CN112194196A - Composite coating agent for ultra-high nickel single crystal ternary positive electrode material and preparation method and application thereof - Google Patents
Composite coating agent for ultra-high nickel single crystal ternary positive electrode material and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 48
- 239000013078 crystal Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 131
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 238000001354 calcination Methods 0.000 claims abstract description 33
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- -1 ammonium salt compound Chemical class 0.000 claims abstract description 15
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000010406 cathode material Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 238000007873 sieving Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010902 jet-milling Methods 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 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
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910020027 (NH4)3AlF6 Inorganic materials 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 31
- 239000003513 alkali Substances 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 239000007788 liquid Substances 0.000 description 18
- 229910052742 iron Inorganic materials 0.000 description 14
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 7
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 7
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000011572 manganese Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 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 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910011011 Ti(OH)4 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a composite coating agent for an ultrahigh nickel single crystal ternary positive electrode material, and a preparation method and application thereof, and belongs to the technical field of lithium ion power batteries for new energy automobiles. A composite coating agent for an ultrahigh nickel single crystal ternary positive electrode material comprises: at least one of metal and/or nonmetal oxide, ammonium salt compound and solvent is prepared by at least one of ball milling, airflow crushing, calcining, wet mixing and spray drying. The prepared composite coating agent forms a uniform coating layer on the surface of a single crystal material through coating and calcining, and can reduce the residual alkali level on the surface and improve the cycle performance and safety performance of the material.
Description
Technical Field
The invention belongs to the technical field of lithium ion power batteries for new energy automobiles, and particularly relates to a composite coating agent for an ultrahigh nickel single crystal ternary positive electrode material, and a preparation method and application thereof.
Background
Because the single crystal ternary positive electrode material has better cycle performance and thermal stability than the same type of polycrystalline ternary material, the existing ternary secondary ball is gradually replaced, 523/622 series single crystals are mainly used in the mainstream commercial large-scale mass production in the current market, but the nickel content is low, the endurance mileage of the electric automobile is short, and the cobalt content is high, so that the processing cost is high, and the high-nickel and low-cobalt state is the development trend of the future ternary material.
At present, most of high-nickel ternary positive electrode materials in the market are polycrystalline secondary spheres formed by agglomeration of nanoscale primary particles, but as the content of nickel is higher, the activity of the ternary materials is higher, the cycle performance and the thermal stability are greatly reduced, and as the content of nickel is increased, the residual alkali level on the surfaces of the materials is also higher, so that the gas generation of the battery is serious, and the safety performance of the battery is seriously influenced and limited.
Patent 201910952126.1 discloses a lithium phosphate coated lithium ion battery high-nickel single crystal ternary positive electrode material and a preparation method thereof, the specific capacity prepared by the method is higher, and the cycle and rate performance are both better, but the patent adopts sodium salt and the like, and the content of impurity elements such as sodium in the obtained product material is higher through the stirring and drying process, and the overall performance of the material can be influenced; patent 201911180410.8 discloses a method for preparing a high nickel single crystal positive electrode material, a positive electrode material and a lithium ion battery, wherein the method comprises the steps of precursor crushing treatment, dry coating, pre-oxidation, lithium mixing primary calcination, wet treatment and secondary calcination, and although the obtained high nickel single crystal material has uniform particle size distribution and good crystallinity, the process is complicated, the cost is high, and the method is not suitable for large-scale industrialization.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides a composite coating agent for an ultra-high nickel single crystal ternary cathode material, and a preparation method and application thereof.
The solution of the invention for solving the technical problem is as follows:
a composite coating agent for an ultrahigh nickel single crystal ternary positive electrode material comprises the following raw materials: at least one of metal and/or nonmetal oxide, ammonium salt compound; the metal oxide is MgO and Al2O3、La2O3、ZrO2、Nb2O5At least one of; the non-metal oxide is SiO2(ii) a The ammonium salt compound is NH4F、(NH4)3AlF6、NH4H2PO4、(NH4)2WO4At least one of (1).
Further, the metal and/or nonmetal oxide is nano-sized particles, D50Is 20-200 nm.
Further, the raw materials are processed by at least one of ball milling, airflow crushing, calcining, wet mixing and spray drying to obtain the composite coating agent.
Further, the ball-milling ball-material ratio is 1:1-5:1, and the ball-milling time is 4-12 h; wherein the ball is at least one of polyurethane ball and agate ball.
Further, the jet milling parameters are as follows: the crushing pressure is 0.8MPa-1.0MPa, the feeding frequency is 3-15Hz, the grading frequency is 80-180Hz, and the induced air frequency is 20-40 Hz.
Further, the equipment used for calcination is an atmosphere furnace, the calcination atmosphere is air or oxygen, the calcination temperature is 400-700 ℃, and the calcination time is 4-15 h.
