CN114122380A - Preparation method of zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary positive electrode material and prepared positive electrode material - Google Patents
Preparation method of zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary positive electrode material and prepared positive electrode material Download PDFInfo
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 title claims abstract description 45
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010406 cathode material Substances 0.000 claims abstract description 50
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 150000000703 Cerium Chemical class 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 9
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000463 material Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical group 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 1
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary positive electrode material, relating to the technical field of lithium ion positive electrode materials and comprising the following steps of: (1) after ball milling and mixing the nickel-cobalt-manganese hydroxide precursor, a lithium source and a zirconium source, sintering to obtain a zirconium-doped nickel-cobalt-manganese ternary positive electrode material; (2) and (2) mixing the cerium salt solution with the nickel-cobalt-manganese ternary cathode material doped with zirconium in the step (1), stirring, adding an ammonium fluoride solution, reacting, drying and calcining to obtain the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material. The invention has the beneficial effects that: the ternary cathode material prepared by the invention has the advantages of reduced surface residual alkali, high discharge specific capacity and cycle performance and high capacity retention rate.
Description
Technical Field
The invention relates to the technical field of lithium ion cathode materials, in particular to a preparation method of a zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material and a prepared cathode material.
Background
Lithium Ion Batteries (LIBs) have the advantages of high voltage, high specific capacity, long cycle life, small self-discharge, small volume, less environmental pollution, etc., are considered as the most promising chemical power sources, and are always the focus and key points of research. Lithium ion batteries are widely used in portable electronic products such as mobile phones, and have a wide application prospect in the field of electric vehicles. In the process of rapid development of lithium ion batteries, the anode material is a bottleneck that restricts large-scale popularization and application of the lithium ion batteries and even occupies the market, so that the most critical point in the process of commercialization of the lithium ion batteries is to prepare the anode material with excellent cost performance. Currently used anode materials include lithium cobaltate, lithium manganate, ternary materials, lithium iron phosphate, nickel cobalt manganese (NCA), Nickel Cobalt Manganese (NCM), and the like.
The nickel-cobalt-manganese ternary positive electrode material has the advantages of relatively low cost, good cycle performance, large discharge capacity and good structural stability, but also has the defects of relatively low platform and low first charge-discharge efficiency. At present, the electrochemical performance of the nickel-cobalt-manganese ternary cathode material is improved mainly by doping and coating.
Firstly, the coating modification can prevent the contact of active substances and electrolyte, inhibit the occurrence of side reactions and improve the cycle performance of the anode material; secondly, the fluoride has a stable effect on HF, so that the corrosion of HF on the electrode material can be effectively prevented, and the rate capability of the material can be improved. For example, patent publication No. CN 103367740A discloses a method for preparing lithium nickel cobalt manganese oxide positive electrode material by using CaF2And the capacity retention rate of the positive electrode material is improved by coating. The scheme can reduce the reaction of the electrolyte and the anode material to a certain extent. However, the coating layer is still not uniform, and a small amount of side reaction still occurs, thereby resulting in poor material capacity and cycle performance.
Disclosure of Invention
The invention aims to solve the technical problem that the fluoride-coated cathode material in the prior art still has poor capacity and cycle performance.
The invention solves the technical problems through the following technical means:
the preparation method of the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material comprises the following steps of:
(1) after ball milling and mixing the nickel-cobalt-manganese hydroxide precursor, a lithium source and a zirconium source, sintering to obtain a zirconium-doped nickel-cobalt-manganese ternary positive electrode material;
(2) and (2) mixing the cerium salt solution with the nickel-cobalt-manganese ternary cathode material doped with zirconium in the step (1), stirring, adding an ammonium fluoride solution, reacting, drying and calcining to obtain the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material.
