CN113299906A - Cation and fluorine anion double-doped modified ternary cathode material and preparation method thereof - Google Patents
Cation and fluorine anion double-doped modified ternary cathode material and preparation method thereof Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 64
- 150000001768 cations Chemical class 0.000 title claims abstract description 55
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 239000010405 anode material Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000002019 doping agent Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 60
- 238000005245 sintering Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 25
- -1 cation salt Chemical class 0.000 claims description 25
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 11
- 239000010955 niobium Substances 0.000 claims description 11
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- 239000002612 dispersion medium Substances 0.000 claims description 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 3
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 24
- 229910052759 nickel Inorganic materials 0.000 abstract description 12
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 abstract description 10
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 21
- 238000000498 ball milling Methods 0.000 description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 10
- 239000011812 mixed powder Substances 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 2
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 2
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910019714 Nb2O3 Inorganic materials 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Chemical class 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229940006444 nickel cation Drugs 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a cation and fluorine anion double-doped modified ternary positive electrode material with a chemical formula of LiNi1‑x‑y‑αCoxMnyMαO2‑βFβX is more than or equal to 0 and less than or equal to 0.4, y is more than or equal to 0 and less than or equal to 0.4, 1-x-y-alpha is more than or equal to 0.6 and less than or equal to 1, alpha is more than or equal to 0 and less than or equal to 0.05, beta is more than or equal to 0 and less than or equal to 6 alpha; wherein M is a dopant cation, and the outer shell has d0Electronic configuration. The cation and fluorine anion double-doped modified ternary cathode material provided by the invention solves the problem of lithium-nickel mixed discharge of a high-nickel cathode material and solves the problem that the cathode material is in a lithium-removing stateThe problem that the lower lattice oxygen is easily oxidized is solved, the structural stability and the cycling stability of the material are improved, and therefore the electrochemical performance of the anode material is improved. The invention also provides a preparation method of the cation and fluorine anion double-doped modified ternary cathode material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrode materials, in particular to a modified ternary positive electrode material with double doping of cations and fluorine anions and a preparation method thereof.
Background
With the rapid development of new energy automobiles, the lithium ion battery industry enters a rapid development stage. The endurance mileage of the new energy automobile is an important reason for restricting the popularization of the new energy automobile. Increasing the energy density of lithium ion batteries is an effective way to increase mileage. Lithium ions which can migrate inside the lithium ion battery are completely provided by the anode material, and the actual specific capacity of the anode material limits the specific capacity of the lithium ion battery. Thus, the ternary layered oxide material LiNi1-x-yCoxMnyO2The lithium ion battery cathode material is widely used due to high theoretical capacity, but Li in the lithium ion battery cathode material cannot be completely extracted, the method for improving the reversible lithium ion extraction amount of the ternary cathode material is to improve the nickel content, and the high-nickel ternary cathode material is considered to be the next generation lithium ion battery cathode material.
LiNi1-x-yCoxMnyO2Is a layered oxide structure, but the actually prepared material is accompanied by cation shuffling, which limits the electrochemical performance of the material. Among them, Co is mainly used to promote the formation of a layered structure, Mn is mainly used to stabilize the structure, and Ni is mainly used to participate in the redox reaction in the electrochemical process to provide capacity. With the further increase of the Ni content, the Co and Mn content is reduced, the mixed arrangement of lithium and nickel cations is aggravated, the structural stability is poor, and the cycle performance of the anode material is reduced.
During deep charging, lattice oxygen becomes unstable and is easily oxidized to form oxygen defects, and irreversible phase transition occurs in the material, resulting in a decrease in cycle life. Meanwhile, the high-nickel anode material in a charging state has poor thermal stability and is easy to react with electrolyte.
The two problems of lithium-nickel cation mixed discharge and lattice oxygen oxidation are intrinsic problems of the high-nickel ternary cathode material, and the problems can be fundamentally solved only by doping the material from the structure of the material.
Chinese patent CN 108336318A discloses a lithium-rich cathode material doped with molybdenum/fluorine and coated with spinel in situ and a preparation method thereof. The chemical formula of the cathode material is Li1.2-δMnaNib-λCocMoλO2-δFδBelonging to lithium-rich cathode materials. Soluble salts of lithium, nickel, cobalt and manganese, molybdenum salt and fluoride are adopted, complexing agent is added, mixed solution is prepared, heated and stirred uniformly, cooled to form gel, and freeze-dried to prepare precursor powder. The method has the advantages of complex operation, high equipment cost, low reactant concentration and low yield. Has little significance for industrial mass production. In addition, the Mo and F doping in the patent mainly solves the problems of poor stability of the internal and surface interface structures of the lithium-rich cathode material and low lithium ion diffusion rate.
Chinese patent CN 108832096A discloses a double-doped lithium ion battery anode material, a preparation method thereof and a lithium ion battery. The chemical formula of the cathode material is Li2Mn0.75M0.25O2F, belonging to a lithium-rich cathode material, wherein M is + 6-valent metal. The lithium ion battery anode material is obtained by performing ball milling on a lithium source, a manganese source, an M metal source and an F source for 5-80 h. The method has long ball milling time, needs protective atmosphere, and has harsh preparation environment, extreme and high noise. The patent is doped with high-valence + 6-valence ions mainly for reducing the valence state of Mn of a positive electrode material to enable the Mn to exist in a + 2-valence state, so that Mn is utilized2+/Mn4+The reversible redox couple increases the overall energy density of the material. And the lithium-rich cathode material has high specific discharge capacity, but poor rate performance is a difficult problem which is not overcome yet, so that the commercial application of the lithium-rich cathode material is restricted. In contrast, the coprecipitation method for preparing the precursor for the current ternary cathode material is commercially usedMature, and is simpler and more feasible to modify on the basis of preparing a precursor by the existing coprecipitation method.
Chinese patent CN 109888261A discloses a modified nickel-rich ternary composite electrode material and a preparation method thereof. The method is implemented by simply mixing LiO, NiO, CoO, MnO and a doped oxide Nb2O3Or MoO3And after mixing, carrying out dry mixing ball milling, and sintering to obtain the anode material. Pure oxide of three elements of nickel, cobalt and manganese and doped oxide Nb2O3Or MoO3Various elements are difficult to be uniformly mixed on an atomic layer by a ball milling method, and the electrochemical data of the cathode material prepared by the method is poor.
Chinese patent CN 110323432A discloses an anion-cation co-doped modified lithium ion battery anode material and a preparation method thereof. Has a chemical formula of Li1.2Mn0.54Ni0.16Co0.1-xAlxO2-yFyWherein x is more than 0 and less than or equal to 0.05, and y is more than 0 and less than or equal to 0.05, and belongs to a lithium-rich anode material. The method is characterized in that cations are precipitated through a coprecipitation method, and then lithium fluoride is added during the process of mixing the precursors with lithium to be sintered together to prepare the cathode material. The doping cation of the material is Al3+The anion is F-ion. This method can only introduce the cations to be doped at the precursor stage, but cannot be used for cations that cannot be precipitated by co-precipitation.
In conclusion, the intrinsic problems of two high-nickel ternary cathode materials, namely lithium-nickel cation mixed-discharge and easy oxidation of lattice oxygen, are not solved in the prior art.
In view of the above, the present invention aims to provide a modified ternary positive electrode material doped with both cations and fluorine anions and a preparation method thereof, so as to solve the intrinsic problems of two high-nickel ternary positive electrode materials, namely cation mixing and inhibition of oxidation of lattice oxygen, and simultaneously improve the electrochemical performance of the positive electrode material.
Disclosure of Invention
The invention aims to solve the technical problems of providing a cation and fluorine anion double-doping modified ternary cathode material, solving the problem of lithium-nickel mixed arrangement of a high-nickel cathode material and the problem that lattice oxygen of the cathode material is easily oxidized in a lithium removal state, and improving the structural stability and the cycling stability of the material, thereby improving the electrochemical performance of the cathode material.
In order to solve the problems, the technical scheme of the invention is as follows:
a modified ternary positive electrode material with double doping of cations and fluorine anions has a chemical formula of LiNi1-x-y-αCoxMnyMαO2-βFβX is more than or equal to 0 and less than or equal to 0.4, y is more than or equal to 0 and less than or equal to 0.4, 1-x-y-alpha is more than or equal to 0.6 and less than or equal to 1, alpha is more than or equal to 0 and less than or equal to 0.05, beta is more than or equal to 0 and less than or equal to 6 alpha; wherein M is a dopant cation, and the outer shell has d0Electronic configuration.
