CN114477314A - Preparation method and application of nickel-cobalt-manganese ternary cathode material - Google Patents
Preparation method and application of nickel-cobalt-manganese ternary cathode material Download PDFInfo
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000010406 cathode material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 17
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 17
- 239000012452 mother liquor Substances 0.000 claims abstract description 16
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012265 solid product Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000007774 positive electrode material Substances 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ALVYXLXQMLKBEB-UHFFFAOYSA-N cobalt(2+) manganese(2+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mn+2].[Co+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] ALVYXLXQMLKBEB-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 9
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 150000001768 cations Chemical class 0.000 abstract description 6
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 239000013078 crystal Substances 0.000 description 20
- 238000005303 weighing Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229940023462 paste product Drugs 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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
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Abstract
The invention relates to the technical field of preparation of battery anode materials, and particularly discloses a preparation method and application of a nickel-cobalt-manganese ternary anode material. The method comprises the following steps: (1) adding a precipitator into the solution containing nickel ions, cobalt ions and manganese ions to obtain reaction mother liquor. (2) Carrying out hydrothermal reaction on the reaction mother liquor, and separating out a solid product after the hydrothermal reaction is finished to obtain a precursor material NixCoyMn(1‑x‑y)(HO)2Wherein x is more than or equal to 0.6 and less than or equal to 0.9, and y is more than or equal to 0.05 and less than or equal to 0.2. (3) Subjecting the precursor material and a lithium source to different temperature stages under an oxygen atmosphereAnd (4) carrying out sectional calcination to obtain the nickel-cobalt-manganese ternary cathode material (NCM). According to the invention, a novel ternary material preparation process is constructed by utilizing the intrinsic structure of a specific material, the better ion diffusion channel can well inhibit the cation mixed-arrangement effect, the lithium-nickel mixed-arrangement effect of the ternary material is reduced, and the rate capability of the ternary material is effectively improved.
Description
Technical Field
The invention relates to the technical field of preparation of battery anode materials, in particular to a preparation method and application of a nickel-cobalt-manganese ternary anode material.
Background
The information in this background section is disclosed to enhance understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms part of the prior art already known to a person of ordinary skill in the art.
The positive electrode material is the main limiting factor of the electrochemical performance of the lithium battery, and the material property of the positive electrode material directly determines the energy density, the service life and the safety of the battery, thereby influencing the comprehensive performance of the battery. Meanwhile, the proportion of the anode material in the cost of the lithium battery material is 30-40%, and the cost directly determines the overall cost of the battery, so that the anode material has a significant effect in the lithium battery, and the development trend of the lithium battery industry is directly led.
Currently, the mainstream commercial lithium ion battery cathode material comprises a lithium iron phosphate, lithium manganate and nickel cobalt manganese ternary cathode material. The ternary cathode material has the advantages of high and low temperature performance, high energy density and excellent cycle performance, and occupies the leading position of the cathode material, and the research and the leading technical changes in the fields of high nickel and high voltage are revolutionary. With the improvement of the standard of new energy automobiles on endurance mileage, the traditional lithium iron phosphate power battery gradually gives way to the ternary positive electrode material battery.
The high price of cobalt in the ternary material can increase the cost of the battery, while the low-cobalt high-nickel material is the main flow direction, but with the increase of the nickel content and the reduction of the cobalt content, the problem of poor cycle stability of the material becomes the biggest problem, the serious cation mixed discharge phenomenon can cause the rapid deterioration of the thermal stability and the structural stability of the material, and irreversible phase change accumulation can cause the defects of low first charge-discharge efficiency, low cycle life and the like. The reduction of intrinsic conductivity, stability and service life of the material caused by the cation mixed-discharging effect becomes a difficult point which must be solved by the market of the current ternary cathode material.
Although supported by clear market demands, the ternary cathode material has a serious cation mixed-discharging effect and the problems of irreversible phase change and material microcracks in the circulating process, so that the rate capability and the circulating stability of the ternary material are reduced. In addition, due to the fact that the prices of lithium and cobalt are high, the price of cobalt is unstable in recent years, the sudden rise and fall amplitude can reach 200%, and the ternary cathode material faces the influence of intrinsic characteristics of materials and the price of raw materials.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method and application of a nickel-cobalt-manganese ternary positive electrode material. According to the invention, a novel ternary material preparation process is constructed by utilizing the intrinsic structure of a specific material, the better ion diffusion channel can well inhibit the cation mixed-arrangement effect, and the lithium-nickel mixed-arrangement effect of the ternary material is reduced, so that the rate capability of the ternary material is effectively improved. In order to achieve the purpose, the invention discloses the following technical scheme.
