CN113745500A - Preparation method of high-nickel ternary cathode material - Google Patents
Preparation method of high-nickel ternary cathode material Download PDFInfo
- Publication number
- CN113745500A CN113745500A CN202110888058.4A CN202110888058A CN113745500A CN 113745500 A CN113745500 A CN 113745500A CN 202110888058 A CN202110888058 A CN 202110888058A CN 113745500 A CN113745500 A CN 113745500A
- Authority
- CN
- China
- Prior art keywords
- nano
- oxide
- heating
- less
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 61
- 239000010406 cathode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 98
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000010438 heat treatment Methods 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 40
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 235000011837 pasties Nutrition 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000007873 sieving Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000012697 Mn precursor Substances 0.000 claims abstract description 7
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 claims abstract description 7
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims description 8
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910003678 NixCoyMnz(OH)2 Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 2
- 125000005341 metaphosphate group Chemical group 0.000 abstract description 14
- 239000000243 solution Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 18
- 239000011572 manganese Substances 0.000 description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 12
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 12
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 12
- 229910052863 mullite Inorganic materials 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007580 dry-mixing Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910017225 MnxCoy Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- -1 metaphosphate compound Chemical class 0.000 description 1
- RHJYKEDKMHDZBL-UHFFFAOYSA-L metaphosphoric acid (hpo3), magnesium salt Chemical compound [Mg+2].[O-]P(=O)=O.[O-]P(=O)=O RHJYKEDKMHDZBL-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of preparation of ternary cathode materials, and discloses a preparation method of a high-nickel ternary cathode material. The method comprises the following steps: s1, preparing Ni-Co-Mn precursorxCoyMnz(OH)2And the molar ratio of the lithium source to the first nano oxide is 1: 1.0-1.06: mixing at a ratio of 0.001-0.01; s2, sintering the mixed material for the first time in an oxygen atmosphere, cooling and crushing; s3, adding the powder material into a phosphoric acid solution with the concentration of 10-30 mass%, stirring for the first time at a first heating temperature, and adding a second nano oxideThen stirring for the second time at a second heating temperature to form pasty slurry, filtering and drying; and S4, grinding the materials, then sintering for the second time in an oxygen atmosphere, cooling and sieving. The cycle stability and the structural stability of the metaphosphate-coated high-nickel ternary cathode material obtained by the method are greatly improved.
Description
Technical Field
The invention relates to the technical field of preparation of ternary cathode materials, in particular to a preparation method of a high-nickel ternary cathode material.
Background
With the continuous development of new energy industry, the importance of lithium ion batteries as important energy storage devices in the industrial development is greater and greater, and the anode material is the most core part of the lithium ion batteries and becomes an important research direction in the industry. At present, lithium iron phosphate, ternary materials and lithium cobaltate are mainly used as anode materials of lithium ion batteries, wherein the lithium iron phosphate and the ternary materials are mainly used for power batteries for electric automobiles, and the application of the lithium iron phosphate in nearly two years is gradually improved due to high safety and low cost, but the lithium iron phosphate has the greatest disadvantage of low capacity and is difficult to apply to the power batteries for electric automobiles with higher endurance and intelligence; the ternary material, particularly the high-nickel ternary material, has wide application in high-endurance and high-intelligence electric automobiles due to high capacity, and related research institutions show that the cost of the ternary material after large-scale use is expected to reach the level equivalent to that of lithium iron phosphate in 2025 years, so the high-nickel ternary material becomes the main direction for the development in the ternary material industry. The high-nickel ternary material has high content of residual lithium on the surface due to high nickel content and low sintering temperature, further influences the processing performance of the high-nickel ternary material in the process of manufacturing a battery, and simultaneously causes the battery to expand and the cycle performance to be poor in the later use process. At present, the development of the high-nickel ternary material is mainly to perform surface treatment on the high-nickel ternary material, adjust the surface state of the high-nickel ternary material through various coating modes and improve the stability of the high-nickel ternary material. Most of modification schemes adopt wet treatment after primary sintering to remove residual lithium, and then nano oxide or hydroxide is added for dry mixing for coating, wherein the wet treatment can effectively remove the residual lithium, but if the process conditions are not properly treated, the crystal structure lithium can be easily removed, the capacity and the circulation of the material are influenced, and the addition of the nano oxide or hydroxide for dry mixing and coating is difficult to obtain uniform coating, and the later circulation of the material is also poor.
Chinese patent CN112125352A discloses a method for preparing a high-nickel cathode material, which comprises the steps of pretreating a precursor by a wet method, specifically, adding the precursor into a solution system containing hydrogen peroxide and a lithium source, stirring and mixing uniformly, reacting at a certain temperature to make the lithium source form lithium peroxide with higher activity under the oxidation action of the hydrogen peroxide, filtering and drying, sintering at a high temperature, crushing after sintering, and performing secondary sintering coating with a coating agent at a low temperature.
Disclosure of Invention
The invention aims to overcome the defects that in the prior art, hydrogen peroxide with strong oxidizing property is adopted in the preparation process of a high-nickel cathode material, and a precursor is possibly oxidized in the wet treatment process, so that the difficulty of subsequent sintering reaction is increased, the required sintering temperature is higher, the lithium-nickel mixed degree of a product is increased, and the capacity and the cycle are reduced. Meanwhile, hydrogen peroxide is three carcinogens, flammable and explosive substances, and the strong oxidizing property of the hydrogen peroxide can meet higher requirements on production equipment, so that the problem of difficulty in large-scale industrial production and utilization is solved. Meanwhile, in the subsequent sintering process, the nano oxide and the phosphoric acid can form metaphosphate, and because the metaphosphate can effectively prevent the release of free oxygen in the material, the metaphosphate can adsorb the free oxygen to form more stable phosphate radical, so that the material is more effectively protected in the circulating process, and the circulating stability and the structural stability of the metaphosphate-coated high-nickel ternary positive electrode material are greatly improved; in addition, the common commercial metaphosphate is a large-agglomeration irregular blocky material, and the metaphosphate formed by the in-situ chemical reaction has the effect of fine and uniform particles and is beneficial to coating.