Has the advantages that: according to the zirconium-doped nickel-cobalt-manganese ternary cathode material, zirconium is doped into the nickel-cobalt-manganese ternary cathode material, so that the intrinsic conductivity of the nickel-cobalt-manganese ternary cathode material can be improved, the compatibility between the surface of the material and an electrolyte is improved, the resistance borne by lithium ions during migration is reduced, the electrochemical performance of the nickel-cobalt-manganese ternary cathode material is improved, and the nickel-cobalt-manganese ternary cathode material has high discharge specific capacity and cycle performance.
According to the invention, the nickel-cobalt-manganese ternary positive electrode material is coated with cerium fluoride at high temperature, the surface of the nickel-cobalt-manganese ternary positive electrode material is coated with cerium fluoride, the cerium element is lanthanide, the cerium fluoride has good electrochemical inertia at high temperature, the nickel-cobalt-manganese ternary positive electrode material has good stability in an acidic environment, and the ionic conductivity is very high at room temperature. And the cerium fluoride has an effect on the stability of HF, inhibits the side reaction between the anode material and the electrolyte, reduces the residual alkali on the surface of the material, effectively improves the electrochemical performance of the material, and has better performance after coating.
Compared with the prior art, the invention dopes zirconium, the particle size of the doped material is reduced, and the Li is shortened+Diffusion path of (2) in favor of Li+The de-intercalation in the layered structure improves the de-intercalation rate of lithium ions and improves the cycling stability of the battery.
Preferably, the lithium source is one or more of lithium dihydrogen phosphate, lithium carbonate, strong lithium oxide, lithium oxalate, lithium acetate and lithium nitrate.
Preferably, the zirconium source is one or more of zirconia, zirconium nitrate and zirconium chloride.
Preferably, the sintering conditions in the step (1) are as follows: heating to 450-500 ℃ in a tubular furnace filled with oxygen at the heating rate of 2-5 ℃/min, preserving heat for 3-8h, heating to 780-820 ℃ at the heating rate of 2-5 ℃/min, and preserving heat for 10-18 h.
Preferably, the general formula of the nickel-cobalt-manganese ternary cathode material is LiNixCoyMn1-x-yO2Wherein 0.8<x≤1、0<y≤0.1。
Preferably, the mass ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese hydroxide precursor is 8:1: 1.
the nickel-cobalt-manganese ternary positive electrode material coated in the prior art is LiNi1/3Co1/3Mn1/3O2The mass ratio of nickel, cobalt and manganese is 1:1:1, the mass ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary positive electrode material coated by the invention is 8:1:1, the higher the nickel content is, the more Ni is2+Due to the presence of Li+The dislocation phenomenon occurs to deteriorate the cycle performance of the material, which shows that the cycle of the nickel-cobalt-manganese ternary cathode material disclosed in the patent publication No. CN 103367740A is superior to that of the nickel-cobalt-manganese ternary cathode material disclosed by the invention.
Preferably, the solvent of the cerium salt solution is absolute ethanol.
Preferably, the cerium salt is one or more of cerium nitrate, cerium chloride and cerium acetate.
Preferably, the ratio of the amount of material of the cerium nitrate solution to the ammonium fluoride solution is 1:3, resulting in cerium fluoride.
Preferably, in the step (2), the drying condition is 80 ℃ for drying overnight, and the calcining condition is 450 ℃ for heat preservation and calcination for 2 h.
The invention also provides the ternary cathode material prepared by the method.
Has the advantages that: the ternary cathode material prepared by the invention has the advantages of reduced surface residual alkali, high discharge specific capacity and cycle performance and high capacity retention rate.
The invention has the advantages that: according to the zirconium-doped nickel-cobalt-manganese ternary cathode material, zirconium is doped into the nickel-cobalt-manganese ternary cathode material, so that the intrinsic conductivity of the nickel-cobalt-manganese ternary cathode material can be improved, the compatibility between the surface of the material and an electrolyte is improved, the resistance borne by lithium ions during migration is reduced, the electrochemical performance of the nickel-cobalt-manganese ternary cathode material is improved, and the nickel-cobalt-manganese ternary cathode material has high discharge specific capacity and cycle performance.