In a first aspect of the invention, a preparation method of a nickel-cobalt-manganese ternary cathode material is disclosed, which comprises the following steps:
(1) adding a precipitator into the solution containing nickel ions, cobalt ions and manganese ions to obtain reaction mother liquor.
(2) Carrying out hydrothermal reaction on the reaction mother liquor, and separating out a solid product after the hydrothermal reaction is finished to obtain a precursor material NixCoyMn(1-x-y)(HO)2Wherein x is more than or equal to 0.6 and less than or equal to 0.9, and y is more than or equal to 0.05 and less than or equal to 0.2.
(3) And (3) performing sectional calcination on the precursor material and the lithium source at different temperature stages in an oxygen atmosphere to obtain the nickel-cobalt-manganese ternary positive electrode material (NCM).
Further, in the step (1), the nickel ions are provided by at least one of nickel nitrate, nickel acetate, nickel carbonate, nickel hydroxide and the like. The cobalt ions are provided by at least one of cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt hydroxide and the like. The manganese ions are provided by at least one of manganese nitrate, manganese acetate, manganese carbonate, manganese hydroxide and the like.
In step (1), the ratio of the nickel ions, the cobalt ions and the manganese ions is set according to the atomic number ratio of each metal element in the precursor material in step (2).
Further, in the step (1), the precipitating agent includes any one of urea, ammonia water, ammonium fluoride and the like. Optionally, the molar ratio of precipitant to metal ion is in the range of 1: 1 to 1: 2, the metal ions refer to the sum of nickel ions, cobalt ions and manganese ions. In the invention, the effect of the precipitant comprises promoting the codeposition of transition metal ions and regulating the pH value of the solution to be in an alkaline range.
Further, in the step (1), the solution is a mixed solution of ethanol and water. Optionally, the volume ratio of ethanol to water is in the range of 1: 3 to 1: 4.
further, in the step (2), the temperature of the hydrothermal reaction is 150-200 ℃, and the reaction time is 5-15 h. In the hydrothermal reaction process, the nickel ions, the cobalt ions and the manganese ions form alpha-type nickel-cobalt-manganese trimetal layered hydroxide to obtain the precursor material NixCoyMn(1-x-y)(HO)2The precursor material has large interlayer spacing and can be reserved in the final cathode material, and the structural stability and the electrochemical performance of the cathode material are effectively improved.
Further, in the step (3), the molar ratio of the precursor material to the lithium source is 1: 1.02-1: 1.05. optionally, the lithium source includes at least one of lithium hydroxide solids, lithium acetate solids, lithium nitrate solids, lithium carbonate solids, and the like.
Further, in the step (3), the precursor material and the lithium source are uniformly mixed by ball milling or liquid phase dispersion, and then the step calcination is performed. During the calcination process, oxidized precursor particles react with a lithium source to form primary particles, and the primary particles are further agglomerated to form secondary particles, namely the cathode material. The ion diffusion channel of the secondary particle structure part for retaining the precursor provides powerful support for improving the rate capability of the anode material.
Further, in the step (3), the stage calcination includes: calcining at 350-450 ℃ for 150-200 min, heating to 700-850 ℃ and continuing calcining for 1100-1300 min, wherein the precursor is presintered at 300-500 ℃ to facilitate the synthesis of the NCM anode material with a good-order layered structure, and the calcination at high temperature of 700-900 ℃ determines the Li of the synthesized NCM anode material+/Ni2+Degree of shuffling and crystal structure integrity.
In a second aspect of the invention, the application of the nickel-cobalt-manganese ternary cathode material of the lithium ion battery prepared by the method in an energy storage device is disclosed.
Compared with the prior art, the invention has the following beneficial and unique effects:
(1) the nickel-cobalt-manganese ternary cathode material has a secondary particle structure with a larger ion transmission channel, and the rate capability of the ternary cathode material is effectively improved. This is due to: by preparing alpha type nickel-cobalt-manganese trimetal layered hydroxide (chemical formula Ni)xCoyMn(1-x-y)(HO)2) As a precursor, a framework for ion transfer is constructed between petal-shaped layers of the precursor, and the nickel-cobalt-manganese ternary cathode material is obtained by mixing the precursor with a lithium source and calcining at high temperature, so that the obtained ternary cathode material has a lower lithium-nickel mixed-discharge effect, the cation mixed-discharge effect of the low-cobalt high-nickel material is effectively relieved, the cycle life and the conductivity of the material are improved, and the nickel-cobalt-manganese ternary cathode material prepared by the method has higher rate capability while keeping higher capacity.