Further, the temperature of the spray drying is 200-250 ℃.
The composite coating agent for the ultra-high nickel single crystal ternary cathode material is prepared by the preparation method.
The application of the composite coating agent for the ultra-high nickel single crystal ternary cathode material is used for preparing the ultra-high nickel single crystal ternary cathode material, and specifically comprises the following steps:
s1, adding the primary calcined and crushed ultrahigh nickel ternary cathode material and water into a reaction kettle according to a water-material ratio of 0.5:1-5:1, and mixing to obtain a reaction material; controlling the temperature of the reaction kettle, adding a reagent for reaction, and drying after the reaction is finished to obtain a mixed material;
s2, mixing the mixed material and the composite coating agent in the S1, placing the mixture in an atmosphere furnace for aerobic calcination at the temperature of 700-810 ℃ for 6-10h, and then crushing, sieving and demagnetizing to obtain the ultra-high nickel ternary single crystal anode material.
Specifically, the reagent accounts for 4% -8% of the mass of the reaction material; the reagent is a commodity wet coating solution sold by Tianjin Runsheng constant technology development Limited.
Specifically, the adding amount of the composite coating agent is 0.12-0.35% of the mass of the mixed material.
Specifically, the preparation of the once-calcined and pulverized ultra-high nickel single crystal ternary cathode material comprises the following steps: mixing the ultrahigh nickel ternary precursor with lithium hydroxide according to the molar ratio of lithium to metal of 1.01-1.10:1, adding a dopant, and calcining in an oxygen atmosphere at the temperature of 750-820 ℃ for 8-15h to obtain the primary calcined and pulverized ultrahigh nickel single crystal ternary cathode material.
Specifically, the dopant is Al (OH)3、Mg(OH)2、Ti(OH)4、Sr(OH)2、Zr(OH)4、SiO2、Y2O3、Nb2O5、WO3、ZrO2、MoO3、SrO、SnO2The addition amount of the dopant is 0.3-1% of the mass of the ultra-high nickel ternary precursor.
Specifically, the preparation method of the composite coating agent for the ultrahigh nickel single crystal ternary material can be used for coating modification of the ultrahigh nickel single crystal ternary material, is not limited to the ultrahigh nickel single crystal ternary material, can also be used for polycrystalline secondary sphere ternary materials, can be doped with other metal or nonmetal elements except nickel, cobalt, manganese and aluminum according to needs, and can be used for randomly adjusting the proportion of various elements.
Specifically, the atmosphere of the aerobic calcination is air or oxygen.
The invention has the beneficial effects that:
(1) compared with the traditional coating process, the invention adopts the composite coating agent, and compared with the original process, the composite coating agent is singly coated, and is compounded by adopting at least one metal or nonmetal or ammonium salt compound, so that the composite coating agent can be coated on the surface of the single crystal anode material to play a synergistic effect of at least more than two elements, and the cycle performance of the material can be effectively improved.
(2) Compared with the traditional coating process, the invention adopts the composite coating agent, and the adopted composite coating can simultaneously lead the residual alkali (CO 3) on the surface of the material to be in the process of providing the coating effect2-、OH-) The reaction is carried out for removal, so that free lithium on the surface is combined with other coated elements to form a new compound, the residual alkali on the surface of the material is greatly reduced, and meanwhile, the formed new lithium salt compound can effectively isolate the contact between electrolyte and the interior of the material, thereby improving the cycle performance and the thermal stability of the material.
The traditional coating process generally refers to mechanical mixing of a ternary positive electrode material with a single nano or non-nano compound coating agent.
Drawings
FIG. 1 is a high power scanning electron microscope image of a lithium nickel cobalt manganese oxide positive electrode material according to a first embodiment of the present invention;
FIG. 2 is a second high power scanning electron microscope image of the lithium nickel cobalt manganese oxide positive electrode material according to the first embodiment of the present invention;
Detailed Description
The conception, specific structure, and technical effects of the present application will be described clearly and completely with reference to the following embodiments, so that the purpose, features, and effects of the present application can be fully understood. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
Comparative example 1:
a preparation method of an ultrahigh nickel single crystal ternary cathode material comprises the following steps:
s1, adding Ni0.90Co0.05Mn0.05(OH)2Mixing the ternary precursor with battery-grade lithium hydroxide monohydrate in a molar ratio of lithium to metal of 1.08:1, and adding ZrO with 0.3% of the mass of the cobalt-nickel-containing ternary precursor2Then, calcining the mixture for 15 hours at the temperature of 790 ℃ in an oxygen atmosphere to obtain a primary calcined material; wherein the ternary precursor-containing medium particle diameter D503.20 μm, a specific surface area of 7.5m2(g) apparent density of 1.12g/cm3Tap density of 1.95g/cm3；
S2, carrying out coarse crushing and fine crushing on the primary calcined material, wherein the coarse crushing is carried out through jaw crushing, and the gap between double-roll crack is 0.35 mm; the fine crushing parameters are induced air frequency of 18Hz and grading frequency of 80 Hz;
s3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 2:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 60 ℃, taking commercial wet coating liquid according to 6% of the mass fraction of the washing material, adding the commercial wet coating liquid into the reaction kettle at a constant speed, controlling the addition to be completed within about 10min, continuously stirring and reacting for 40min after the coating liquid is completely added, performing filter pressing, and then putting the mixture into a drying oven to dry for 8h at 110 ℃ to obtain a mixed material;
s4, mixing and addingNb is 0.25 percent of the mass of the mixed material2O5Uniformly mixing, then placing in an atmosphere furnace for calcining at 750 ℃ for 8h, crushing (with the same crushing parameter of S2), sieving, and demagnetizing by using an iron remover for 2h, wherein the proportion of iron slag is less than 0.5%, thus obtaining the ultra-high nickel single crystal ternary cathode material.