In order to achieve the aim, the invention provides a preparation method of a high-nickel ternary cathode material, which comprises the following steps:
s1, preparing Ni-Co-Mn precursorxCoyMnz(OH)2And the molar ratio of the lithium source to the first nano oxide is 1: 1.0-1.06: mixing at a ratio of 0.001-0.01;
s2, sintering the mixed material obtained in the step S1 for the first time in an oxygen atmosphere, cooling and crushing;
s3, adding the powder material obtained in the step S2 into a phosphoric acid solution with the concentration of 10-30 mass%, stirring for the first time at a first heating temperature, adding a second nano oxide, stirring for the second time at a second heating temperature to form pasty slurry, filtering, and drying;
s4, grinding the material obtained in the step S3, then carrying out secondary sintering in an oxygen atmosphere, cooling and sieving to obtain the high-nickel ternary cathode material LiaNixCoyMnzMbNcO2M, N are cationic elements in the first nano-oxide and the second nano-oxide, respectively, M, N are the same or different,
wherein a is more than 1 and less than 1.08, x is more than 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than 0 and less than 0.2, b is more than 0 and less than 0.2, c is more than 0 and less than 0.2, and x + y + z is 1.
Preferably, Ni is added into the nickel-cobalt-manganese precursorxCoyMnz(OH)2And the high-nickel ternary cathode material LiaNixCoyMnzMbNcO2In the formula, a is more than 1 and less than 1.03; x is more than 0.8 and less than 0.95; y is more than 0.03 and less than 0.15; z is more than 0.03 and less than 0.15.
Preferably, in step S1, the nickel cobalt manganese precursor NixCoyMnz(OH)2The particle size of (A) is 10-12 μm.
Preferably, in step S1, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium phosphate or lithium chloride.
Preferably, in step S1, the first nano-oxide is one or more of Al, Zr, Ti, Mg, Zn, W, Y or B metal oxides.
Preferably, in step S1, the mixing speed is 600-900rpm, and the mixing time is 15-30 min.
Preferably, in step S2, the first sintering process is: heating to 400-800 ℃ at a heating rate of 3-5 ℃/min, and keeping the temperature for 2-6h, and then heating to 750-800 ℃ at a heating rate of 1-3 ℃/min, and keeping the temperature for 10-14 h.
Preferably, in step S3, the second nano-oxide is one or more of nano-magnesium oxide, nano-aluminum oxide, nano-yttrium oxide or nano-strontium oxide.
Preferably, the adding amount of the second nano oxide is 0.1 to 0.35 mass% of the powder material obtained in the step S2.
Preferably, in step S3, the first heating temperature is 60 to 70 ℃, and the second heating temperature is 70 to 90 ℃.
Preferably, in step S3, the time for the first stirring is 10-20 min.
Preferably, in step S3, the first stirring and the second stirring are performed at a rate of 150-300 rpm.
Preferably, in step S4, the second sintering process is: heating to 500-600 ℃ at the heating rate of 3-5 ℃/min and preserving the heat for 6-8 h.
The beneficial effects of the invention are mainly embodied in the following aspects:
1. the residual lithium on the surface of the high-nickel material is high, the alkalinity of the material is high, and in the process of preparing the battery, the high alkalinity can cause the PVDF (polyvinylidene fluoride) binder to lose efficacy, so that the slurry is in a jelly state, and the subsequent coating and the battery preparation are influenced; meanwhile, the high alkalinity also increases side reactions during the charging and discharging processes of the battery, so that the cycle performance of the battery is poor. The inventor finds that a weakly acidic phosphoric acid system is adopted in the coating process, the weakly acidic phosphoric acid can react with strongly basic residual lithium on the surface of a high-nickel material, the residual lithium on the surface of the high-nickel ternary material can be well removed, and the material can not be damaged due to the weak acidity of the phosphoric acid while the residual lithium is removed.
2. Compared with dry mixing, the invention adopts wet system mixing to ensure the uniformity of the whole material in the coating mixing process and also ensure the uniformity of removing residual lithium on the surface of the material.
3. In the coating process, the nanometer oxide and phosphoric acid act to generate water-soluble hydrated dihydric phosphate, the dihydric phosphate gradually loses extra-molecular crystal water under the first heating action in a phosphoric acid system to form dihydric salt, and then water in molecules is removed in the second heating process to form nonpolymeric metaphosphate coated on the surface of the high-nickel ternary material. Metaphosphate is introduced for in-situ reaction coating, a layer of metaphosphate compound is formed on the surface of the high-nickel material, the full battery cycle performance of the material can be enhanced, the service life is prolonged, the metaphosphate can adsorb free oxygen and trace moisture in the material, phosphate with a more stable structure is formed, and the service life of the material is further prolonged.
