of the total molar amount of three elements of nickel, cobalt and manganese in the ternary positive electrode material precursor to the molar amount of lithium in a lithium salt is 1.04. Uniformly mixing the mixed powder with niobium oxide and aluminum hydroxide weighed according to a proportion to obtain a mixed material, wherein the molar ratio of the total mole of Ni, co and Mn to the mole of Al and Nb is 0.0316.
S12：And (3) sintering the prepared mixed material in a tube furnace. The first sintering temperature is 500 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 400sccm, the sintering time is 4 hours, and pre-lithiation and crystal water removal are carried out. The second sintering temperature is 730 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 500sccm, the sintering time is 12 hours, and the completion of lithiation and crystal growth is promoted. The heating rate and the cooling rate are both 5 ℃/min.
And (3) crushing and refining the sintered sample, but not destroying the structure of the aggregate, and finally preparing the ternary cathode material.
The X-ray diffraction pattern (scan speed 5 °/min) of the ternary cathode material prepared in this example is shown in fig. 1, and is comparable to that of PDF card LiNiO 2 (PDF # 85-1966) are complexed. FIB-SEM characterization test, FIG. 2 is after slicingEDX tests the mapping diagram of Al element, wherein white spots represent the Al element, and it can be seen from the diagram that the doped metal element forms a layer of compact coating on the surface, and Al ions are uniformly distributed in the material, and the solid nuclear magnetic resonance test shows that the aluminum ions enter the material body after high-temperature sintering. Preparing the prepared ternary cathode material into a cathode, wherein the ternary cathode material comprises the following components in parts by weight: conductive agent: the mass ratio of the binder is 92 -1 About, after 210 cycles, the discharge capacity is 174.3mAhg -1 The capacity retention rate was 89.3%, and the cycle was very stable.
Example 2
A preparation method of a ternary cathode material comprises the following steps:
S21：9.165 grams (Ni) 0.89 Co 0.04 Mn 0.07 )(OH) 2 The high nickel ternary precursor and 4.402 grams of lithium hydroxide monohydrate are uniformly mixed, wherein the molar ratio of the lithium hydroxide to the ternary precursor nickel cobalt manganese is 1.05. And then uniformly mixing the mixed powder with niobium oxide and aluminum hydroxide weighed according to a certain proportion to obtain a mixed material, wherein the molar ratio of the total mole of Ni, co and Mn to the mole of Al and Nb is 0.955.
S22：And (3) sintering the prepared mixed material in a tube furnace. The first sintering temperature is 500 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 200sccm, the sintering time is 4 hours, and pre-lithiation and crystal water removal are carried out. The second sintering temperature is 750 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 500sccm, the sintering time is 12 hours, and the completion of lithiation and crystal growth is promoted. The heating rate and the cooling rate are both 5 ℃/min.
The sintered sample is crushed and refined, but the structure of the aggregate is not damaged. Finally preparing the ternary cathode material.
Preparing the prepared ternary cathode material into a cathode, wherein the ternary cathode material comprises the following components in parts by weight:conductive agent: the mass ratio of the binder is 92 -1 About, after 200 cycles, the discharge capacity is 185.1mAhg -1 The capacity retention rate was 96.6%, and the cycle was very stable.
Example 3
A preparation method of a ternary cathode material comprises the following steps:
S31：9.165 grams (Ni) 0.89 Co 0.04 Mn 0.07 )(OH) 2 The high nickel ternary precursor and 4.402 grams of lithium hydroxide monohydrate are uniformly mixed, wherein the molar ratio of the lithium hydroxide to the ternary precursor nickel cobalt manganese is 1.04. Uniformly mixing the mixed powder with niobium oxide and aluminum hydroxide weighed according to a proportion to obtain a mixed material, wherein according to the molar ratio of Ni, co and Mn to Al and Nb being 0.032 to 0.011, the excessive doped metal cations react with residual alkali to construct an oxide coating layer.
S32：And (3) sintering the prepared mixed material in a tube furnace. The first sintering temperature is 500 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 200sccm, the sintering time is 4 hours, and pre-lithiation and crystal water removal are carried out. The second sintering temperature is 750 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 500sccm, the sintering time is 12 hours, and the completion of lithiation and crystal growth is promoted. The heating rate and the cooling rate are both 5 ℃/min.
And (3) crushing and refining the sintered sample, but not destroying the structure of the aggregate, and finally preparing the ternary cathode material.
Preparing the prepared ternary cathode material into a cathode, wherein the ternary cathode material comprises the following components in parts by weight: conductive agent: the mass ratio of the binder is 92 -1 About, after 200 cycles, the discharge capacity was 171.1mAhg -1 The capacity retention rate was 94.0%, and the cycle was very stable.