Example 1:
preference is given to D50MgO powder of 20nm and NH4And F, respectively weighing and mixing the crystals according to the molar ratio of metal magnesium ions to fluorine ions of 1:2, wherein the mass is 1000g in total, placing the mixed materials in a ball milling tank, selecting polyurethane balls, carrying out ball milling for 12h according to the ball-to-material ratio of 2:1, placing the mixed materials in a jet mill for fine crushing, wherein jet milling parameters are that the crushing pressure is 0.8MPa, the feeding frequency is 3Hz, the grading frequency is 130Hz, and the induced air frequency is 20Hz, collecting the fine crushed materials, and sieving the fine crushed materials with a 400-mesh sieve to obtain a product, which is marked as a modified coating agent 1.
The application comprises the following steps:
s1, adding Ni0.90Co0.05Mn0.05(OH)2Mixing the ternary precursor with battery-grade lithium hydroxide monohydrate in a molar ratio of lithium to metal of 1.08:1, and adding Al (OH) accounting for 0.5 percent of the mass of the cobalt-nickel-containing ternary precursor3And ZrO 0.3% of the mass of the cobalt-nickel-containing ternary precursor2Then, calcining the mixture for 15 hours at the temperature of 790 ℃ in an oxygen atmosphere to obtain a primary calcined material; wherein the ternary precursor-containing medium particle diameter D503.20 μm, a specific surface area of 7.5m2(g) apparent density of 1.12g/cm3Tap density of 1.95g/cm3；
S2, carrying out coarse crushing and fine crushing on the primary calcined material, wherein the coarse crushing is carried out through jaw crushing, and the gap between double-roll crack is 0.15 mm; the fine crushing parameters are induced air frequency of 28Hz and grading frequency of 120 Hz;
s3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 2:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 60 ℃, taking commercial wet coating liquid according to 6% of the mass fraction of the washing material, adding the commercial wet coating liquid into the reaction kettle at a constant speed, controlling the addition to be completed within about 10min, continuously stirring and reacting for 40min after the coating liquid is completely added, performing filter pressing, and then putting the mixture into a drying oven to dry for 8h at 110 ℃ to obtain a mixed material;
s4, uniformly mixing the mixed material with the modified coating agent 1 with the addition amount of 0.12% of the mixed material by mass, then placing the mixture in an atmosphere furnace for calcining at 750 ℃ for 8 hours, crushing (with the same crushing parameters of S2), sieving, and demagnetizing for 2 hours by using an iron remover, wherein the proportion of iron slag is less than 0.5%, thus obtaining the ultra-high nickel single crystal ternary cathode material.
Example 2:
preference is given to D5040nm of Al2O3Powder and (NH4)3AlF6Respectively weighing and mixing the crystals according to the molar ratio of metal aluminum ions to fluorine ions of 1:3, wherein the mass is 1000g in total, placing the mixture into a ball milling tank, selecting agate balls, carrying out ball milling for 5h according to the ball-material ratio of 2:1, placing the mixed material into an atmosphere furnace for calcining for 6h at 550 ℃ in an oxygen atmosphere, finely crushing the calcined material by using a jet mill, wherein the jet milling parameters are that the milling pressure is 0.90MPa, the feeding frequency is 5Hz, the grading frequency is 180Hz, and the induced air frequency is 35Hz, collecting the finely crushed material, and sieving the finely crushed material by using a 400-mesh sieve to obtain a product, which is marked as a modified coating agent 2.