Drawings
FIG. 1 is a scanning electron micrograph of a high nickel ternary positive electrode material prepared in example 1;
FIG. 2 is a scanning electron micrograph of a high nickel ternary positive electrode material prepared in example 2;
FIG. 3 is a scanning electron micrograph of a high nickel ternary positive electrode material prepared in example 3;
FIG. 4 is a scanning electron micrograph of a high nickel ternary positive electrode material prepared according to comparative example 1;
FIG. 5 is a scanning electron micrograph of a high nickel ternary positive electrode material prepared according to comparative example 2;
FIG. 6 is a graph of normal temperature cycle performance of the high nickel ternary positive electrode materials prepared in examples 1-3 and comparative examples 1-3 after they are assembled into a battery;
fig. 7 is a graph of high temperature cycling performance after the high nickel ternary cathode materials prepared in examples 1-3 and comparative examples 1-3 were assembled into batteries.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The preparation method of the high-nickel ternary cathode material provided by the invention comprises the following steps of:
s1, preparing Ni-Co-Mn precursorxCoyMnz(OH)2And the molar ratio of the lithium source to the first nano oxide is 1: 1.0-1.06: mixing at a ratio of 0.001-0.01;
s2, sintering the mixed material obtained in the step S1 for the first time in an oxygen atmosphere, cooling and crushing;
s3, adding the powder material obtained in the step S2 into a phosphoric acid solution with the concentration of 10-30 mass%, stirring for the first time at a first heating temperature, adding a second nano oxide, stirring for the second time at a second heating temperature to form pasty slurry, filtering, and drying;
s4, grinding the material obtained in the step S3, then carrying out secondary sintering in an oxygen atmosphere, cooling and sieving to obtain the high-nickel ternary cathode material LiaNixCoyMnzMbNcO2M, N are respectively the first nanometerThe cationic elements, M, N, in the oxide and the second nano-oxide are the same or different,
wherein a is more than 1 and less than 1.08, x is more than 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than 0 and less than 0.2, b is more than 0 and less than 0.2, c is more than 0 and less than 0.2, and x + y + z is 1.
According to the method, a nickel-cobalt-manganese precursor, a lithium source and a first nano oxide are mixed according to a specific ratio, then first sintering is carried out, the first nano oxide, the precursor and the lithium source are doped, then coating is carried out in a mode of adding the nano oxide into a phosphoric acid solution under a heating condition, and after second sintering, the nano oxide and phosphoric acid form metaphosphate to form a high-nickel ternary material coated by the polymeric metaphosphate. In the invention, the prepared high-nickel ternary cathode material LiaNixCoyMnzMbNcO2M, N in (1) are cationic elements in the first nano-oxide and the second nano-oxide, respectively; Ni-Co-Mn precursor NixCoyMnz(OH)2The values of middle x, y and z and the high nickel ternary anode material LiaNixCoyMnzMbNcO2The values of x, y and z are consistent.
In the coating process, the nanometer oxide and phosphoric acid act to generate water-soluble hydrated dihydric phosphate, the dihydric phosphate gradually loses extra-molecular crystal water under the heating action of the first heating temperature in a phosphoric acid system to form dihydric salt, and then water in molecules is removed in the heating process of the second heating temperature to form nonpolymeric metaphosphate coated on the surface of the high-nickel ternary material.
In the method, the concentration of the phosphoric acid solution has great influence on the material performance, the lithium in the material crystal lattice is lost due to the over-high concentration of the phosphoric acid, so that the capacity is reduced, the cycle is poor, the residual lithium on the surface of the material is higher due to the over-low concentration of the phosphoric acid, and the cycle performance of the material is poor due to the reduction of the purity of the generated coating. In specific embodiments, the concentration of the phosphoric acid solution may be 10 mass%, 15 mass%, 20 mass%, 25 mass%, or 30 mass%.
In a preferred embodiment, Ni is added to the Ni-Co-Mn precursorxCoyMnz(OH)2And the high-nickel ternary cathode material LiaNixCoyMnzMbNcO2In the formula, a is more than 1 and less than 1.03; x is more than 0.8 and less than 0.95; y is more than 0.03 and less than 0.15; z is more than 0.03 and less than 0.15. The values of a, x, y and z are limited in the range, and the prepared high-nickel ternary cathode material has higher cycle performance.
In a preferred embodiment, in order to mix the nickel-cobalt-manganese precursor with the lithium source and the first nano-oxide uniformly and to calcine the mixture more fully, in step S1, the nickel-cobalt-manganese precursor Ni is addedxCoyMnz(OH)2The particle size of (B) may be 10 to 12 μm, for example 10 μm, 10.2 μm, 10.4 μm, 10.6 μm, 10.8 μm, 11 μm, 11.2 μm, 11.4 μm, 11.6 μm, 11.8 μm or 12 μm.
In the method of the present invention, the lithium source may be a conventional choice in the art. In a specific embodiment, in step S1, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium phosphate or lithium chloride, and preferably lithium hydroxide.
In the method of the present invention, the first nano-oxide may be a doped oxide conventionally selected in the art. In a specific embodiment, in step S1, the first nano-oxide may be one or more of Al, Zr, Ti, Mg, Zn, W, Y, or B metal oxides.
In a preferred embodiment, Ni is used as a precursor of Ni, Co, MnxCoyMnz(OH)2The lithium source and the first nano oxide are uniformly mixed, and can be mixed by a high-speed mixer, wherein the mixing speed can be 600-900rpm, such as 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, 850rpm or 800 rpm; the mixing time may be 15-30min, for example 15min, 20min, 25min or 30 min.
In a preferred embodiment, in order to improve the stability and electrochemical performance of the prepared material, the first sintering is performed in a segmented sintering mode. The first sintering process may be: heating to 400-800 ℃ at a heating rate of 3-5 ℃/min, and keeping the temperature for 2-6h, and then heating to 750-800 ℃ at a heating rate of 1-3 ℃/min, and keeping the temperature for 10-14 h.
In the method of the present invention, the second nano-oxide may be a coating oxide conventionally used in the art. In a preferred embodiment, in order to improve the cycle performance of the prepared high-nickel ternary material, in step S3, the second nano oxide is one or more of nano magnesium oxide, nano aluminum oxide, nano yttrium oxide or nano strontium oxide.