(2) The nickel-cobalt-manganese ternary positive electrode material prepared by the method builds an ionic nickel-cobalt-manganese structure with unequal valence states in a material crystal lattice through sectional calcination, so that the valence state of transition metal ions in the final positive electrode material is increased or decreased, holes or electrons are generated, the energy band structure of the material is changed, and the intrinsic electronic conductivity is improved. Meanwhile, the Li/Ni mixed arrangement degree in the anode material is reduced, the crystal lattice is supported, the structure of the anode material is stabilized, and the electrochemical cycle performance and the thermal stability of the nickel-cobalt-manganese ternary anode material prepared by the invention are effectively improved.
(3) The alpha-type nickel-cobalt-manganese ternary positive electrode material obtained by design is used as a precursor, and the precursor has a large interlayer spacing, so that more anions and water molecules can be contained in the large interlayer, and the precursor still has the characteristic of large interlayer spacing after high-temperature calcination, and a channel is provided for lithium ions to migrate in the electrode material in the charging and discharging process, so that the ion diffusion rate of the positive electrode material is improved, the rate capability and the cycle performance of the nickel-cobalt-manganese ternary positive electrode material prepared by the invention are obviously improved, and the practicability of the positive electrode material is greatly improved. The test results show that: the nickel-cobalt-manganese ternary cathode material prepared by the embodiment of the invention has the advantages of stable structure, excellent cycle performance, high thermal stability and rate capability, and stable low rate performance after large-current charging and discharging.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is an SEM image of an α -type nickel cobalt manganese layered hydroxide synthesized in the following first example.
Fig. 2 is an SEM image of the nickel-cobalt-manganese cathode material synthesized in the following first example.
Fig. 3 is a graph of cycle performance tests of nickel-cobalt-manganese cathode materials synthesized by the following first and second examples at different current densities.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described in this invention are exemplary only. The invention will now be further described with reference to the drawings and detailed description of the specification.
First embodiment
A preparation method of a nickel-cobalt-manganese ternary cathode material comprises the following steps:
(1) according to the molar ratio of nickel ions to cobalt ions to manganese ions of 6: 2: 2, weighing Ni (NO)3)2·6H2O crystal 0.4852g, weighing Co (NO)3)2·6H20.4852g of O crystal, and measuring Mn (NO) with mass fraction of 50%3)20.5965 g of solution. The three raw materials and 0.6g of urea are added into a mixed solvent (48 ml of ethanol and 12ml of water), and the mixture is stirred to completely dissolve the crystals, so that reaction mother liquor is obtained.
(2) And (2) transferring the reaction mother liquor obtained in the step (1) into the inner liner of a reaction kettle, reacting for 480min at 180 ℃ in a homogeneous reaction furnace, cleaning a solid product by using a suction filtration and centrifugation method after the reaction is finished, and then drying the solid product in a blast oven at 70 ℃ for 12 h. Ball-milling the dried solid in a ball mill at the rotating speed of 800rpm for 8 hours, and sieving the grinding powder with a 500-mesh sieve to obtain a precursor Ni6Co2Mn2(HO)2And (3) powder.
(3) 0.9635g of precursor powder and 0.4406g of lithium hydroxide monohydrate powder were weighed, mixed by dispersing the solution in anhydrous ethanol uniformly and sufficiently, dried for 6 hours, and then the mixture was spread in a porcelain boat. Introducing oxygen with the purity of 99.9 percent into the tube, firstly calcining at 450 ℃ for 180min, then raising the temperature to 735 ℃ for 1200min, and then naturally cooling to room temperature and taking out. And ball-milling the sintered nickel-cobalt-manganese ternary material in a ball mill for 24 hours, and then sieving the sintered nickel-cobalt-manganese ternary material with a 800-mesh sieve to obtain nickel-cobalt-manganese ternary positive electrode material powder (marked as NCM 622).
Second embodiment
A preparation method of a nickel-cobalt-manganese ternary cathode material comprises the following steps:
(1) according to the molar ratio of nickel ions to cobalt ions to manganese ions of 8: 1: 1, weighing Ni (NO)3)2·6H2O crystal 1.7400g, weighing Co (NO)3)2·6H20.2177g of O crystal, and measuring Mn (NO) with mass fraction of 50%3)20.2627 g of solution. The three raw materials and 0.6g of urea are added into a mixed solvent (48 ml of ethanol and 12ml of water), and the mixture is stirred to completely dissolve the crystals, so that reaction mother liquor is obtained.