The application comprises the following steps:
s1, adding Ni0.92Co0.04Mn0.04(OH)2Mixing the ternary precursor with battery-grade lithium hydroxide monohydrate in a molar ratio of lithium to metal of 1.03:1, and adding Ti (OH) accounting for 0.25 percent of the mass of the cobalt-nickel-containing ternary precursor4And SiO with the mass of 0.6 percent of the cobalt-nickel-containing ternary precursor2Then, the mixture is calcined for 12 hours at the temperature of 770 ℃ in the oxygen atmosphere to obtain a primary calcined material; wherein the ternary precursor-containing medium particle diameter D503.05 μm, a specific surface area of 13.5m2(g) apparent density of 1.08g/cm3Tap density of 1.87g/cm3；
S2, carrying out coarse crushing and fine crushing on the primary calcined material, wherein the coarse crushing is carried out through jaw crushing, and the gap between double-roll crack is 0.10 mm; the fine crushing parameters are induced air frequency of 35Hz and grading frequency of 150 Hz.
S3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 1.5:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 25 ℃, taking commercial wet coating liquid according to 8% of the mass fraction of the washing material, adding the commercial wet coating liquid into the reaction kettle at a constant speed, controlling the addition to be completed within about 10min, continuously stirring and reacting for 2h after the coating liquid is completely added, performing filter pressing, and then drying in a drying oven at 150 ℃ for 6h to obtain a mixed material;
s4, uniformly mixing the mixed material with a modified coating agent 2 with the addition amount of 0.2 percent of the mass of the mixed material, then placing the mixed material in an atmosphere furnace for calcination at 700 ℃ for 6 hours, crushing (with the same crushing parameters of S2), sieving, and demagnetizing by using an iron remover for 2.2 hours, wherein the proportion of iron slag is less than 0.5 percent, thus obtaining the ultra-high nickel single crystal anode ternary material.
Example 3:
preference is given to D50ZrO of 50nm2Powder and D50Nb of 200nm2O5Respectively weighing and mixing the zirconium ions and the niobium ions according to the molar ratio of 1:1, wherein the total weight is 1000g, placing the mixture into a ball milling tank, selecting agate balls, carrying out ball milling for 12h according to the ball material ratio of 3:1, placing the mixed material into an atmosphere furnace for keeping the temperature at 700 ℃ for 4h, grinding and coarsely crushing the calcined material by using a mortar, and finely crushing the calcined material by using a jet mill, wherein the jet milling parameters comprise that the milling pressure is 0.85MPa, the feeding frequency is 5Hz, the grading frequency is 150Hz, and the induced air frequency is 40Hz, collecting the finely crushed material, and sieving the finely crushed material by using a 400-mesh sieve to obtain a product which is marked as a modified coating agent 3.
The application comprises the following steps:
s1, adding Ni0.88Co0.09Mn0.03(OH)2Mixing the ternary precursor with battery-grade lithium hydroxide monohydrate in a molar ratio of lithium to metal of 1.06:1, and adding Sr (OH) accounting for 0.07 percent of the mass of the cobalt-nickel-containing ternary precursor2And Nb with the mass of 0.30 percent of the cobalt-nickel-containing ternary precursor2O5Then calcining at 810 ℃ for 8 hours in an oxygen atmosphere to obtain a primary calcined material; wherein the ternary precursor-containing medium particle diameter D503.50 μm, a specific surface area of 7.0m2(g) apparent density of 1.08g/cm3Tap density of 1.85g/cm3；
S2, carrying out coarse crushing and fine crushing on the primary calcined material, wherein the coarse crushing is carried out through jaw crushing, and the gap between double-roll crack is 0.25 mm; the fine crushing parameters are induced air frequency of 5Hz and grading frequency of 100 Hz.
S3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 1:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 45 ℃, taking commercial wet coating liquid according to 8% of the mass fraction of the washing material, adding the commercial wet coating liquid into the reaction kettle at a constant speed, controlling the addition to be completed within 15min, continuously stirring and reacting for 1h after the coating liquid is completely added, performing filter pressing, and then putting the mixture into a drying oven for drying for 2h at the temperature of 250 ℃ to obtain a mixed material;
s4, uniformly mixing the mixed material with a modified coating agent 3 with the addition amount of 0.25 percent of the mass of the mixed material, then placing the mixed material in an atmosphere furnace for calcination at 800 ℃ for 10 hours, crushing (with the same crushing parameters of S2), sieving, and demagnetizing by using an iron remover for 2.5 hours, wherein the proportion of iron slag is less than 0.5 percent, thus obtaining the ultra-high nickel single crystal ternary cathode material.