In a preferred embodiment, to further enhance the Ni-Co-Mn precursor Ni preparedxCoyMnz(OH)2In the method of the present invention, in step S3, the second nano oxide may be added in an amount of 0.1 to 0.35 mass%, for example, 0.1 mass%, 0.12 mass%, 0.15 mass%, 0.18 mass%, 0.2 mass%, 0.22 mass%, 0.25 mass%, 0.28 mass%, 0.3 mass%, 0.33 mass%, or 0.35 mass% of the pulverized material obtained in step S2.
In the method of the present invention, the second nano-oxide needs to react with phosphoric acid under heating condition during the coating process. Specifically, after the second nano oxide is added into a phosphoric acid solution, the second nano oxide reacts with phosphoric acid to generate water-soluble hydrated dihydric phosphate, the dihydric phosphate gradually loses extra-molecular crystal water under the heating action of a first heating temperature in a phosphoric acid system to form dihydric salt, and then water in molecules is removed in the heating process of a second heating temperature to form nonpolymerized metaphosphate which is coated on the surface of the high-nickel ternary material.
In the present invention, the first heating temperature and the second heating temperature are temperatures higher than normal temperature in a heated state.
In a preferred embodiment, in step S3, the first heating temperature is 60 to 70 ℃, e.g., 60 ℃, 65 ℃, or 70 ℃; the second heating temperature is 70-90 deg.C, such as 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C or 90 deg.C.
In the method of the present invention, in order to uniformly disperse the powder material after the first sintering in the phosphoric acid solution, in step S3, the time of the first stirring is 10 to 20min, specifically, for example, 10min, 12min, 14min, 15min, 16min, 18min, or 20 min.
In step S3, the rate of the first stirring and the second stirring may be 150-300rpm, specifically, for example, 150rpm, 170rpm, 190rpm, 200rpm, 210rpm, 230rpm, 250rpm, 270rpm, or 300 rpm.
In a preferred embodiment, in step S4, the second sintering process may be: heating to 500-600 ℃ at the heating rate of 3-5 ℃/min and preserving the heat for 6-8 h. By adopting the sintering mode, the high-nickel ternary material coated by the polymeric metaphosphate can be formed, and the coating layer can be uniformly coated on the surface of the high-nickel ternary material by nano-scale particles.
The present invention will be described in detail below by way of examples, but the present invention is not limited thereto.
Example 1
(1) 3.5kg of precursor Ni with a particle size D50 of 11.2 μm were weighed0.83Co0.12Mn0.05(OH)21.68kg of lithium hydroxide monohydrate and 9.5g of nano zirconia are added into a high-speed mixer and mixed for 30min at the rotating speed of 750rpm, wherein a precursor Ni0.83Co0.12Mn0.05(OH)2The molar ratio of the lithium hydroxide monohydrate to the nano zirconia is 1:1.06: 0.002;
(2) putting the mixed material obtained in the step (1) into a cordierite-mullite sagger, putting the sagger into a box furnace, heating to 500 ℃ at a speed of 3 ℃/min, keeping the temperature for 5 hours, heating to 800 ℃ at a speed of 3 ℃/min, keeping the temperature for 12 hours, taking oxygen as sintering atmosphere, cooling, discharging, and crushing by using a double-roll machine to obtain a powder material;
(3) measuring 7000mL of phosphoric acid solution with the concentration of 10%, measuring 8.75g of nano magnesium oxide, adding the powder material obtained in the step (2) into the measured phosphoric acid solution, stirring at the rotating speed of 300rpm at 60 ℃, adding the measured nano magnesium oxide (the nano magnesium oxide is 0.2% of the mass of the powder material obtained in the step (2)) into the solution during stirring for 10min, raising the temperature to 90 ℃, continuously stirring until the mixed solution is pasty, then placing the pasty material into a vacuum drying oven at 80 ℃, and drying under-0.2 MPa;
(4) properly grinding the dried material in the step (3) into powder, putting the powder into a cordierite-mullite sagger, heating the powder to 550 ℃ in a box furnace at a temperature of 4 ℃/min, keeping the temperature for 6 hours, taking oxygen as sintering atmosphere, cooling and sieving the powder to obtain the high-nickel ternary cathode material Li1.06Ni0.83Co0.12Mn0.05Zr0.0015Mg0.0012O2。
Example 2
(1) 3.5kg of precursor Ni with a particle size D50 of 11.2 μm were weighed0.83Co0.12Mn0.05(OH)21.68kg of lithium hydroxide monohydrate and 9.5g of nano zirconia are added into a high-speed mixer and mixed for 30min at the rotating speed of 750rpm, wherein a precursor Ni0.83Co0.12Mn0.05(OH)2The molar ratio of the lithium hydroxide monohydrate to the nano zirconia is 1:1.06: 0.002;
(2) putting the mixed material obtained in the step (1) into a cordierite-mullite sagger, putting the sagger into a box furnace, heating to 450 ℃ at a speed of 4 ℃/min, preserving heat for 3h, then heating to 780 ℃ at a speed of 2 ℃/min, preserving heat for 10h, taking oxygen as sintering atmosphere, cooling, discharging, and crushing by using a double-roll machine to obtain a powder material;