Further, the doping cation M is Ti4+，V5+，Zr4+，Nb5+，W6+Or Mo6+。
Further, the ratio of alpha to beta is 1: 0.5-6.
The invention also provides a preparation method of the cation and fluorine anion double-doped modified ternary cathode material, which comprises the following steps:
step S1, the precursor of the ternary anode material is added with d0Adding an M cation salt with an electronic configuration and a fluoride into a dispersion medium, grinding and mixing uniformly;
step S2, adding a lithium source into the mixture obtained in the step S1, grinding uniformly and then drying;
and step S3, sintering at high temperature in the atmosphere of oxygen or air, and cooling to obtain the modified ternary positive electrode material with double doping of cations and fluorine anions.
Further, the precursor contains d0Mixing the electronic configuration M cation salt and fluoride according to a molar ratio of 1:0.0025-0.05: 0.00125-0.3; the molar ratio of the precursor to the lithium source is 1: 1-1.1.
Further, contains d0In the electronic configuration of M cation salt, the doping cation M is Ti4+，V5+，Zr4+，Nb5+，W6+Or Mo6+。
Further, the Mo source adopts ammonium heptamolybdate tetrahydrate or molybdenum trioxide; the W source adopts ammonium tungstate or tungsten trioxide; the Ti source is tetrabutyl titanate or titanium dioxide; the V source adopts ammonium vanadate or vanadium pentoxide; the Zr source adopts zirconium oxychloride or zirconium oxynitrate; the Nb source adopts niobium pentoxide or niobium oxalate.
Further, in step S1, the fluoride is ammonium fluoride or lithium fluoride; the dispersion medium is ethanol, water or isopropanol, the mass ratio of the precursor to the dispersion medium is 5-10:1, and the mixing time is 0.5-2 h.
Further, in step S2, the grinding time is 0.5-6h, the drying time is 0.5-2h, and the drying temperature is 60-130 ℃.
Further, in step S3, the high-temperature sintering process includes: heating to 450-500 ℃ for sintering for 3-5h, and then heating to 700-850 ℃ for sintering for 2-20 h; the heating rate is 3-5 ℃/min.
Compared with the prior art, the cation and fluorine anion double-doped modified ternary cathode material and the preparation method thereof have the beneficial effects that:
the invention provides a cation and fluorine anion double-doped modified ternary positive electrode material and a preparation method thereof, wherein the doped cation is used for partially replacing the position of transition metal ions, and the outer shell layer of the material is provided with d0Electronic configuration. Such electronic configuration not only results in d0The ions have low energy at the location of the distortion and their flexibility to the distortion allows other transition metal ions, such as Ni2+The distortion of the metal coordination polyhedrons can be minimized, and the coordination polyhedrons of the metal coordination polyhedrons keep a comfortable geometric shape, so that the metal coordination polyhedrons occupy the position of the transition metal layer 3a more stably and play a role in reducing the mixed arrangement of lithium and nickel cations; co-doping with fluoride anions, replacing part of O of the lattice with F-2To reduce O2Redox activity of-acting to stabilize the structure; the proportional relation between the mole ratio alpha and beta between the anions and the cations is defined to be used as charge compensation to balance electrovalence. The cation and fluorine anion double-doped modified ternary cathode material provided by the invention has good electrochemical performance.
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 will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, 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 SEM image of a Mo0.5%/F0.5% co-doped cathode material prepared in example 1 of the invention;
FIG. 2 is the XRD refined lithium-nickel mixed-arrangement data of the Mo0.5%/F0.5% co-doped anode material prepared in example 1 of the present invention;
FIG. 3 is an SEM image of Mo 1%/F1% co-doped cathode material prepared in example 2 of the invention;
fig. 4 is an SEM image of an undoped cathode material prepared in comparative example 1;
FIG. 5 shows XRD refined lithium-nickel rearrangement data of the undoped positive electrode material prepared in comparative example 1;
fig. 6 is a schematic diagram of electrochemical cycles of example 1, comparative example 2, and comparative example 3 of the present invention at a current density of 200mA/g at 1C.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides a cation and fluorine anion double-doped modified ternary positive electrode material with a chemical formula of LiNi1-x-y-αCoxMnyMαO2-βFβ，0≤x≤0.4，0≤y≤0.4，0.6≤1-x-y-alpha is less than or equal to 1, alpha is more than or equal to 0 and less than or equal to 0.05, beta is more than or equal to 0 and less than or equal to 6 alpha; wherein M is a dopant cation, and the outer shell has d0Electronic configuration, doping cation M is Ti4+，V5+，Zr4+，Nb5+，W6+Or Mo6 +(ii) a The molar ratio between the anions and cations is controlled by adjusting the proportional relationship between alpha and beta, and in the present invention, the ratio of alpha to beta is 1:0.5-6, such as 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, or other ratios within this range may be used.
The preparation method of the cation and fluorine anion double-doped modified ternary cathode material comprises the following steps:
step S1, the precursor of the ternary anode material is added with d0Adding an M cation salt with an electronic configuration and a fluoride into a dispersion medium, grinding and mixing uniformly;
specifically, the precursor contains d0Mixing the electronic configuration M cation salt and fluoride according to a molar ratio of 1:0.0025-0.05: 0.00125-0.3; the fluoride is ammonium fluoride or lithium fluoride; containing d0In the electronic configuration of M cation salt, the doping cation M is Ti4+，V5+，Zr4+，Nb5+，W6+Or Mo6+(ii) a Wherein the Mo source adopts ammonium heptamolybdate tetrahydrate or molybdenum trioxide; the W source adopts ammonium tungstate or tungsten trioxide; the Ti source is tetrabutyl titanate or titanium dioxide; the V source adopts ammonium vanadate or vanadium pentoxide; the Zr source adopts zirconium oxychloride or zirconium oxynitrate; the Nb source adopts niobium pentoxide or niobium oxalate;
the dispersion medium is ethanol, water or isopropanol, and correspondingly, the doped cation salt is preferably a cation salt which is easily soluble in the ethanol, the water or the isopropanol;
the mass ratio of the precursor to the dispersion medium is 5-10:1, such as 5:1, 6:1, 7:1, 8:1, 9:1 and 10:1, and the mixing time is 30min-2 h.
Step S2, adding a lithium source into the mixture obtained in the step S1, grinding uniformly and then drying;
specifically, the lithium source is selected from lithium hydroxide, lithium carbonate or lithium acetate, the adding amount of the lithium source is adjusted according to the amount of the precursor, and the lithium source meets the following conditions: the molar ratio of the precursor to the lithium source is 1:1-1.1, preferably 1: 1.05;
in the step, the grinding time is controlled to be 30min-6h, the drying time is controlled to be 30min-2h, and the drying temperature is controlled to be 60-130 ℃.
Step S3, sintering at high temperature in oxygen or air atmosphere, and cooling to obtain a modified ternary positive electrode material with double doping of cations and fluorine anions;
specifically, a two-stage sintering process is adopted, the temperature is firstly raised to 450-500 ℃, and sintering is carried out for 3-5h under the condition; then heating to 700-850 ℃, and sintering for 2-20h under the condition; in the temperature rising process, the temperature rising rate is controlled to be 3-5 ℃/min.
The cation and fluorine anion double-doped modified ternary cathode material provided by the invention is explained in detail by specific examples below.
Example 1
The precursor is a commercial hydroxide precursor, and the atomic ratio of Ni to Co to Mn is 0.8304 to 0.1099 to 0.0597.
The preparation method of the cation and fluorine anion double-doped modified ternary cathode material of the embodiment is as follows:
and mixing the precursor with a Mo source and an F source. Adding the precursor (NH) according to the molar ratio of TM (precursor) Mo to F as 1:0.005:0.0054)6Mo7O2·4H2O and NH4F, adding ethanol to dissolve and ball-mill for 0.5h, wherein the mass ratio of the precursor to the ethanol is 5: 1;
li 1:1.05 with Li as Li source LiOH. H2Continuing ball milling for 4h, and drying at 120 ℃ for 0.5 h;
and sintering the obtained mixed powder in a flowing oxygen atmosphere to obtain the Mo0.5%/F0.5% co-doped modified ternary material. The sintering process comprises the following steps: firstly sintering for 4h at 500 ℃, then sintering for 12h at 750 ℃, and controlling the temperature rise speed to be 3 ℃/min in the process.