Example 4:
690.18 g NH were weighed4H2PO4Dissolving the mixture into 2070.54 g of deionized water according to the mass ratio of the mixture to the solvent of 1:3, stirring the mixture by a normal-temperature stirring paddle until the mixture is completely dissolved, and marking the solution as solution A, preferably D50La of 150nm2O3Adding 325.81 g of powder into the solution A, continuously stirring for 1h to obtain a solution B, carrying out spray drying on the solution B, wherein the spray drying temperature is 250 ℃, the dried material is powder C, placing the spray-dried powder C into an airflow pulverizer for fine crushing, wherein the airflow crushing parameters are that the crushing pressure is 1.0MPa, the feeding frequency is 10Hz, the grading frequency is 120Hz, and the induced air frequency is 30Hz, then collecting the fine crushed material, and sieving with a 400-mesh sieve to obtain a product, which is marked as a modified coating agent 4.
The application comprises the following steps:
s1, adding Ni0.88Co0.09Al0.03(OH)2Mixing the ternary precursor with battery-grade lithium hydroxide monohydrate in a molar ratio of lithium to metal of 1.04:1, and adding Mg (OH) accounting for 0.35 percent of the mass of the cobalt-nickel-containing ternary precursor2MoO with 0.15 percent of cobalt-nickel-containing ternary precursor mass3And SrO with the mass of 0.2 percent of the cobalt-nickel-containing ternary precursor, and calcining at 820 ℃ for 15h in an oxygen atmosphere to obtain a primary calcined material; wherein said contains threeMedian particle diameter D of elemental precursor503.30 μm, a specific surface area of 8.7m2(g) apparent density of 1.18g/cm3Tap density of 1.92g/cm3；
S2, carrying out coarse crushing and fine crushing on the primary calcined material, wherein the coarse crushing is carried out through jaw crushing, and the gap between double-roll crack is 0.40 mm; the fine crushing parameters are induced air frequency of 30Hz and grading frequency of 50 Hz.
S3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 3:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 30 ℃, taking commercial wet coating liquid with the mass fraction of 6% of that of the washing material, adding the commercial wet coating liquid into the reaction kettle at a constant speed, controlling the addition to be completed within about 10min, continuously stirring and reacting for 1.5h after the coating liquid is completely added, performing filter pressing, and then drying in a drying oven at 150 ℃ for 4h to obtain a mixed material;
s4, uniformly mixing the mixed material with a modified coating agent 4 with the addition amount of 0.35 percent of the mixed material mass, then placing the mixture in an atmosphere furnace for calcining at 810 ℃ for 8 hours, crushing (with the same crushing parameters of S2), sieving, and demagnetizing by using an iron remover for 1.5 hours, wherein the proportion of iron slag is less than 0.5 percent, thus obtaining the ultra-high nickel single crystal ternary cathode material.
Example 5:
preference is given to D50Is 50nm SiO2Powder and (NH)4)2WO4Respectively weighing and mixing the crystals according to the molar ratio of silicon ions to metal tungsten ions of 1:1.5, wherein the total weight is 1000g, placing the mixed materials in a ball milling tank, selecting polyurethane balls, carrying out ball milling for 4h according to the ball-to-material ratio of 5:1, placing the mixed materials in a jet mill for fine crushing, wherein the jet milling parameters are that the crushing pressure is 0.95MPa, the feeding frequency is 8Hz, the grading frequency is 160Hz, and the induced air frequency is 25Hz, collecting the fine crushed materials, and sieving the fine crushed materials with a 400-mesh sieve to obtain a product, which is marked as a modified coating agent 5.
The application comprises the following steps:
s1, adding Ni0.95Co0.03Mn0.02(OH)2Mixing the ternary precursor with battery-grade lithium hydroxide monohydrate in a molar ratio of lithium to metal of 1.02:1, and adding Zr (OH) accounting for 0.90 percent of the mass of the cobalt-nickel-containing ternary precursor4And cobalt-nickel containingY of 0.10% of the mass of the ternary precursor2O3Then calcining at 750 ℃ for 8 hours in an oxygen atmosphere to obtain a primary calcined material; wherein the ternary precursor-containing medium particle diameter D503.45 μm, a specific surface area of 11.6m2(g) apparent density of 1.09g/cm3Tap density of 1.91g/cm3；
S2, carrying out coarse crushing and fine crushing on the primary calcined material, wherein the coarse crushing is carried out through jaw crushing, and the gap between double-roll crack is 0.2 mm; the fine crushing parameters are induced air frequency of 30Hz and grading frequency of 140 Hz.
S3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 1.5:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 80 ℃, taking commercial wet coating liquid according to 4% of the mass fraction of the washing material, adding the commercial wet coating liquid into the reaction kettle at a constant speed, controlling the addition to be completed within about 10min, continuously stirring and reacting for 0.5h after the coating liquid is completely added, performing filter pressing, and then putting the mixture into a drying oven to dry for 5h at 120 ℃ to obtain a mixed material;
s4, uniformly mixing the mixed material with a modified coating agent 5 with the addition amount of 0.35 percent of the mixed material by mass, then placing the mixed material in an atmosphere furnace for calcination at 700 ℃ for 10 hours, crushing (with the same crushing parameters of S2), sieving, and demagnetizing by using an iron remover for 1.8 hours, wherein the proportion of iron slag is less than 0.5 percent, thus obtaining the ultra-high nickel single crystal ternary cathode material.
Example 6:
preference is given to D50MgO powder of 20nm and NH4And F, respectively weighing and mixing the crystals according to the molar ratio of metal magnesium ions to fluorine ions of 1:2, wherein the mass is 1000g in total, placing the mixed materials in a ball milling tank, selecting polyurethane balls, carrying out ball milling for 12h according to the ball material ratio of 2:1, placing the mixed materials in an atmosphere furnace for calcining for 15h at 400 ℃ in oxygen atmosphere, carrying out grinding coarse crushing and fine crushing by using an airflow crusher, wherein the airflow crushing parameters are that the crushing pressure is 0.9MPa, the feeding frequency is 15Hz, the grading frequency is 100Hz, and the induced air frequency is 30Hz, collecting the fine crushed materials, and sieving by using a 400-mesh sieve to obtain a product A.
690.18 g NH were weighed4H2PO4305.88 g of D5040nm of Al2O3Putting the mixture into a ball milling tank, adding 4980.3 g of absolute ethyl alcohol into the ball milling tank according to the mass ratio of the absolute ethyl alcohol to the solvent being 1:5, putting the mixture into agate balls according to the mass ratio of the absolute ethyl alcohol to the solid being 1:1, carrying out wet ball milling for 5h to obtain emulsion B, carrying out spray drying on the emulsion B, wherein the spray drying temperature is 200 ℃, and obtaining the dried material C powder.
500g of the powder A and the powder C are respectively weighed according to the mass ratio of 1:1 and placed in a ball milling tank, and agate balls are added according to the ball-to-material ratio of 1:1 for ball milling for 5 hours. And (3) placing the mixed material after ball milling into a jet mill for fine crushing, wherein jet milling parameters are that the crushing pressure is 1.0MPa, the feeding frequency is 8Hz, the grading frequency is 180Hz, and the induced air frequency is 35Hz, then collecting the fine crushed material, and sieving the fine crushed material with a 400-mesh sieve to obtain a product, which is marked as a modified coating agent 6.
The application comprises the following steps:
s1, adding Ni0.90Co0.05Al0.05(OH)2Mixing the ternary precursor with battery-grade lithium hydroxide monohydrate in a molar ratio of lithium to metal of 1.05:1, and adding WO (tungsten trioxide) containing 0.25 mass percent of cobalt-nickel ternary precursor3And SnO with the mass of 0.25 percent of the ternary precursor containing cobalt and nickel2Then calcining at 800 ℃ for 10 hours in an oxygen atmosphere to obtain a primary calcined material; wherein the ternary precursor-containing medium particle diameter D503.45 μm, a specific surface area of 9.0m2(g) apparent density of 1.15g/cm3Tap density of 1.97g/cm3；
S2, carrying out coarse crushing and fine crushing on the primary calcined material, wherein the coarse crushing is carried out through jaw crushing, and the gap between double-roll crack is 0.30 mm; the fine crushing parameters are induced air frequency of 10Hz and grading frequency of 65 Hz.
S3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 1.5:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 50 ℃, taking a purchased commodity wet-process coating solution according to 7% of the mass fraction of the washing material, adding the commercial wet-process coating solution into the reaction kettle at a constant speed, controlling the adding to be finished within about 10min, continuously stirring and reacting for 1h after the coating solution is completely added, performing filter pressing, and then putting the mixture into a drying oven to dry for 3h at 200 ℃ to obtain a mixed material;
s4, uniformly mixing the mixed material with a modified coating agent 6 with the addition amount of 0.22 percent of the mass of the mixed material, then placing the mixed material in an atmosphere furnace for calcining at 750 ℃ for 8 hours, crushing (with the same crushing parameters of S2), sieving, and demagnetizing for 2 hours by using an iron remover, wherein the proportion of iron slag is less than 0.5 percent, thus obtaining the ultra-high nickel single crystal ternary cathode material.
TABLE 1 statistical table of residual alkali on the surface of the material of the example
As can be seen from the table, the material obtained by adding the reagent in the wet mixing manner for reaction and coating the composite coating agent by the wet method has low surface alkali residue.
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited to the details of the embodiments, but is capable of various modifications and substitutions without departing from the spirit of the invention.
Claims (9)
1. The composite coating agent for the ultra-high nickel single crystal ternary cathode material is characterized by comprising the following raw materials: at least one of metal and/or nonmetal oxide, ammonium salt compound; the metal oxide is MgO and Al2O3、La2O3、ZrO2、Nb2O5At least one of; the non-metal oxide is SiO2(ii) a The ammonium salt compound is NH4F、(NH4)3AlF6、NH4H2PO4、(NH4)2WO4At least one of (1).