(3) measuring 7000mL of phosphoric acid solution with the concentration of 30%, measuring 8.75g of nano magnesium oxide, adding the powder material obtained in the step (2) into the measured phosphoric acid solution, stirring at 65 ℃ according to the rotating speed of 300rpm, adding the measured nano magnesium oxide (the nano magnesium oxide is 0.2% of the mass of the powder material obtained in the step (2)) into the powder material during stirring for 10min, raising the temperature to 85 ℃, continuously stirring until the mixed solution is pasty, then placing the pasty material into a vacuum drying oven at 80 ℃, and drying under-0.2 MPa;
(4) properly grinding the dried material in the step (3) into powder, putting the powder into a cordierite-mullite sagger, heating the powder to 500 ℃ in a box furnace at a speed of 3 ℃/min, keeping the temperature for 7 hours, taking oxygen as sintering atmosphere, cooling and sieving the powder to obtain the high-nickel ternary cathode materialMaterial Li1.06Ni0.83Co0.12Mn0.05Zr0.0015Mg0.0012O2。
Example 3
(1) 3.5kg of precursor Ni with the particle size D50 of 12.5 mu m are weighed0.94Co0.03Mn0.03(OH)21.67kg of lithium hydroxide monohydrate and 13.2g of nano-alumina are added into a high-speed mixer and mixed for 30min at the rotating speed of 750rpm, wherein a precursor Ni0.94Co0.03Mn0.03(OH)2The molar ratio of the lithium hydroxide monohydrate to the nano-alumina is 1:1.05: 0.001;
(2) putting the mixed material obtained in the step (1) into a cordierite-mullite sagger, putting the sagger into a box furnace, heating to 500 ℃ according to the temperature of 3 ℃/min, preserving heat for 5h, then heating to 760 ℃ according to the temperature of 3 ℃/min, preserving heat for 12h, taking oxygen as sintering atmosphere, cooling, discharging, and crushing by using a double-roll machine to obtain a powder material;
(3) measuring 7000mL of 20% phosphoric acid solution, measuring 4.4g of nano yttrium oxide, adding the powder material obtained in the step (2) into the measured phosphoric acid solution, stirring at the rotating speed of 300rpm at 60 ℃, adding the measured nano yttrium oxide (the nano yttrium oxide is 0.2% of the mass of the powder material obtained in the step (2)) into the solution during stirring for 10min, raising the temperature to 90 ℃, continuously stirring until the mixed solution is pasty, then placing the pasty material into a vacuum drying oven at 80 ℃, and drying under-0.2 MPa;
(4) properly grinding the dried material in the step (3) into powder, putting the powder into a cordierite-mullite sagger, heating the powder to 600 ℃ in a box furnace at a temperature of 4 ℃/min, keeping the temperature for 8 hours, taking oxygen as sintering atmosphere, cooling and sieving the powder to obtain the high-nickel ternary cathode material Li1.05Ni0.94Co0.03Mn0.03Al0.0005Y0.0015O2。
Example 4
(1) 3.5kg of precursor Ni with the particle size D50 of 12.5 mu m are weighed0.94Co0.03Mn0.03(OH)21.67kg of lithium hydroxide monohydrate and 13.2g of nano-alumina are added into a high-speed mixer according to the rotating speed of 750rpm is mixed for 30min, wherein, the precursor Ni0.94Co0.03Mn0.03(OH)2The molar ratio of the lithium hydroxide monohydrate to the nano-alumina is 1:1.05: 0.001;
(2) putting the mixed material obtained in the step (1) into a cordierite-mullite sagger, putting the sagger into a box furnace, heating to 500 ℃ according to the temperature of 3 ℃/min, preserving heat for 5h, then heating to 760 ℃ according to the temperature of 3 ℃/min, preserving heat for 12h, taking oxygen as sintering atmosphere, cooling, discharging, and crushing by using a double-roll machine to obtain a powder material;
(3) measuring 7000mL of 20% phosphoric acid solution, weighing 4.4g of nano alumina, adding the powder material obtained in the step (2) into the measured phosphoric acid solution, stirring at the rotating speed of 300rpm at 60 ℃, adding the weighed nano alumina (the nano alumina is 0.2% of the mass of the powder material obtained in the step (2)) into the solution during stirring for 10min, raising the temperature to 90 ℃, continuously stirring until the mixed solution is pasty, then placing the pasty material into a vacuum drying oven at 80 ℃, and drying under-0.2 MPa;
(4) properly grinding the dried material in the step (3) into powder, putting the powder into a cordierite-mullite sagger, heating the powder to 650 ℃ in a box furnace at a temperature of 4 ℃/min, keeping the temperature for 8 hours, taking oxygen as sintering atmosphere, cooling and sieving the powder to obtain the high-nickel ternary cathode material Li1.05Ni0.94Co0.03Mn0.03Al0.0025O2。
Comparative example 1
The procedure of example 1 was followed, except that in step (3), a 35% phosphoric acid solution was used instead of the 10% phosphoric acid solution.
Comparative example 2
The procedure of example 1 was followed, except that in step (3), a phosphoric acid solution having a concentration of 5% was used instead of the 10% phosphoric acid solution.