(2) And (2) transferring the reaction mother liquor obtained in the step (1) into the inner liner of a reaction kettle, reacting for 480min at 180 ℃ in a homogeneous reaction furnace, cleaning a solid product by using a suction filtration and centrifugation method after the reaction is finished, and then drying the solid product in a blast oven for 24h at 50 ℃. Ball-milling the dried solid in a ball mill at the rotating speed of 800rpm for 8 hours, and sieving the grinding powder with a 500-mesh sieve to obtain a precursor Ni8Co1Mn1(HO)2And (3) powder.
(3) 1.0149 g of precursor powder and 0.4406g of monohydrate lithium hydroxide powder were weighed, mixed uniformly and sufficiently by liquid phase dispersion using absolute ethyl alcohol, and the mixture was spread in a porcelain boat after drying for 6 hours. Introducing oxygen with the purity of 99.9% into the tube, calcining at 450 ℃ for 180min, then raising the temperature to 735 ℃ for 1200min, then naturally cooling to room temperature, and taking out. And ball-milling the sintered nickel-cobalt-manganese ternary material in a ball mill for 24 hours, and then sieving the sintered nickel-cobalt-manganese ternary material with a 800-mesh sieve to obtain nickel-cobalt-manganese ternary positive electrode material powder (marked as NCM 811).
Third embodiment
A preparation method of a nickel-cobalt-manganese ternary cathode material comprises the following steps:
(1) according to the molar ratio of nickel ions to cobalt ions to manganese ions of 9: 0.5: 0.5, weighing Ni (NO)3)2·6H2O crystal 1.7400g, weighing Co (NO)3)2·6H20.0967g of O crystal, and measuring Mn (NO) with mass fraction of 50%3)20.1190g of solution. The three raw materials and 0.6g of urea are added into a mixed solvent (48 ml of ethanol and 12ml of water), and the mixture is stirred to completely dissolve the crystals, so that reaction mother liquor is obtained.
(2) And (2) transferring the reaction mother liquor obtained in the step (1) into the inner liner of a reaction kettle, reacting for 480min at 180 ℃ in a homogeneous reaction furnace, cleaning a solid product by using a suction filtration and centrifugation method after the reaction is finished, and then drying the solid product in a blast oven for 20h at 50 ℃. Ball-milling the dried solid in a ball mill at the rotating speed of 800rpm for 8 hours, and sieving the grinding powder with a 500-mesh sieve to obtain a precursor Ni9Co0.5Mn0.5(HO)2And (3) powder.
(3) 1.1013g of precursor powder and 0.4406g of monohydrate lithium hydroxide powder were weighed, mixed uniformly and sufficiently by liquid phase dispersion using absolute ethyl alcohol, and the mixture was spread in a porcelain boat after drying for 6 hours. Introducing oxygen with the purity of 99.9 percent into the tube, putting the porcelain boat into a muffle furnace, firstly calcining at 450 ℃ for 180min, then raising the temperature to 735 ℃ for 1200min, then naturally cooling to room temperature and taking out. And ball-milling the sintered nickel-cobalt-manganese ternary material in a ball mill for 24 hours, and then sieving the sintered nickel-cobalt-manganese ternary material with a 800-mesh sieve to obtain nickel-cobalt-manganese ternary cathode material powder.
Fourth embodiment
A preparation method of a nickel-cobalt-manganese ternary cathode material comprises the following steps:
(1) according to the molar ratio of nickel ions to cobalt ions to manganese ions of 7: 1: 2, weighing Ni (CH)3COO)2·4H2O crystal, weighing Co (CH)3COO)2·4H2O crystal, measuring Mn (CH) with mass fraction of 50%3COO)2·4H2And (4) O solution. Adding the three raw materials and ammonium fluoride (the molar ratio of the ammonium fluoride to nickel, cobalt and manganese ions is 1: 2) into a mixed solvent (36 ml of ethanol and 12ml of water), and stirring to completely dissolve the crystals to obtain a reaction mother liquor.
(2) And (2) transferring the reaction mother liquor obtained in the step (1) into the inner liner of a reaction kettle, reacting in a homogeneous reaction furnace at 150 ℃ for 900min, cleaning the solid product by using a suction filtration and centrifugation method after the reaction is finished, and then drying the solid product in a blast oven at 50 ℃ for 20 h. Ball-milling the dried solid in a ball mill at the rotating speed of 800rpm for 8 hours, and sieving the grinding powder with a 500-mesh sieve to obtain a precursor Ni9Co0.5Mn0.5(HO)2And (3) powder.