2. The method for preparing the composite coating agent for the ultra-high nickel single crystal ternary positive electrode material as claimed in claim 1, wherein the metal and/or nonmetal oxide is nano-scale particles, D50Is 20-200 nm.
3. The preparation method of the composite coating agent for the ternary cathode material of the ultra-high nickel single crystal as claimed in claim 1, wherein the composite coating agent is obtained by treating the raw materials in at least one of ball milling, jet milling, calcining, wet mixing and spray drying.
4. The preparation method of the composite coating agent for the ultra-high nickel single crystal ternary positive electrode material as claimed in claim 3, wherein the ball-milling ball-to-material ratio is 1:1-5:1, and the ball-milling time is 4-12 h; wherein the ball is at least one of polyurethane ball and agate ball.
5. The preparation method of the composite coating agent for the ultra-high nickel single crystal ternary positive electrode material as claimed in claim 3, wherein the jet milling parameters are as follows: the crushing pressure is 0.8MPa-1.0MPa, the feeding frequency is 3-15Hz, the grading frequency is 80-180Hz, and the induced air frequency is 20-40 Hz.
6. The method for preparing the composite coating agent for the ternary cathode material of the ultra-high nickel single crystal as claimed in claim 3, wherein the equipment used for calcination is an atmosphere furnace, the calcination atmosphere is air or oxygen, the calcination temperature is 400-700 ℃, and the calcination time is 4-15 h.
7. The method for preparing the composite coating agent for the ultra-high nickel single crystal ternary cathode material as claimed in claim 3, wherein the temperature of the spray drying is 200-250 ℃.
8. The composite coating agent for the ultra-high nickel single crystal ternary cathode material is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The application of the composite coating agent for the ultrahigh nickel single crystal ternary cathode material is characterized in that the composite coating agent is used for preparing the ultrahigh nickel single crystal ternary cathode material, and specifically comprises the following components in percentage by weight:
s1, adding the primary calcined and crushed ultrahigh nickel ternary cathode material and water into a reaction kettle according to a water-material ratio of 0.5:1-5:1, and mixing to obtain a reaction material; controlling the temperature of the reaction kettle, adding a reagent for reaction, and drying after the reaction is finished to obtain a mixed material;
s2, mixing the mixed material and the composite coating agent in the S1, placing the mixture in an atmosphere furnace for aerobic calcination at the temperature of 700-810 ℃ for 6-10h, and then crushing, sieving and demagnetizing to obtain the ultra-high nickel ternary single crystal anode material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114524468A (en) * | 2022-02-14 | 2022-05-24 | 浙江格派钴业新材料有限公司 | Preparation method of modified single-crystal ultrahigh-nickel quaternary NCMA positive electrode material |
| WO2023097937A1 (en) | 2021-11-30 | 2023-06-08 | 天津巴莫科技有限责任公司 | Composite coating method for highly-compacted nickelic layered positive electrode material of solid-state battery |
| WO2023232596A1 (en) | 2022-06-03 | 2023-12-07 | Evonik Operations Gmbh | Cathode active material particles encapsulated in pyrogenic, nanostructured magnesium oxide, and methods of making and using the same |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102956895A (en) * | 2012-11-15 | 2013-03-06 | 北大先行科技产业有限公司 | Surface composite coated anode material, preparation method thereof and lithium ion battery |
| CN104409700A (en) * | 2014-11-20 | 2015-03-11 | 深圳市贝特瑞新能源材料股份有限公司 | Anode material for nickel-base lithium ion battery and preparation method of anode material |
| CN106025254A (en) * | 2016-06-24 | 2016-10-12 | 常熟理工学院 | Surface coating modification method of LiNi0.5Mn1.5O4 cathode material |
| CN106505195A (en) * | 2016-12-30 | 2017-03-15 | 宁波金和锂电材料有限公司 | A kind of nickelic positive electrode and preparation method thereof and lithium ion battery |
| CN108400309A (en) * | 2017-11-29 | 2018-08-14 | 灌云天骄科技开发有限公司 | The method that compound coating prepares modified high voltage monocrystalline tertiary cathode material |
| CN108598447A (en) * | 2018-06-26 | 2018-09-28 | 浙江天能能源科技股份有限公司 | A kind of polynary nickelic positive electrode and preparation method thereof of dioxygen compound cladding |
| CN108878827A (en) * | 2018-06-26 | 2018-11-23 | 浙江天能能源科技股份有限公司 | A kind of nickelic tertiary cathode material and preparation method thereof of dioxygen compound cladding |
| CN109411733A (en) * | 2018-11-06 | 2019-03-01 | 烟台卓能锂电池有限公司 | Modified anode material for lithium-ion batteries of compound coating and preparation method thereof, anode and lithium ion battery |
| CN109742346A (en) * | 2018-12-26 | 2019-05-10 | 格林美（无锡）能源材料有限公司 | Si/Al coats nickel cobalt manganese anode material for lithium-ion batteries and preparation method thereof altogether |
| CN110436531A (en) * | 2019-06-20 | 2019-11-12 | 浙江美都海创锂电科技有限公司 | High Ni-monocrystal tertiary cathode material of low surface residual alkali and preparation method thereof |
| CN110931797A (en) * | 2019-12-09 | 2020-03-27 | 宁波容百新能源科技股份有限公司 | High-nickel positive electrode material with composite coating layer and preparation method thereof |
| CN111463411A (en) * | 2019-01-18 | 2020-07-28 | 天津国安盟固利新材料科技股份有限公司 | High-nickel ternary cathode material with single crystal morphology and preparation method thereof |
-
2020
- 2020-08-27 CN CN202010880742.3A patent/CN112194196A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102956895A (en) * | 2012-11-15 | 2013-03-06 | 北大先行科技产业有限公司 | Surface composite coated anode material, preparation method thereof and lithium ion battery |
| CN104409700A (en) * | 2014-11-20 | 2015-03-11 | 深圳市贝特瑞新能源材料股份有限公司 | Anode material for nickel-base lithium ion battery and preparation method of anode material |
| CN106025254A (en) * | 2016-06-24 | 2016-10-12 | 常熟理工学院 | Surface coating modification method of LiNi0.5Mn1.5O4 cathode material |
| CN106505195A (en) * | 2016-12-30 | 2017-03-15 | 宁波金和锂电材料有限公司 | A kind of nickelic positive electrode and preparation method thereof and lithium ion battery |
| CN108400309A (en) * | 2017-11-29 | 2018-08-14 | 灌云天骄科技开发有限公司 | The method that compound coating prepares modified high voltage monocrystalline tertiary cathode material |
| CN108598447A (en) * | 2018-06-26 | 2018-09-28 | 浙江天能能源科技股份有限公司 | A kind of polynary nickelic positive electrode and preparation method thereof of dioxygen compound cladding |
| CN108878827A (en) * | 2018-06-26 | 2018-11-23 | 浙江天能能源科技股份有限公司 | A kind of nickelic tertiary cathode material and preparation method thereof of dioxygen compound cladding |
| CN109411733A (en) * | 2018-11-06 | 2019-03-01 | 烟台卓能锂电池有限公司 | Modified anode material for lithium-ion batteries of compound coating and preparation method thereof, anode and lithium ion battery |
| CN109742346A (en) * | 2018-12-26 | 2019-05-10 | 格林美（无锡）能源材料有限公司 | Si/Al coats nickel cobalt manganese anode material for lithium-ion batteries and preparation method thereof altogether |
| CN111463411A (en) * | 2019-01-18 | 2020-07-28 | 天津国安盟固利新材料科技股份有限公司 | High-nickel ternary cathode material with single crystal morphology and preparation method thereof |
| CN110436531A (en) * | 2019-06-20 | 2019-11-12 | 浙江美都海创锂电科技有限公司 | High Ni-monocrystal tertiary cathode material of low surface residual alkali and preparation method thereof |
| CN110931797A (en) * | 2019-12-09 | 2020-03-27 | 宁波容百新能源科技股份有限公司 | High-nickel positive electrode material with composite coating layer and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 冯泽: "富镍三元层状氧化物LiNi0.8Co0.1Mn0.1O2正极材料", 《化学进展》 * |
| 张闻煦: "锂离子电池层状富锂正极材料的表面改性研究", 《中国知网优秀硕士学位论文数据库》 * |
| 李钊: "富锂锰基正极材料的表面改性研究进展", 《化 学 学 报》 * |
| 连芳: "《电化学储能器件及关键材料》", 31 July 2019 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023097937A1 (en) | 2021-11-30 | 2023-06-08 | 天津巴莫科技有限责任公司 | Composite coating method for highly-compacted nickelic layered positive electrode material of solid-state battery |
| CN114524468A (en) * | 2022-02-14 | 2022-05-24 | 浙江格派钴业新材料有限公司 | Preparation method of modified single-crystal ultrahigh-nickel quaternary NCMA positive electrode material |
| CN114524468B (en) * | 2022-02-14 | 2023-09-29 | 浙江格派钴业新材料有限公司 | Preparation method of modified monocrystal ultrahigh nickel quaternary NCMA positive electrode material |
| WO2023232596A1 (en) | 2022-06-03 | 2023-12-07 | Evonik Operations Gmbh | Cathode active material particles encapsulated in pyrogenic, nanostructured magnesium oxide, and methods of making and using the same |
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