Referring to fig. 1 and fig. 2 in combination, fig. 1 is an SEM image of the mo 0.5%/F0.5% co-doped cathode material prepared in example 1 of the present invention; FIG. 2 is the XRD refined lithium-nickel mixed-arrangement data of the Mo0.5%/F0.5% co-doped cathode material prepared in example 1 of the present invention. As can be seen from FIGS. 1 and 2, the positive electrode material codoped with Mo0.5%/F0.5% has a more stable structure, and the number of lithium-nickel mixed rows is less than 1%, which is 0.12%.
Weighing 0.4g of Mo0.5%/F0.5% codoped ternary material sample, adding 0.05g of conductive carbon black and 0.05g of PVDF, manually mixing and grinding in an agate mortar for 20min, adding a proper amount of NMP (N-methylpyrrolidone), and preparing into slurry with a certain viscosity. Coating the prepared slurry on 18 μm thick aluminum foil, drying at 120 deg.C under vacuum, making into 14mm electrode sheet with a puncher, and using Cellgard2400 as separator (diameter 19mm) and LiPF6(the solvent is EC/DMC/EMC, the volume ratio is 1:1:1) the electrolyte is used for assembling the 2025 button cell, the charging and discharging voltage range is 2.8-4.3V, the charging and discharging cycle is measured for 100 times under the current density of 1C-200 mA/g, and the capacity retention rate is 96.79%.
Example 2
The precursor is a commercial hydroxide precursor, and the atomic ratio of Ni to Co to Mn is 0.8304 to 0.1099 to 0.0597.
The preparation method of the cation and fluorine anion double-doped modified ternary cathode material of the embodiment is as follows:
the precursor is mixed with a Mo source and an F source. Adding a precursor and a Mo source (NH) according to a molar ratio of TM, Mo and F being 1:0.01:0.014)6Mo7O2·4H2O and NH4F, adding ethanol for dissolving, and performing ball milling for 0.5h, wherein the mass ratio of the precursor to the ethanol is 5: 1;
li 1:1.05 with Li as Li source LiOH. H2O, continuing ball milling for 4 hours, and drying at 120 ℃ for 0.5 hour;
and sintering the obtained mixed powder in a flowing oxygen atmosphere to obtain the Mo 1%/F1% co-doped modified ternary material. The sintering process comprises the following steps: firstly sintering for 4h at 500 ℃, then sintering for 12h at 750 ℃, and controlling the temperature rise speed to be 3 ℃/min in the process. An SEM image of the Mo 1%/F1% co-doped cathode material of the embodiment is shown in FIG. 3.
Example 3
The precursor is a commercial hydroxide precursor, and the atomic ratio of Ni to Co to Mn is 0.8304 to 0.1099 to 0.0597.
The preparation method of the cation and fluorine anion double-doped modified ternary cathode material of the embodiment is as follows:
the precursor is mixed with a source of Ti, F. Adding a precursor, tetrabutyl titanate and NH according to a molar ratio of TM, Ti and F being 1:0.01:0.0054F, adding ethanol for dissolving, and performing ball milling for 2 hours, wherein the mass ratio of the precursor to the ethanol is 10: 1;
li 1:1.05 with Li as Li source LiOH. H2O, continuing ball milling and mixing for 4 hours, and drying at 120 ℃ for 0.5 hour;
and sintering the obtained mixed powder in a flowing oxygen atmosphere to obtain the Ti 1%/F0.5% co-doped modified ternary material. The sintering process comprises the following steps: firstly sintering for 4h at 500 ℃, then sintering for 12h at 750 ℃, and controlling the temperature rise speed to be 3 ℃/min in the process.
Example 4
The precursor is a commercial hydroxide precursor, and the atomic ratio of Ni to Co to Mn is 0.8304 to 0.1099 to 0.0597.
The preparation method of the cation and fluorine anion double-doped modified ternary cathode material of the embodiment is as follows:
the precursor is mixed with a Nb source and an F source. Adding Nb source niobium pentoxide and fluorine source LiF according to the molar ratio of TM to Nb to F of 1:0.0025:0.0125, adding isopropanol to dissolve, and ball-milling for 4 hours; the mass ratio of the precursor to the isopropanol is 8: 1;
li 1:1.05 with Li as Li source LiOH. H2O, ball milling and mixing for 4 hours, and drying for 2 hours at 80 ℃;
the mixed powder is sintered in flowing oxygen atmosphere to obtain the ternary material codoped and modified by Nb0.25%/F1.25%. The sintering process comprises the following steps: firstly sintering for 4h at 500 ℃, then sintering for 12h at 750 ℃, and controlling the temperature rise speed to be 3 ℃/min in the process.
Example 5
The precursor is a commercial hydroxide precursor, and the atomic ratio of Ni to Co to Mn is 0.8304 to 0.1099 to 0.0597.
The preparation method of the cation and fluorine anion double-doped modified ternary cathode material of the embodiment is as follows:
the precursor is mixed with a W source and an F source. Adding W source ammonium tungstate and fluorine source ammonium fluoride according to a molar ratio of TM, W and F being 1:0.0025:0.015, adding water for dissolving, and performing ball milling for 2 hours; the mass ratio of the precursor to the water is 10: 1;
li 1:1.05 with Li as Li source LiOH. H2O, ball milling and mixing for 4 hours, and drying for 1 hour at 120 ℃;
and sintering the obtained mixed powder in a flowing oxygen atmosphere to obtain the W0.25%/F1.5% co-doped modified ternary material. The sintering process comprises the following steps: firstly sintering for 4h at 500 ℃, then sintering for 12h at 750 ℃, and controlling the temperature rise speed to be 3 ℃/min in the process.
Example 6
The precursor is a commercial hydroxide precursor, and the atomic ratio of Ni to Co to Mn is 0.8304 to 0.1099 to 0.0597.
The preparation method of the cation and fluorine anion double-doped modified ternary cathode material of the embodiment is as follows:
the precursor is mixed with a Mo source and an F source. Adding Mo source ammonium molybdate and fluorine source ammonium fluoride according to a molar ratio of TM to Mo to F of 1:0.0025:0.00125, adding water to dissolve, and performing ball milling for 2 hours; the mass ratio of the precursor to the water is 10: 1;
li 1:1.05 with Li as Li source LiOH. H2O, ball milling and mixing for 4 hours, and drying for 1 hour at 120 ℃;
and sintering the obtained mixed powder in a flowing oxygen atmosphere to obtain the Mo0.25%/F0.125% co-doped modified ternary material. The sintering process comprises the following steps: firstly sintering for 4h at 500 ℃, then sintering for 12h at 750 ℃, and controlling the temperature rise speed to be 3 ℃/min in the process.
Example 7
The precursor is a commercial hydroxide precursor, and the atomic ratio of Ni to Co to Mn is 0.8304 to 0.1099 to 0.0597.
The preparation method of the cation and fluorine anion double-doped modified ternary cathode material of the embodiment is as follows:
the precursor is mixed with a W source and an F source. Adding W source ammonium tungstate and fluorine source according to a molar ratio of TM, W and F being 1:0.005:0.03, adding water for dissolving, and performing ball milling for 2 hours; the mass ratio of the precursor to the water is 10: 1;
li 1:1.05 with Li as Li source LiOH. H2O，Ball milling and mixing for 4h, and drying at 120 ℃ for 1 h;
and sintering the obtained mixed powder in a flowing oxygen atmosphere to obtain the W0.5%/F3% co-doped modified ternary material. The sintering process comprises the following steps: firstly sintering for 4h at 500 ℃, then sintering for 12h at 750 ℃, and controlling the temperature rise speed to be 3 ℃/min in the process.
In addition to the above examples, the precursor contains d0The electron configuration M cation salt and fluoride may be mixed in a molar ratio of 1:0.05:0.3, or other mixing ratios within the range of 1:0.0025-0.05: 0.00125-0.3.
Comparative example 1
The precursor is a commercial hydroxide precursor, and the atomic ratio of Ni to Co to Mn is 0.8304 to 0.1099 to 0.0597.
The preparation process of the ternary cathode material of comparative example 1 is as follows: with reference to the procedure described in example 1, lithium (containing no dopant ions) was added only in the amount of 1:1.05 (TM: Li), mixed by grinding with alcohol and the solvent was evaporated, the lithium source being LiOH. H2O, and the sintering process to form the mixed powder was the same as in example 1.
Please refer to fig. 4 and 5 in combination, wherein fig. 4 is an SEM image of the undoped anode material prepared in comparative example 1; fig. 5 is XRD-refined lithium nickel rearrangement data of the undoped cathode material prepared in comparative example 1. As can be seen from fig. 4 and 5, the undoped positive electrode material has an unstable structure, and the number of lithium-nickel mixed rows reaches 2.78%.
Weighing 0.4g of undoped ternary material sample, adding 0.05g of conductive carbon black and 0.05g of PVDF, manually mixing and grinding in an agate mortar for 20min, adding a proper amount of NMP, and preparing into slurry with a certain viscosity. Coating the prepared slurry on 18 μm thick aluminum foil, drying at 120 deg.C under vacuum, making into 14mm electrode sheet with a puncher, and using Cellgard2400 as separator (diameter 19mm) and LiPF6(the solvent is EC/DMC/EMC, the volume ratio is 1:1:1) the electrolyte is used for assembling the 2025 button cell, the charging and discharging voltage range is 2.8-4.3V, the charging and discharging cycle is measured for 100 times under the current density of 1C-200 mA/g, and the capacity retention rate is 88.4%.
Comparative example 2
The precursor is a commercial hydroxide precursor, and the atomic ratio of Ni to Co to Mn is 0.8304 to 0.1099 to 0.0597.
The preparation process of the ternary cathode material of comparative example 2 is as follows: mixing the precursor with Mo source, adding Mo source (NH) according to molar ratio of TM: Mo to 1:0.0054)6Mo7O2·4H2O, adding ethanol, dissolving, mixing and grinding for 0.5h, wherein the mass ratio of the precursor to the ethanol is 5: 1;
the subsequent addition of a lithium source and sintering process were the same as in example 1, resulting in a ternary material doped with 0.5% mo.
Weighing 0.4g of Mo0.5% doped ternary material sample, adding 0.05g of conductive carbon black and 0.05g of PVDF, manually mixing and grinding in an agate mortar for 20min, adding a proper amount of NMP, and preparing into slurry with a certain viscosity. Coating the prepared slurry on 18 μm thick aluminum foil, drying at 120 deg.C under vacuum, making into 14mm electrode sheet with a puncher, and using Cellgard2400 as separator (diameter 19mm) and LiPF6(the solvent is EC/DMC/EMC, the volume ratio is 1:1:1) the electrolyte is used as the electrolyte to assemble the 2025 button cell, the charging and discharging voltage range is 2.8-4.3V, the charging and discharging cycle is measured for 100 times under the current density of 1C-200 mA/g, and the capacity retention rate is 88.82%.
Comparative example 3
The precursor is a commercial hydroxide precursor, and the atomic ratio of Ni to Co to Mn is 0.8304 to 0.1099 to 0.0597.
The preparation process of the ternary cathode material of the embodiment is as follows: mixing the precursor with F source, adding NH at a molar ratio of TM to F of 1 to 0.0054F, adding ethanol to dissolve, mix and grind for 0.5 h;
grinding and mixing TM Li 1:1.05 with alcohol and evaporating solvent, the Li source is LiOH. H2O；
And sintering the mixed powder at high temperature to obtain the F0.5% doped ternary material. The sintering process was the same as in example 1.
Weighing 0.4g of ternary material sample doped with 0.5% of F, adding 0.05g of conductive carbon black and 0.05g of PVDF, manually mixing and grinding in an agate mortar for 20min, adding a proper amount of NMP, and preparing into slurry with a certain viscosity. Mixing the prepared slurryCoating on 18 μm aluminum foil, drying at 120 deg.C under vacuum, making into 14mm electrode sheet with Cellgard2400 as separator (diameter 19mm), and LiPF6(the solvent is EC/DMC/EMC, the volume ratio is 1:1:1) the electrolyte is used for assembling the 2025 button cell, the charging and discharging voltage range is 2.8-4.3V, the charging and discharging cycle is measured for 100 times under the current density of 1C-200 mA/g, and the capacity retention rate is 82.54%.
Fig. 6 is a schematic diagram of electrochemical cycles of example 1, comparative example 2, and comparative example 3 according to the present invention at a current density of 200mA/g at 1C. As can be seen from FIG. 6 and the application examples of example 1, comparative example 2 and comparative example 3, d is used0In an electrochemical cycle test, the capacity retention rate after 100 cycles is more than 96%, and the capacity retention rate after 100 cycles of the undoped positive electrode material prepared under the same condition is 89%. Therefore, the ternary cathode material provided by the invention has better electrochemical performance.
Meanwhile, d of the present invention0The electron-configuration cation and F anion co-doped ternary cathode material can effectively relieve the cracking degree of secondary particles and the dissolution of transition metal ions after 200 cycles of 1C circulation, so that the ternary cathode material has lasting structural stability and circulation stability, and the electrochemical performance of the cathode material is improved.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (10)
1. A cation and fluorine anion double-doped modified ternary positive electrode material is characterized in that the chemical formula is LiNi1-x-y-αCoxMnyMαO2-βFβX is more than or equal to 0 and less than or equal to 0.4, y is more than or equal to 0 and less than or equal to 0.4, 1-x-y-alpha is more than or equal to 0.6 and less than or equal to 1, alpha is more than or equal to 0 and less than or equal to 0.05, beta is more than or equal to 0 and less than or equal to 6 alpha; wherein M is a dopant cation, the shell thereofLayer having d0Electronic configuration.
2. The cation and fluorine anion double-doped modified ternary cathode material as claimed in claim 1, wherein the doped cation M is Ti4+，V5+，Zr4+，Nb5+，W6+Or Mo6+。
3. The ionic and fluorine anion double doped modified ternary cathode material of claim 1, wherein the ratio of α to β is 1: 0.5-6.
4. The preparation method of the cation and fluorine anion double-doped modified ternary cathode material of claim 1, characterized by comprising the following steps:
step S1, the precursor of the ternary anode material is added with d0Adding an M cation salt with an electronic configuration and a fluoride into a dispersion medium, grinding and mixing uniformly;
step S2, adding a lithium source into the mixture obtained in the step S1, grinding uniformly and then drying;
and step S3, sintering at high temperature in the atmosphere of oxygen or air, and cooling to obtain the modified ternary positive electrode material with double doping of cations and fluorine anions.
5. The method for preparing the cation and fluorine anion double-doped modified ternary cathode material according to claim 4, wherein the precursor comprises d0Mixing the electronic configuration M cation salt and fluoride according to a molar ratio of 1:0.0025-0.05: 0.00125-0.3; the molar ratio of the precursor to the lithium source is 1: 1-1.1.
6. The method for preparing the cation and fluorine anion double-doped modified ternary cathode material according to claim 4, wherein the modified ternary cathode material contains d0In the electronic configuration of M cation salt, the doping cation M is Ti4+，V5+，Zr4+，Nb5+，W6+Or Mo6+。
7. The preparation method of the cation and fluoroanion double-doped modified ternary cathode material according to claim 6, wherein the Mo source is ammonium heptamolybdate tetrahydrate or molybdenum trioxide; the W source adopts ammonium tungstate or tungsten trioxide; the Ti source is tetrabutyl titanate or titanium dioxide; the V source adopts ammonium vanadate or vanadium pentoxide; the Zr source adopts zirconium oxychloride or zirconium oxynitrate; the Nb source adopts niobium pentoxide or niobium oxalate.
8. The method for preparing the cation and fluorine anion double-doped modified ternary cathode material according to claim 4, wherein in the step S1, the fluoride is ammonium fluoride or lithium fluoride; the dispersion medium is ethanol, water or isopropanol, the mass ratio of the precursor to the dispersion medium is 5-10:1, and the mixing time is 0.5-2 h.
9. The method for preparing the cation and fluorine anion double-doped modified ternary cathode material according to claim 4, wherein in the step S2, the grinding time is 0.5-6h, the drying time is 0.5-2h, and the drying temperature is 60-130 ℃.
10. The method for preparing the cation and fluorine anion double-doped modified ternary cathode material according to claim 4, wherein in the step S3, the high-temperature sintering process comprises: heating to 450-500 ℃ for sintering for 3-5h, and then heating to 700-850 ℃ for sintering for 2-20 h; the heating rate is 3-5 ℃/min.
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| CN114031120A (en) * | 2021-11-09 | 2022-02-11 | 蜂巢能源科技有限公司 | Iron-manganese-based positive electrode material, preparation method thereof and lithium ion battery |
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| CN114864908A (en) * | 2022-05-31 | 2022-08-05 | 蜂巢能源科技股份有限公司 | Lithium-rich cathode material and preparation method and application thereof |
| CN114864908B (en) * | 2022-05-31 | 2024-04-05 | 蜂巢能源科技股份有限公司 | Lithium-rich positive electrode material and preparation method and application thereof |
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