According to the invention, the nickel-cobalt-manganese ternary positive electrode material is coated with cerium fluoride at high temperature, the surface of the nickel-cobalt-manganese ternary positive electrode material is coated with cerium fluoride, the cerium element is lanthanide, the cerium fluoride has good electrochemical inertia at high temperature, the nickel-cobalt-manganese ternary positive electrode material has good stability in an acidic environment, and the ionic conductivity is very high at room temperature. And the cerium fluoride has an effect on the stability of HF, inhibits the side reaction between the anode material and the electrolyte, reduces the residual alkali on the surface of the material, effectively improves the electrochemical performance of the material, and has better performance after coating.
Compared with the prior art, the invention dopes zirconium, the particle size of the doped material is reduced, and the Li is shortened+Diffusion path of (2) in favor of Li+The de-intercalation in the layered structure improves the de-intercalation rate of lithium ions and improves the cycling stability of the battery.
The ternary cathode material prepared by the invention has the advantages of reduced surface residual alkali, high discharge specific capacity and cycle performance and high capacity retention rate.
Drawings
FIG. 1 is an SEM image of a nickel-cobalt-manganese ternary cathode material prepared in comparative example 1 of the present invention, with magnification of 20000 times;
fig. 2 is an SEM image of the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary positive electrode material prepared in example 2 of the present invention, with a magnification of 20000 times;
fig. 3 is an XRD chart of the nickel-cobalt-manganese ternary positive electrode materials prepared in example 2, comparative example 1 and comparative example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The preparation method of the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material specifically comprises the following steps of:
(1) ball milling 100g of nickel cobalt manganese hydroxide precursor powder, 47.94g of lithium hydroxide powder (the lithiation proportion is 1.05) and 0.2026g of zirconia for 2 hours at the rotating speed of a ball mill of 300r/min, heating to 480 ℃ at the heating rate of 2 ℃/min in an oxygen-filled tube furnace, preserving heat for 5 hours (first-step sintering), and heating to 800 ℃ at the heating rate of 2 ℃/min, preserving heat for 15 hours (second-step sintering); and cooling along with the furnace, grinding and sieving to obtain nickel-cobalt-manganese-lithium oxide powder, namely the zirconium-doped nickel-cobalt-manganese ternary cathode material. In this example, the ratio of nickel in the nickel-cobalt-manganese hydroxide precursor: cobalt: the mass ratio of manganese is 8:1: 1.
(2) weighing cerium nitrate, putting the cerium nitrate into appropriate absolute ethyl alcohol, performing ultrasonic treatment to obtain a cerium nitrate solution, adding the nickel-cobalt-manganese-lithium oxide powder obtained in the step 1, stirring uniformly, adding an ammonium fluoride aqueous solution, mixing the cerium nitrate solution and the ammonium fluoride aqueous solution at a mass ratio of 1:3 for 4 hours at 60 ℃, performing suction filtration and washing with ethanol, finally obtaining cerium fluoride with a total mass of 0.5% of the weight of the nickel-cobalt-manganese-lithium oxide powder, drying at 80 ℃ overnight, and calcining the obtained solid powder at 450 ℃ in an air atmosphere for 2 hours to obtain the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material 1.
Electrochemical performance test
And (3) positive electrode: taking a zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary positive electrode material 1 as an active substance, SP as a conductive agent, PVDF as a binder, N-methyl-2-pyrrolidone (NMP) as a dispersing agent, and mixing the components in parts by weight: SP: PVDF 80: 10: 10, and coating the aluminum foil to prepare the electrode plate. The lithium metal sheet is used as a negative electrode, the polypropylene microporous membrane is used as a diaphragm, and 1mol/L LiPF6For the electrolyte, a CR2032 type cell was produced in a glove box filled with argon gas. And (3) performing a 0.2C constant-current charge and discharge test at normal temperature, wherein the charge and discharge cutoff voltage is 2.8V-4.3V. The measurement results are shown in table 1.