(3) According to the following steps of 1: weighing the precursor powder prepared in the step (2) and a lithium acetate solid according to the molar ratio of 1.02, uniformly and fully mixing by using absolute ethyl alcohol for liquid phase dispersion, drying for 6 hours, and then spreading the mixture in a porcelain boat. Introducing oxygen with the purity of 99.9 percent into the tube, placing the porcelain boat in a muffle furnace, firstly calcining at 350 ℃ for 200min, then raising the temperature to 700 ℃ for 1300min, then naturally cooling to room temperature and taking out. And ball-milling the sintered nickel-cobalt-manganese ternary material in a ball mill for 24 hours, and then sieving the sintered nickel-cobalt-manganese ternary material with a 800-mesh sieve to obtain nickel-cobalt-manganese ternary cathode material powder.
Fifth embodiment
A preparation method of a nickel-cobalt-manganese ternary cathode material comprises the following steps:
(1) according to the molar ratio of nickel ions to cobalt ions to manganese ions of 8: 1.5: 0.5, weighing Ni (OH)2Crystal, weighing Co (OH)2Taking the crystal and Mn (OH) with the mass fraction of 50%2And (3) solution. Adding the three raw materials and ammonia water (the molar ratio of the ammonia water to nickel, cobalt and manganese ions is 1: 1) into a mixed solvent (36 ml of ethanol and 12ml of water), and stirring to completely dissolve the crystals to obtain a reaction mother liquor.
(2) And (2) transferring the reaction mother liquor obtained in the step (1) into the inner liner of a reaction kettle, reacting for 300min at 200 ℃ in a homogeneous reaction furnace, cleaning the solid product by using a suction filtration and centrifugation method after the reaction is finished, and then drying the solid product in a blast oven for 20h at 50 ℃. Ball-milling the dried solid in a ball mill at the rotating speed of 800rpm for 8 hours, and sieving the grinding powder with a 500-mesh sieve to obtain a precursor Ni9Co0.5Mn0.5(HO)2And (3) powder.
(3) According to the following steps of 1: weighing the precursor powder prepared in the step (2) and the lithium nitrate solid according to the molar ratio of 1.05, uniformly and fully mixing by using absolute ethyl alcohol for liquid phase dispersion, drying for 6 hours, and then spreading the mixture in a porcelain boat. Introducing oxygen with the purity of 99.9 percent into the tube, placing the porcelain boat into a muffle furnace, firstly calcining at 400 ℃ for 150min, then raising the temperature to 850 ℃ and calcining for 1100min, then naturally cooling to room temperature and taking out. And ball-milling the sintered nickel-cobalt-manganese ternary material in a ball mill for 24 hours, and then sieving the sintered nickel-cobalt-manganese ternary material with a 800-mesh sieve to obtain nickel-cobalt-manganese ternary cathode material powder.
Performance testing
Mixing the nickel-cobalt-manganese ternary positive electrode material powder prepared in the first and second embodiments with PVDF and acetylene black according to a mass ratio of 8: 1: 1, adding a proper amount of N-methyl pyrrolidone into the obtained mixture until the mixture can slightly flow, fully stirring the mixture until the mixture is uniform, coating the obtained paste product on an aluminum foil with the thickness of 12 mu m, and then drying the aluminum foil in a vacuum drying oven at 60 ℃ for 12 hours to obtain the NCM positive pole piece.
And cutting the NCM positive pole piece into a circular pole piece with the diameter of 14mm, weighing 6 pole pieces with similar mass, and vacuum-drying for 12 h. In the glove box, an NCM pole piece is used as a positive electrode, a metal lithium piece is used as a negative electrode, a ceramic diaphragm is used as the diaphragm, the electrolyte is special commercial high-nickel ternary material electrolyte, 2032 button cells are assembled, 6 cells are assembled on each sample, a blue CT2001 cell test is used for electrochemical performance test, and the test temperature is constant at 25 ℃. The electrochemical test voltage range is 3-4.3V, and the multiplying power test is performed by using 1C, 2C, 3C, 4C, 5C, 10C and 1C.