Comparative example 3
(1) 3.5kg of precursor Ni with a particle size D50 of 11.2 μm were weighed0.83Co0.12Mn0.05(OH)21.68kg of lithium hydroxide monohydrate and 9.5g of nano-zirconia were added to a high-speed mixer and mixed at 750rpm for 30min, wherein the precursor is Ni0.83Co0.12Mn0.05(OH)2The molar ratio of the lithium hydroxide monohydrate to the nano zirconia is 1:1.06: 0.002;
(2) putting the mixed material obtained in the step (1) into a cordierite-mullite sagger, putting the sagger into a box furnace, heating to 500 ℃ at a speed of 3 ℃/min, keeping the temperature for 5 hours, heating to 800 ℃ at a speed of 3 ℃/min, keeping the temperature for 12 hours, taking oxygen as sintering atmosphere, cooling, discharging, and crushing by using a double-roll machine to obtain a powder material;
(3) weighing 8.75g of commercial magnesium metaphosphate, adding into the powder material obtained in the step (2), and then mixing for 30min in a high-speed mixer at the rotating speed of 600 rpm;
(4) properly grinding the material obtained in the step (3) into powder, putting the powder into a cordierite-mullite sagger, heating the powder to 550 ℃ in a box furnace at a speed of 4 ℃/min, keeping the temperature for 6 hours, taking oxygen as sintering atmosphere, cooling and sieving the powder to obtain the high-nickel ternary cathode material Li1.06Ni0.83Co0.12Mn0.05Zr0.0015Mg0.0012O2。
Comparative example 4
(1) 3.5kg of precursor Ni with a particle size D50 of 11.2 μm were weighed0.83Co0.12Mn0.05(OH)21.68kg of lithium hydroxide monohydrate and 9.5g of nano zirconia are added into a high-speed mixer and mixed for 30min at the rotating speed of 750rpm, wherein a precursor Ni0.83Co0.12Mn0.05(OH)2The molar ratio of the lithium hydroxide monohydrate to the nano zirconia is 1:1.06: 0.002;
(2) putting the mixed material obtained in the step (1) into a cordierite-mullite sagger, putting the sagger into a box furnace, heating to 500 ℃ at a speed of 3 ℃/min, keeping the temperature for 5 hours, heating to 800 ℃ at a speed of 3 ℃/min, keeping the temperature for 12 hours, taking oxygen as sintering atmosphere, cooling, discharging, and crushing by using a double-roll machine to obtain a powder material;
(3) adding the powder material obtained in the step (2) and 1.9g of nano magnesium oxide into a high-speed mixer, and mixing for 30min at the rotating speed of 600 rpm;
(4) properly grinding the dried material in the step (3) into powder, filling the powder into a cordierite-mullite sagger,heating to 550 ℃ at a rate of 4 ℃/min in a box furnace, keeping the temperature for 6h, taking oxygen as sintering atmosphere, cooling, and sieving to obtain the high-nickel ternary cathode material Li1.06Ni0.83Co0.12Mn0.05Zr0.0015Mg0.0012O2。
Test example
1. The high nickel ternary materials prepared in examples 1-3 and comparative examples 1-2 were subjected to morphology analysis in a scanning electron microscope.
Scanning electron micrographs of the high-nickel ternary materials prepared in examples 1-3 and comparative examples 1-2 are shown in fig. 1-5, respectively, and it can be seen that the high-nickel ternary materials in examples 1-3 have a clear surface on which uniform coating of nano-scale particles can be seen, and that the nano-scale particles in comparative examples 1-2 have extremely non-uniform coating and form islands.
2. The samples prepared in examples 1 to 4 and comparative examples 1 to 4 were used to prepare CR2025 type coin cells using a lithium plate as a negative electrode, and the discharge capacities were measured at 0.1C and 1C in a voltage range of 3.0 to 4.3V, and the specific data are shown in table 1.
3. The high nickel ternary materials prepared in examples 1 to 3 and comparative examples 1 to 3 were prepared into full cells, and the cycle performance at room temperature and 45 ℃ was tested, as shown in fig. 6 to 7, it can be found that the cycle performance of the high nickel ternary materials prepared in the examples is due to the materials prepared in the comparative examples; therefore, the high-nickel ternary material prepared by the method has more excellent cycle performance under the same test condition.
TABLE 1
The results in table 1 show that the high nickel ternary material prepared by the method of the embodiment of the present invention has better electrochemical properties such as charge-discharge capacity, first discharge efficiency, 1C discharge capacity, etc. at 4.3V than the comparative example.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A preparation method of a high-nickel ternary cathode material is characterized by comprising the following steps:
s1, preparing Ni-Co-Mn precursorxCoyMnz(OH)2And the molar ratio of the lithium source to the first nano oxide is 1: 1.0-1.06: mixing at a ratio of 0.001-0.01;
s2, sintering the mixed material obtained in the step S1 for the first time in an oxygen atmosphere, cooling and crushing;
s3, adding the powder material obtained in the step S2 into a phosphoric acid solution with the concentration of 10-30 mass%, stirring for the first time at a first heating temperature, adding a second nano oxide, stirring for the second time at a second heating temperature to form pasty slurry, filtering, and drying;
s4, grinding the material obtained in the step S3, then carrying out secondary sintering in an oxygen atmosphere, cooling and sieving to obtain the high-nickel ternary cathode material LiaNixCoyMnzMbNcO2M, N are cationic elements in the first nano-oxide and the second nano-oxide, respectively, M, N are the same or different,
wherein a is more than 1 and less than 1.08, x is more than 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than 0 and less than 0.2, b is more than 0 and less than 0.2, c is more than 0 and less than 0.2, and x + y + z is 1.
2. The method of claim 1, wherein Ni is present in the nickel-cobalt-manganese precursorxCoyMnz(OH)2And the high-nickel ternary cathode material LiaNixCoyMnzMbNcO2In the formula, a is more than 1 and less than 1.03; x is more than 0.8 and less than 0.95; y is more than 0.03 and less than 0.15; z is more than 0.03 and less than 0.15.
3. The method of claim 1 or 2, wherein in step S1, the nickel cobalt manganese precursor NixCoyMnz(OH)2The particle size of (A) is 10-12 μm.
4. The method according to claim 1 or 2, wherein in step S1, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium phosphate, or lithium chloride;
preferably, in step S1, the first nano-oxide is one or more of Al, Zr, Ti, Mg, Zn, W, Y or B metal oxides.
5. The method as claimed in claim 1, wherein in step S1, the mixing speed is 600-900rpm, and the mixing time is 15-30 min.