Example 2
This embodiment is different from embodiment 1 in that: in the step (2), the total mass of the cerium fluoride accounts for 1% of the weight of the nickel-cobalt-manganese-lithium oxide powder, so as to obtain the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material 2. A battery positive electrode was fabricated and tested in the same procedure as in example 1, and the electrochemical properties of the product are shown in table 1.
Example 3
This embodiment is different from embodiment 1 in that: in the step (2), the total mass of the cerium fluoride accounts for 2% of the weight of the nickel-cobalt-manganese-lithium oxide powder, so that the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material 3 is obtained. A battery positive electrode was fabricated and tested in the same procedure as in example 1, and the electrochemical properties of the product are shown in table 1.
Comparative example 1
Unmodified nickel cobalt manganese materials
Ball-milling 100g of nickel-cobalt-manganese hydroxide precursor powder and 47.94g of lithium hydroxide powder (the lithiation ratio is 1.05) for 2h at the rotating speed of a ball mill of 300r/min, heating to 480 ℃ at the heating rate of 2 ℃/min in an oxygen-filled tube furnace, preserving heat for 5h, and heating to 800 ℃ at the heating rate of 2 ℃/min, preserving heat for 15 h; and (4) cooling along with the furnace, grinding and sieving to obtain the unmodified nickel-cobalt-manganese ternary cathode material. Nickel in the nickel cobalt manganese hydroxide precursor in this comparative example: cobalt: the mass ratio of manganese is 8:1: 1. a battery positive electrode was fabricated and tested in the same procedure as in example 1, and the electrochemical properties of the product are shown in table 1.
Comparative example 2
Zirconium doped nickel cobalt manganese materials
Ball milling 100g of nickel cobalt manganese hydroxide precursor powder, 47.94g of lithium hydroxide powder (the lithiation ratio is 1.05) and 0.2026g of zirconia for 2 hours at the rotating speed of a ball mill of 300r/min, heating to 480 ℃ at the heating rate of 2 ℃/min in an oxygen-filled tube furnace, preserving heat for 5 hours, and heating to 800 ℃ at the heating rate of 2 ℃/min, preserving heat for 15 hours; and (4) cooling along with the furnace, grinding and sieving to obtain the zirconium-doped nickel-cobalt-manganese ternary cathode material. Nickel in the nickel cobalt manganese hydroxide precursor in this comparative example: cobalt: the mass ratio of manganese is 8:1: 1. a battery positive electrode was fabricated and tested in the same procedure as in example 1, and the electrochemical properties of the product are shown in table 1.
Comparative example 3
The present comparative example differs from comparative example 1 in that: the sintering temperature in the first step is raised to 450 ℃ at the heating rate of 2 ℃/min and is kept for 5 h. A battery positive electrode was fabricated and tested in the same procedure as in example 1, and the electrochemical properties of the product are shown in table 1.
Comparative example 4
This comparative example is the same as comparative example 1 except that: the sintering temperature in the first step is raised to 500 ℃ at the heating rate of 2 ℃/min and is kept for 5 h. A battery positive electrode was fabricated and tested in the same procedure as in example 1, and the electrochemical properties of the product are shown in table 1.
Comparative example 5
This comparative example is the same as comparative example 1 except that: the sintering temperature in the second step is increased to 780 ℃ at the heating rate of 2 ℃/min and is kept for 15 h. A battery positive electrode was fabricated and tested in the same procedure as in example 1, and the electrochemical properties of the product are shown in table 1.
Comparative example 6
This comparative example is the same as comparative example 1 except that: the sintering temperature in the second step is increased to 820 ℃ at the heating rate of 2 ℃/min and is kept for 15 h. A battery positive electrode was fabricated and tested in the same procedure as in example 1, and the electrochemical properties of the product are shown in table 1.
Table 1 shows the results of measuring the electrochemical properties of the ternary positive electrode materials obtained in each of examples and comparative examples
TABLE 2 residual alkali test results
As can be seen from fig. 1-2, the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary positive electrode material prepared by the method is spherical, the surface of the material coated with cerium fluoride is rough, and cerium fluoride small particles are present.
As can be seen from fig. 3, the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary positive electrode material prepared by the method has an obvious layered structure and no hetero peak, and probably because the cerium fluoride coating amount is small, no diffraction peak is observed.
As can be seen from table 1, the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary positive electrode material prepared in (example 1-3) has an advantage in first discharge specific capacity and a good capacity retention rate after 50 cycles, compared with the unmodified nickel-cobalt-manganese ternary positive electrode material in (comparative example 1) and the zirconium-doped nickel-cobalt-manganese ternary positive electrode material in (comparative example 2).
In the embodiment 2 of the invention, under the coating sample magnification of 1C, the cycle retention rate of 50 circles is 95.2%; the invention has better effect as shown by the cycle retention rate of 94.24% at 50 circles under the condition that the multiplying power of a patent coating sample with the publication number of CN 103367740A is 0.5C.
When the coating amount of the cerium fluoride is 1%. The electrochemical performance of the zirconium-doped nickel-cobalt-manganese ternary cathode material is obviously improved, so that the embodiment 2 is the best embodiment, and the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material provided by the invention has better electrochemical performance.
As can be seen from the preparation of the unmodified nickel-cobalt-manganese ternary cathode material (comparative example 1-comparative example 6), the optimal sintering temperature is that the sintering temperature in the first step is heated to 480 ℃ at the heating rate of 2 ℃/min and is kept for 5h, and the sintering temperature in the second step is heated to 800 ℃ at the heating rate of 2 ℃/min and is kept for 15 h.
As can be seen from the test results in table 2, the residual alkali amount is large in comparative example 1 due to no coating due to doping, compared to example 2; while comparative example 2 was uncoated after doping with zirconium, the amount of residual alkali was reduced compared to comparative example 1 but still inferior to example 2. The coating layer of cerium fluoride inhibits the corrosion of HF generated by electrolyte in the circulation process to the ternary material, thereby reducing the decomposition of active materials, reducing the impedance of the battery and improving the residual alkali and electrochemical properties of the surface of the material.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material is characterized by comprising the following steps of: the method comprises the following steps:
(1) after ball milling and mixing the nickel-cobalt-manganese hydroxide precursor, a lithium source and a zirconium source, sintering to obtain a zirconium-doped nickel-cobalt-manganese ternary positive electrode material;
(2) and (2) mixing the cerium salt solution with the nickel-cobalt-manganese ternary cathode material doped with zirconium in the step (1), stirring, adding an ammonium fluoride solution, reacting, drying and calcining to obtain the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material.
2. The method for preparing the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: the lithium source is one or more of lithium dihydrogen phosphate, lithium carbonate, strong lithium oxide, lithium oxalate, lithium acetate and lithium nitrate.
3. The method for preparing the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: the zirconium source is one or more of zirconium oxide, zirconium nitrate and zirconium chloride.
4. The method for preparing the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: the sintering conditions in the step (1) are as follows: heating to 450-500 ℃ in a tubular furnace filled with oxygen at the heating rate of 2-5 ℃/min, preserving heat for 3-8h, heating to 780-820 ℃ at the heating rate of 2-5 ℃/min, and preserving heat for 10-18 h.
5. The method for preparing the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: the mass ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese hydroxide precursor is 8:1: 1.
6. the method for preparing the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: the solvent of the cerium salt solution is absolute ethyl alcohol.
7. The method for preparing the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: the cerium salt is one or more of cerium nitrate, cerium chloride and cerium acetate.
8. The method for preparing the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: the mass ratio of the cerium salt solution to the ammonium fluoride solution was 1: 3.
9. The method for preparing the zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material according to claim 1, wherein the method comprises the following steps: in the step (2), the drying condition is drying at 80 ℃ overnight, and the calcining condition is heat preservation calcining at 450 ℃ for 2 h.
10. The zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary cathode material prepared by the preparation method of any one of claims 1 to 9.
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