Example 4
A preparation method of a ternary cathode material comprises the following steps:
S41：9.165 grams (Ni) 0.89 Co 0.04 Mn 0.07 )(OH) 2 The high nickel ternary precursor and 4.402 grams of lithium hydroxide monohydrate are uniformly mixed, wherein the molar ratio of the lithium hydroxide to the ternary precursor nickel cobalt manganese is 1.05. And then uniformly mixing the mixed powder with weighed niobium oxide and tantalum oxide to obtain a mixed material, wherein the molar ratio of the total mol of Ni, co and Mn to the mol of Ta and Nb is 0.0053, and the excessive doped metal cations are reacted with residual alkali to construct an oxide coating layer.
S41：And (3) sintering the prepared mixed material in a tube furnace. The first sintering temperature is 500 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 200sccm, the sintering time is 4 hours, and the crystal water and the pre-lithiation are removed. The second sintering temperature is 750 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 500sccm, the sintering time is 12 hours, and the completion of lithiation and crystal growth is promoted. The heating rate and the cooling rate are both 5 ℃/min.
And (3) crushing and refining the sintered sample, but not destroying the structure of the aggregate, and finally preparing the ternary cathode material.
Preparing the prepared ternary cathode material into a cathode, wherein the ternary cathode material comprises the following components in parts by weight: conductive agent: the mass ratio of the binder is 92 -1 About 180 circles, the discharge capacity is 169.4mAhg -1 The capacity retention rate is 91.4%, and the cycle is stable.
Example 5
A preparation method of a ternary cathode material comprises the following steps:
S51：9.165 grams (Ni) 0.89 Co 0.04 Mn 0.07 )(OH) 2 The high nickel ternary precursor and 4.402 grams of lithium hydroxide monohydrate are uniformly mixed, wherein the molar ratio of the lithium hydroxide to the ternary precursor nickel cobalt manganese is 1.04. Then evenly mixing the mixed powder with weighed niobium oxide and tantalum oxide to obtain a mixed material,the molar ratio of the total mole of Ni, co and Mn to the mole of Ta and Nb is 0.98.
S52：And (3) sintering the prepared mixed material in a tube furnace. The first sintering temperature is 500 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 200sccm, the sintering time is 4 hours, and the crystal water and the pre-lithiation are removed. The second sintering temperature is 750 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 500sccm, the sintering time is 12 hours, and the completion of lithiation and crystal growth is promoted. The heating rate and the cooling rate are both 5 ℃/min.
And (3) crushing and refining the sintered sample, but not destroying the structure of the aggregate, and finally preparing the ternary cathode material.
Preparing the prepared ternary cathode material into a cathode, wherein the ternary cathode material comprises the following components in parts by weight: conductive agent: the mass ratio of the binder is 92 -1 About, after 200 circles, the discharge capacity is 174.4mAhg -1 The capacity retention rate was 91.7%, and the cycle was very stable.
Example 6
A preparation method of a ternary cathode material comprises the following steps:
S61：9.165 grams (Ni) 0.89 Co 0.04 Mn 0.07 )(OH) 2 The high nickel ternary precursor and 4.402 grams of lithium hydroxide monohydrate are uniformly mixed, wherein the molar ratio of the lithium hydroxide to the ternary precursor nickel cobalt manganese is 1.04. And then, uniformly mixing the mixed powder with two of the weighed tantalum oxide and aluminum hydroxide, wherein according to the molar ratio of the total mole of Ni, co and Mn to the mole of Al and Ta being 0.985, the excessive doped metal cations react with the residual alkali to construct an oxide coating layer.
S62：And (3) sintering the prepared mixed material in a tube furnace. The first sintering temperature is 500 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 200sccm, the sintering time is 4 hours, the crystal water is removed, and the pre-lithiation is carried out. The second sintering temperature is 750 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 500sccm, the sintering time is 12 hours, and the completion of lithiation and crystal growth is promoted. The heating rate and the cooling rate are both 5 ℃/min.
And (3) crushing and refining the sintered sample without destroying the structure of the aggregate, and finally preparing the ternary cathode material.
Preparing the prepared ternary cathode material into a cathode, wherein the ternary cathode material comprises the following components in parts by weight: conductive agent: the mass ratio of the binder is 92 -1 About, after 200 circles, the discharge capacity is 175.0mAhg -1 The capacity retention rate was 90.9%, and the cycle was very stable.
Comparative example 1
A preparation method of a ternary cathode material comprises the following steps:
9.165 grams (Ni) 0.89 Co 0.04 Mn 0.07 )(OH) 2 The high nickel ternary precursor and 4.402 grams of lithium hydroxide monohydrate are uniformly mixed, wherein the molar ratio of the lithium hydroxide to the ternary precursor nickel cobalt manganese is 1.04. The mixture prepared above was sintered in a tube furnace: the first sintering temperature is 500 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 200sccm, the sintering time is 4 hours, and the crystal water and the pre-lithiation are removed. The second sintering temperature is 750 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 500sccm, the sintering time is 12 hours, and the completion of lithiation and crystal growth is promoted. The heating rate and the cooling rate are both 5 ℃/min. Grinding and refining the sintered sample without destroying the structure of the aggregate, and finally preparing the LiNi 0.89 Co 0.04 Mn 0.07 O 2 A ternary positive electrode material.
Preparing the prepared ternary cathode material into a cathode, wherein the ternary cathode material comprises the following components in parts by weight: conductive agent: the mass ratio of the binder is 92 -1 About, after 180 circles, the discharge capacity is 117.8mAhg -1 Capacity retention of onlyAnd (7) percent. Without multi-element doping or cladding, the capacity retention is very low.
Comparative example 2
A preparation method of a ternary cathode material comprises the following steps:
9.165 g (Ni) 0.89 Co 0.04 Mn 0.07 )(OH) 2 Uniformly mixing the high-nickel ternary precursor and 4.402 g of lithium hydroxide monohydrate, wherein the molar ratio of the lithium hydroxide to the ternary precursor nickel-cobalt-manganese is 1.05. And then uniformly mixing the mixed powder with weighed aluminum hydroxide to obtain a mixed material, wherein the molar ratio of the total mole of Ni, co and Mn in the ternary precursor to the mole of Al is 0.96. Placing the mixed material in a tube furnace for sintering: the first sintering temperature is 500 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 200sccm, the sintering time is 4 hours, and the crystal water and the pre-lithiation are removed. The second sintering temperature is 750 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 500sccm, the sintering time is 12 hours, and the completion of lithiation and crystal growth is promoted. The heating rate and the cooling rate are both 5 ℃/min.
The sintered sample is crushed and refined, but the structure of the aggregate is not destroyed, and finally Li is prepared a (Ni 0.89 Co 0.04 Mn 0.07 ) 0.96 Al 0.04 O 2 A ternary positive electrode material.
Preparing the prepared ternary cathode material into a cathode, wherein the ternary cathode material comprises the following components in parts by weight: conductive agent: the mass ratio of the binder is 92 -1 About, after 180 circles, the discharge capacity is 150.9mAhg -1 The capacity retention rate was 81.8%, and the cycle stability was general.
Comparative example 3
A preparation method of a ternary cathode material comprises the following steps:
9.165 g (Ni) 0.89 Co 0.04 Mn 0.07 )(OH) 2 Uniformly mixing the high-nickel ternary precursor and 4.402 g of lithium hydroxide monohydrate, wherein the molar ratio of the lithium hydroxide to the ternary precursor nickel-cobalt-manganeseIs 1.05. And then uniformly mixing the mixed powder with weighed niobium oxide to obtain a mixed material, wherein the molar ratio of the total mole of Ni, co and Mn in the ternary precursor to the mole of Nb is 0.99. Placing the mixed material in a tube furnace for sintering: the first sintering temperature is 500 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 200sccm, the sintering time is 4 hours, and the crystal water and the pre-lithiation are removed. The second sintering temperature is 750 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 500sccm, the sintering time is 12 hours, and the completion of lithiation and crystal growth is promoted. The heating rate and the cooling rate are both 5 ℃/min.
The sintered sample is crushed and refined, but the structure of the aggregate is not destroyed, and finally Li is prepared a (Ni 0.89 Co 0.04 Mn 0.07 ) 0.99 Nb 0.01 O 2 A ternary positive electrode material.
Preparing the prepared ternary cathode material into a cathode, wherein the ternary cathode material comprises the following components in parts by weight: conductive agent: the mass ratio of the binder is 92 -1 About, after 180 circles, the discharge capacity is 150.9mAhg -1 The capacity retention rate was 81.8%, and the cycle stability was general.
Comparative example 4
For comparison, the preparation method for synthesizing the ternary cathode material by using the wet method comprises the following steps:
S71：9.165 g (Ni) 0.89 Co 0.04 Mn 0.07 )(OH) 2 Uniformly mixing a high-nickel ternary precursor and 4.402 g of lithium hydroxide monohydrate, wherein the molar ratio of the total molar amount of three elements of nickel, cobalt and manganese in the ternary positive electrode material precursor to the molar amount of lithium in a lithium salt is 1.04, placing the mixture in 100ml of deionized water, and continuously stirring by magnetic force. Then adding aluminum sulfate and ammonium niobate oxalate, wherein the molar ratio of the total mole of Ni, co and Mn in the ternary precursor to the mole of Al and Nb is 0.965. Heating while magnetically stirring until drying.
S72：And (3) sintering the prepared mixed material in a tube furnace. The first sintering temperature is 500 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 400sccm, the sintering time is 4 hours, and pre-lithiation and crystal water removal are carried out. The second sintering temperature is 730 ℃, pure oxygen atmosphere is introduced, the oxygen flow is 500sccm, the sintering time is 12 hours, and the completion of lithiation and crystal growth is promoted. The heating rate and the cooling rate are both 5 ℃/min.
Finally preparing the ternary cathode material.
Preparing the prepared ternary cathode material into a cathode, wherein the ternary cathode material comprises the following components in parts by weight: conductive agent: the mass ratio of the binder is 92 -1 About, after 180 circles, the discharge capacity is 140.0mAhg -1 The capacity retention rate was 77.5%, and the capacity retention rate was very low.
Residual alkali test
In addition, the residual alkali of the examples and the comparative examples is tested, and the results are shown in table 2, and the content of the residual alkali (tested by a Switzerland 916Ti-Touch automatic point titration apparatus) of the ternary cathode material prepared in the examples of the application is obviously reduced compared with that of the comparative example. In the comparative example, no excess metal element was used for doping, and the residual alkali content was high.
TABLE 2 residual alkali content of ternary cathode materials
According to the embodiment and the comparative example, the preparation method of the pure solid-phase multi-element doped, alkali-removing and coated ternary cathode material can improve the cycle stability of the ternary cathode material; can obviously reduce residual alkali (OH) - ，CO 3 2- ) And (4) content.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a ternary cathode material is characterized by comprising the following steps:
mixing a ternary positive electrode material precursor, a lithium salt and a doped metal source to obtain a mixed material; the doped metal source is selected from oxide and/or hydroxide of doped metal, the doped metal source contains at least two doped metals, and the total amount of the doped metals is calculated by the balance after being doped in the precursor of the ternary cathode material;
and sintering the mixed material to obtain the ternary cathode material.
2. The method according to claim 1, wherein the ternary positive electrode material precursor has a general formula of Ni x Co y Mn 1-x-y (OH) z (ii) a Wherein x is more than or equal to 0.85 and less than or equal to 0.90,0 and less than or equal to 0.15, x + y is more than or equal to 1.0,1.8 and less than or equal to 2.2;
the ratio of the total molar weight of the nickel, the cobalt and the manganese in the obtained ternary cathode material to the total molar weight of the doped metal elements is n: m, and 0 & lt 1-n & lt m & lt 0.05.
3. The production method according to claim 2, wherein the molar ratio of the total molar amount of the three elements of nickel, cobalt, and manganese in the ternary positive electrode material precursor to the lithium element in the lithium salt is (1.
4. The method of claim 1, wherein the dopant metal of the dopant metal source is selected from at least two of the group consisting of aluminum, niobium, and tantalum.
5. The method of claim 4, wherein when the doping metal includes aluminum element, the source of the doping metal corresponding to the aluminum element is selected from at least one of aluminum oxide and aluminum hydroxide;
when the doped metal comprises niobium, the doped metal source corresponding to the niobium is selected from at least one of niobium oxide and niobium hydroxide;
when the doped metal comprises tantalum, the doped metal source corresponding to the tantalum is selected from at least one of tantalum oxide and tantalum hydroxide.
6. The method according to claim 1, wherein the lithium salt is at least one selected from the group consisting of lithium hydroxide and lithium carbonate.
7. The method according to any one of claims 1 to 6, wherein the subjecting of the mixed material to a sintering treatment comprises: placing the mixed material in a sintering furnace, firstly preserving heat for 3-5 h at 490-600 ℃, then raising the temperature to 700-800 ℃ and preserving heat for 8-20 h; and/or the presence of a gas in the atmosphere,
the method for mixing the ternary positive electrode material precursor, the lithium salt and the doped metal source comprises the following steps: and mechanically mixing the ternary positive electrode material precursor, the lithium salt and the doped metal source.
8. The method according to claim 7, wherein the mixed material is placed in a sintering furnace, and sintering is performed after an oxygen atmosphere is introduced into the sintering furnace; and/or the presence of a gas in the atmosphere,
the heating rate of heating to 700-800 ℃ is 2-5 ℃/min.
9. A ternary cathode material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 8.
10. A lithium ion battery, characterized in that the ternary cathode material prepared by the preparation method of any one of claims 1 to 8 is used as the cathode of the lithium ion battery.
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| CN115632125A (en) * | 2022-12-22 | 2023-01-20 | 松山湖材料实验室 | Positive electrode active material, and preparation method and application thereof |
| CN116143189A (en) * | 2022-12-28 | 2023-05-23 | 浙江华友钴业股份有限公司 | Positive electrode material, preparation method thereof and battery |
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