6. The method of claim 1, wherein in step S2, the first sintering process is: heating to 400-800 ℃ at a heating rate of 3-5 ℃/min, and keeping the temperature for 2-6h, and then heating to 750-800 ℃ at a heating rate of 1-3 ℃/min, and keeping the temperature for 10-14 h.
7. The method of claim 6, wherein in step S3, the second nano-oxide is one or more of nano-magnesium oxide, nano-aluminum oxide, nano-yttrium oxide or nano-strontium oxide;
preferably, in step S3, the amount of the second nano oxide added is 0.1 to 0.35 mass% of the powder material obtained in step S2.
8. The method according to claim 1, wherein in step S3, the first heating temperature is 60-70 ℃ and the second heating temperature is 70-90 ℃.
9. The method according to claim 1, wherein in step S3, the time of the first stirring is 10-20 min;
preferably, the rate of the first agitation and the second agitation is 150-.
10. The method according to any one of claims 1, 8 and 9, wherein in step S4, the second sintering process is: heating to 500-600 ℃ at the heating rate of 3-5 ℃/min and preserving the heat for 6-8 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110888058.4A CN113745500B (en) | 2021-08-03 | 2021-08-03 | Preparation method of high-nickel ternary positive electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110888058.4A CN113745500B (en) | 2021-08-03 | 2021-08-03 | Preparation method of high-nickel ternary positive electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113745500A true CN113745500A (en) | 2021-12-03 |
| CN113745500B CN113745500B (en) | 2023-05-05 |
Family
ID=78729999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110888058.4A Active CN113745500B (en) | 2021-08-03 | 2021-08-03 | Preparation method of high-nickel ternary positive electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113745500B (en) |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011043255A1 (en) * | 2009-10-06 | 2011-04-14 | 国立大学法人長岡技術科学大学 | Positive electrode material for lithium ion secondary battery, and process for production thereof |
| CN102479952A (en) * | 2010-11-23 | 2012-05-30 | 清华大学 | Lithium ion battery electrode composite material and preparation method and battery thereof |
| US20180351199A1 (en) * | 2015-12-02 | 2018-12-06 | Nec Corporation | Positive electrode active substance for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery, and methods for producing these |
| CN109244436A (en) * | 2018-11-20 | 2019-01-18 | 宁波容百新能源科技股份有限公司 | A kind of nickelic positive electrode and preparation method thereof and a kind of lithium ion battery |
| CN109461907A (en) * | 2018-10-09 | 2019-03-12 | 郑州中科新兴产业技术研究院 | A kind of preparation method of nickelic tertiary cathode material |
| CN109713284A (en) * | 2018-12-29 | 2019-05-03 | 蜂巢能源科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof and battery |
| US20190140265A1 (en) * | 2017-11-08 | 2019-05-09 | Samsung Electronics Co., Ltd. | Positive electrode active material, methods for the manufacture thereof, and electrochemical cell comprising the positive electrode active material |
| CN110061203A (en) * | 2019-03-19 | 2019-07-26 | 北京泰丰先行新能源科技有限公司 | A kind of lithium anode material and preparation method thereof of the compound metaphosphate cladding of rare earth |
| CN110137488A (en) * | 2019-05-28 | 2019-08-16 | 郑州中科新兴产业技术研究院 | A kind of nickelic positive electrode of secondary lithium batteries and preparation method thereof |
| CN110190254A (en) * | 2019-05-15 | 2019-08-30 | 华南理工大学 | A kind of preparation method of lithium phosphate coated lithium ion battery tertiary cathode material |
| CN110400929A (en) * | 2019-09-02 | 2019-11-01 | 中南大学 | A kind of metal-doped ternary positive electrode active material of Phosphate coating and its preparation and application |
| CN110534733A (en) * | 2019-07-21 | 2019-12-03 | 浙江美都海创锂电科技有限公司 | A kind of large single crystal lithium ion battery nickle cobalt lithium manganate method for preparing anode material |
| KR20200034298A (en) * | 2018-09-21 | 2020-03-31 | 세종대학교산학협력단 | Method for producing positive electrode active material having coating layer, positive electrode prepared therefrom, and sodium ion secondary battery containing the same |
| CN111446434A (en) * | 2020-04-23 | 2020-07-24 | 华鼎国联四川电池材料有限公司 | Metaphosphate modified anode material and preparation method thereof |
| CN111916724A (en) * | 2020-08-05 | 2020-11-10 | 浙江中金格派锂电产业股份有限公司 | Preparation method and application of washing-free high-nickel monocrystal nickel cobalt lithium manganate positive electrode material |
| CN112080800A (en) * | 2020-05-26 | 2020-12-15 | 宜宾锂宝新材料有限公司 | Modification method of single crystal ternary cathode material |
| CN112811403A (en) * | 2020-12-31 | 2021-05-18 | 南通瑞翔新材料有限公司 | Mg/Ti co-doped Li3PO4Coated high-nickel ternary cathode material and preparation method thereof |
-
2021
- 2021-08-03 CN CN202110888058.4A patent/CN113745500B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011043255A1 (en) * | 2009-10-06 | 2011-04-14 | 国立大学法人長岡技術科学大学 | Positive electrode material for lithium ion secondary battery, and process for production thereof |
| CN102479952A (en) * | 2010-11-23 | 2012-05-30 | 清华大学 | Lithium ion battery electrode composite material and preparation method and battery thereof |
| US20180351199A1 (en) * | 2015-12-02 | 2018-12-06 | Nec Corporation | Positive electrode active substance for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery, and methods for producing these |
| US20190140265A1 (en) * | 2017-11-08 | 2019-05-09 | Samsung Electronics Co., Ltd. | Positive electrode active material, methods for the manufacture thereof, and electrochemical cell comprising the positive electrode active material |