The microstructures of the precursor material and the cathode material (NCM 622) prepared in the first example are shown in fig. 1 and fig. 2, respectively, and the electrochemical performance test of the NCM cathode material is shown in fig. 3. As can be seen from figure 1, the prepared precursor material has an obvious petal-shaped ball structure, and the larger interlayer spacing for the petal structure to be opened can be visually seen, so that the interlayer spacing can be utilized to obtain the precursor material with high diffusion rate through anions and water moleculesAn ion diffusion channel. Through a two-stage high-temperature sintering calcination mode, the precursor is beneficial to synthesizing the positive electrode material with a layered structure with good orderliness in the pre-sintering stage, and the Li of the synthesized positive electrode material is determined in the high-temperature calcination stage+/Ni2+Degree of shuffling and crystal structure integrity. As is clear from the microstructure of the NCM811 cathode material shown in fig. 2, the NCM811 cathode material is formed by agglomerating and stacking primary particles. The secondary particles are agglomerated into spherical particles with the diameter of about 6 mu m, an electrode pole piece is manufactured by screened uniform powder to carry out electrochemical performance test, the multiplying power test result is shown in figure 3, and the battery capacity retention rate of the NCM622 and NCM811 material under the multiplying power of 5C reaches more than 65% under the state of 1C, and the retention rate under the 10C reaches about 40% under the state of 1C by carrying out charging and discharging test of different multiplying powers on the activated button battery. Under the low-rate (1C) charging condition after the high-rate charge and discharge, the battery capacity is maintained to be about 93 percent (NCM 811) and 99 percent (NCM 622) of the initial 1C, and the structure of the battery is kept stable in the high-current charge and discharge process. This benefits from the complete crystal structure resulting from the staged calcination procedure and the ion diffusion channels that remain during the precursor pre-firing stage.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a nickel-cobalt-manganese ternary cathode material is characterized by comprising the following steps:
(1) adding a precipitator into the solution containing nickel ions, cobalt ions and manganese ions to obtain reaction mother liquor;
(2) carrying out hydrothermal reaction on the reaction mother liquor, and separating out a solid product after the hydrothermal reaction is finished to obtain a precursor material NixCoyMn(1-x-y)(HO)2Wherein x is more than or equal to 0.6 and less than or equal to 0.9, and y is more than or equal to 0.05 and less than or equal to 0.2;
(3) and carrying out sectional calcination on the precursor material and the lithium source at different temperature stages in an oxygen atmosphere to obtain the nickel-cobalt-manganese ternary cathode material.
2. The method for preparing a nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (1), the nickel ions are provided by at least one of nickel nitrate, nickel acetate, nickel carbonate and nickel hydroxide;
or, in the step (1), the cobalt ions are provided by at least one of cobalt nitrate, cobalt acetate, cobalt carbonate and cobalt hydroxide;
or in the step (1), the manganese ions are provided by at least one of manganese cobalt nitrate, manganese acetate, manganese carbonate and manganese hydroxide.
3. The method for preparing a nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (1), the ratio of the nickel ions, the cobalt ions and the manganese ions is configured according to the atomic number ratio of each metal element in the precursor material in the step (2).
4. The method for preparing the nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (1), the precipitating agent comprises any one of urea, ammonia water and ammonium fluoride; preferably, the molar ratio of the precipitant to the metal ion is in the range of 1: 1 to 1: 2, the metal ions refer to the sum of nickel ions, cobalt ions and manganese ions.
5. The method for preparing the nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (1), the solution is a mixed solution of ethanol and water; preferably, the volume ratio of ethanol to water is in the range of 1: 4 to 1: 3.
6. the method for preparing the nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (2), the temperature of the hydrothermal reaction is 150-200 ℃ and the reaction time is 5-15 h.
7. The method for preparing a nickel-cobalt-manganese ternary positive electrode material according to claim 1, wherein in the step (3), the molar ratio of the precursor material to the lithium source is 1: 1.02-1: 1.05; preferably, the lithium source comprises at least one of lithium hydroxide solids, lithium carbonate, lithium acetate, lithium nitrate.
8. The method for preparing the nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (3), the precursor material and the lithium source are uniformly mixed by ball milling or liquid phase dispersion, and then the step calcination is performed.
9. The method for producing a nickel-cobalt-manganese ternary positive electrode material according to any one of claims 1 to 8, wherein in the step (3), the stepwise calcination includes: calcining at 350-450 ℃ for 150-200 min, then heating to 700-850 ℃ and continuing calcining for 1100-1300 min.
10. The use of the nickel-cobalt-manganese ternary positive electrode material of the lithium ion battery obtained by the preparation method according to any one of claims 1 to 9 in an energy storage device.
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