| KR20200034298A (en) * | 2018-09-21 | 2020-03-31 | 세종대학교산학협력단 | Method for producing positive electrode active material having coating layer, positive electrode prepared therefrom, and sodium ion secondary battery containing the same |
| CN109461907A (en) * | 2018-10-09 | 2019-03-12 | 郑州中科新兴产业技术研究院 | A kind of preparation method of nickelic tertiary cathode material |
| CN109244436A (en) * | 2018-11-20 | 2019-01-18 | 宁波容百新能源科技股份有限公司 | A kind of nickelic positive electrode and preparation method thereof and a kind of lithium ion battery |
| CN109713284A (en) * | 2018-12-29 | 2019-05-03 | 蜂巢能源科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof and battery |
| CN110061203A (en) * | 2019-03-19 | 2019-07-26 | 北京泰丰先行新能源科技有限公司 | A kind of lithium anode material and preparation method thereof of the compound metaphosphate cladding of rare earth |
| CN110190254A (en) * | 2019-05-15 | 2019-08-30 | 华南理工大学 | A kind of preparation method of lithium phosphate coated lithium ion battery tertiary cathode material |
| CN110137488A (en) * | 2019-05-28 | 2019-08-16 | 郑州中科新兴产业技术研究院 | A kind of nickelic positive electrode of secondary lithium batteries and preparation method thereof |
| CN110534733A (en) * | 2019-07-21 | 2019-12-03 | 浙江美都海创锂电科技有限公司 | A kind of large single crystal lithium ion battery nickle cobalt lithium manganate method for preparing anode material |
| CN110400929A (en) * | 2019-09-02 | 2019-11-01 | 中南大学 | A kind of metal-doped ternary positive electrode active material of Phosphate coating and its preparation and application |
| CN111446434A (en) * | 2020-04-23 | 2020-07-24 | 华鼎国联四川电池材料有限公司 | Metaphosphate modified anode material and preparation method thereof |
| CN112080800A (en) * | 2020-05-26 | 2020-12-15 | 宜宾锂宝新材料有限公司 | Modification method of single crystal ternary cathode material |
| CN111916724A (en) * | 2020-08-05 | 2020-11-10 | 浙江中金格派锂电产业股份有限公司 | Preparation method and application of washing-free high-nickel monocrystal nickel cobalt lithium manganate positive electrode material |
| CN112811403A (en) * | 2020-12-31 | 2021-05-18 | 南通瑞翔新材料有限公司 | Mg/Ti co-doped Li3PO4Coated high-nickel ternary cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘大亮等: "高镍三元正极材料后处理降碱工艺", 《电池》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113745500B (en) | 2023-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111490243B (en) | Composite positive electrode material for lithium ion battery, preparation method and application thereof | |
| CN112952049A (en) | Method for repairing surface structure of high-nickel anode material, high-nickel anode material obtained by method and lithium ion battery | |
| CN110931768A (en) | Ternary positive electrode material of high-nickel monocrystal lithium ion battery and preparation method | |
| CN112928252A (en) | Sodium-ion battery positive electrode material and preparation method and application thereof | |
| CN110649252A (en) | Ternary material LiNi of lithium battery0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3Method (2) | |
| CN110863245A (en) | Ternary cathode material, preparation method thereof, lithium ion battery and electric automobile | |
| CN113571679A (en) | Spinel oxide coated lithium-rich manganese-based positive electrode material | |
| CN114551835A (en) | Ultrahigh nickel quaternary positive electrode material and preparation method and application thereof | |
| CN113644274B (en) | O2 type lithium ion battery anode material and preparation method and application thereof | |
| CN114843497A (en) | Modified high-nickel ternary cathode material and preparation method thereof | |
| CN111293286A (en) | Coating modified lithium ion battery anode material and preparation method thereof | |
| CN113488620A (en) | Ternary positive electrode precursor and preparation method thereof, ternary positive electrode material and preparation method thereof, and lithium ion battery | |
| CN116565180A (en) | High tap density lithium iron phosphate positive electrode material, and preparation method and application thereof | |
| CN114937779B (en) | High-nickel monocrystal ternary positive electrode material for lithium ion battery and preparation method thereof | |
| CN115663134A (en) | Novel surface nano-coating and gradient doping integrated modified ultra-high nickel ternary cathode material and preparation method thereof | |
| CN110867575A (en) | Ternary cathode material, preparation method thereof, lithium ion battery and electric automobile | |
| CN112599736B (en) | Boron-doped lithium phosphate coated lithium ion battery positive electrode material and preparation method thereof | |
| CN113745500B (en) | Preparation method of high-nickel ternary positive electrode material | |
| CN113707870A (en) | Cobalt-free cathode material and preparation method and application thereof | |
| CN109037607B (en) | Preparation method of coated lithium manganate composite material | |
| CN112086679A (en) | High-nickel ternary material, surface modification method and lithium ion battery | |
| CA2803990A1 (en) | Lithium iron silicate cathode material and its production | |
| CN114695875A (en) | High-capacity single crystal ternary cathode material and preparation method thereof | |
| Sun et al. | Preparation of CeO2-coated Li1. 2Mn0. 54Co0. 13Ni0. 13O2 as cathode materials for Lithium Ion Batteries | |
| CN111293285A (en) | Coating modified lithium ion battery anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 435100 No. 66 Changle Avenue, Luojiaqiao Street, Daye City, Huangshi City, Hubei Province Applicant after: Hubei Rongtong High tech Advanced Materials Group Co.,Ltd. Address before: 435100 No. 66 Changle Avenue, Luojiaqiao Street, Daye City, Huangshi City, Hubei Province Applicant before: HUBEI RT ADVANCED MATERIALS Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |