CN111224089A - Ternary cathode material NCM811 for lithium ion battery prepared by molten salt method and preparation method thereof - Google Patents
Ternary cathode material NCM811 for lithium ion battery prepared by molten salt method and preparation method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 150000003839 salts Chemical class 0.000 title claims abstract description 45
- 239000010406 cathode material Substances 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 20
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 16
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical group [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 claims description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 6
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical group [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 229910013553 LiNO Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 239000007774 positive electrode material Substances 0.000 abstract description 13
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 239000012429 reaction media Substances 0.000 abstract description 7
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 16
- 238000001354 calcination Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910011116 LiM2O4 Inorganic materials 0.000 description 1
- 229910016118 LiMn1.5Ni0.5O4 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 241001633106 Lithocarpus Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 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
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- -1 nickel-cobalt-aluminum Chemical compound 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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Abstract
The invention discloses a ternary cathode material NCM811 of a lithium ion battery prepared by a molten salt method and a preparation method thereof, wherein the preparation method comprises the following steps: mixing a nickel source, a cobalt source and a manganese source to obtain a mixture A; mixing a lithium source and molten salt to obtain a mixture B; mixing the obtained mixture A and the mixture B, carrying out roasting reaction under gradient after pretreatment, and cooling after the reaction is finished to obtain a block-shaped object; grinding, washing and drying the massive object to obtain an NCM811 positive electrode material; according to the invention, molten salt is used as a reaction medium, and the NCM811 positive electrode material with good cycle performance and high rate performance is prepared by regulating and controlling the reaction temperature and the type and the amount of nickel, cobalt and manganese, so that the NCM811 positive electrode material with submicron size is prepared, and the diffusion requirement of lithium ions can be met while the integrity and the uniformity of crystal grains of the material are ensured; in addition, the preparation method has the advantages of simple process, low production cost, energy conservation and high efficiency.
Description
Technical Field
The invention belongs to the field of battery material preparation, and relates to a lithium ion battery ternary cathode material NCM811 prepared by a molten salt method and a preparation method thereof.
Background
The positive electrode material of the lithium ion battery mainly comprises layered lithium cobaltate (LiCoO)2) Spinel lithium manganate (LiMn)2O4) Olivine lithium iron phosphate (LiFePO)4) And ternary nickel-cobalt-manganese (NCM) and nickel-cobalt-aluminum (NCA). The ternary cathode material integrates LiCoO2Stability of (2), LiMnO2Low cost of LiNO and LiNO2The high-capacity performance has the advantages of high specific energy, low cost, low cyclicity, good safety performance, low toxicity and the like.
LiNi0.8Co0.1Mn0.1O2(NCM811) has been used in power and energy storage fields, but because of its serious cation mixing and nickel-rich material LiNi0.8Co0.1Mn0.1O2The structure is easily changed in the delithiated state, and the capacity is reduced. Its application is still limited, especially in the field of power. With the requirements of high safety, high energy density, high power density and long service life of power batteries, the further improvement of LiNi is required0.8Co0.1Mn0.1O2The properties of (2) are of particular importance. Against LiNi0.8Co0.1Mn0.1O2The nickel-rich gradient material is used as a lithium ion battery anode material, and researchers usually improve the electrochemical performance of the lithium ion battery anode material by means of ion doping, preparation of a nickel-rich gradient material, carbon coating and the like.
At present, LiNi0.8Co0.1Mn0.1O2The preparation methods of the material are various, including a spray pyrolysis method, a coprecipitation method, a sol-gel method, a hydrothermal method, a high-temperature solid phase method and the like, and the high-temperature solid phase method is mainly adopted for synthesis in the current industrial production. Although the method has simple process, the solid phase compound is difficult to be mixed uniformly, the synthesis time is long, the energy consumption is high, the efficiency is low, the particles are large, impurities are mixed, and the batch stability is poor.
The molten salt method is attracting wide attention due to the characteristics of simple process, short reaction time and the like. These lithium-containing positive electrode materials are generally synthesized by, for example, LiCl, LiF, LiCO3LiOH or LiNO3And lithium salts, which serve both as a solvent and provide a source of lithium for the target product. The primary role of the molten salt is to act as a "solvent" and diffusion medium throughout the reaction. The reaction raw materials generally have certain solubility in the selected salt, so that the reactants can be contacted in a liquid phase on an atomic scale; in addition, the reactants have a greater diffusion rate in the molten salt, e.g., the ion mobility rate in the molten salt is 1 × 10-5～1×10- 8cm2S, and only 1X 10 in the solid phase-8cm2These two effects allow the reaction to take place in a shorter time and at a lower temperature.
LiMn with excellent cycle performance is synthesized by Duke et al (Lithocarpus, Lu, Hurong, Pengzhong. inorganic chemistry Proc., 2006(05):867-2O4The capacity average attenuation rate of the previous 100 times is about 0.05 percent; the rate capability is also very excellent, and the capacity at 8C discharge is more than 93% of 1C discharge capacity.
Chen et al (H.Chen, C.P.Grey. adv.Mater., 2008, 20, 2206-3)2As a raw material, petal-shaped cluster sphere LiCoO2 is prepared in mixed salt consisting of LiOH, KOH and CsOH, and has good electrochemical performance and is particularly suitable for large-rate discharge.
Kim et al (J.H.Kim, S.T.Myung, Y.K.Sun.Electrochim.acta, 2004, 49, 219-2Selecting LiCl and LiOH mixed salt as a precursor, controlling the temperature to be 700-900 ℃, and synthesizing the spinel LiM2O4Structural LiMn1.5Ni0.5O4。
Chang et al (Yangtze. electric automobile composite power research and simulation analysis [ D)]University of changan, 2010.) the ternary hydroxide precursor was mixed with molten salts LiOH and LiNO3Mixing to obtain Li (Ni)1/3Co1/3Mn1/3)O2A ternary material. At 0.2mA/cm2And the discharge specific capacity is high and the cycle performance is stable under the charging and discharging conditions of 3.0-4.3V.
Subsequent studies of Fey (g.t.k.fey, y.c.lin, h.m.kao.electrochim. acta, 2012, 8041-.
The method can be seen that the existing molten salt method for preparing the powder material can improve the crystallinity of the material and the confirmed density of the material, thereby improving the cycle performance and the rate performance of the battery, but the LiNi with high performance cannot be prepared by the molten salt method at present0.8Co0.1Mn0.1O2。
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a ternary cathode material NCM811 for a lithium ion battery prepared by a molten salt method, which has the advantages of simple process, low production cost, energy conservation and high efficiency, and a preparation method thereof, so that the cathode material NCM811 with submicron size is prepared, the integrity and uniformity of material crystal grains are ensured, and the diffusion requirement of lithium ions can be met.
In order to achieve the above object, the present invention adopts the following technical solutions.
A method for preparing a ternary cathode material NCM811 of a lithium ion battery by a molten salt method comprises the following steps:
(1) according to the mole ratio of nickel, cobalt and manganese elements of 8:1:1, respectively taking a nickel source, a cobalt source and a manganese source, and mixing to obtain a mixture A;
(2) taking a lithium source according to 4 times of the sum of the molar weight of the nickel source, the molar weight of the cobalt source and the molar weight of the manganese source, taking molten salt according to 2-3 times of the sum of the mass of the nickel source, the molar weight of the cobalt source and the molar weight of the manganese source, and mixing the lithium source and the molten salt to obtain a mixture B;
(3) mixing the mixture A obtained in the step (1) and the mixture B obtained in the step (2), roasting at the temperature of 300-320 ℃ for 1-3h, then roasting at the temperature of 700-750 ℃ for 2-3h, and finally roasting at the temperature of 850-900 ℃ for 6-9h after pretreatment, and cooling after the roasting reaction is finished to obtain a block-shaped object;
(4) and (4) grinding, washing and drying the block-shaped object obtained in the step (3) to obtain the ternary cathode material NCM811 of the lithium ion battery.
Further, in the step (1), the nickel source is nickel hydroxide or nickel sulfate, the cobalt source is cobaltous oxide or cobalt sulfate, and the manganese source is manganese dioxide or manganese sulfate.
Further, in the step (2), the lithium source is lithium nitrate and lithium hydroxide.
Further, the lithium source in the step (2) includes 38% of LiOH and 62% of LiNO in a molar ratio3。
Further, the molten salt in the step (2) is sodium chloride, potassium chloride or a combination of the two.
Further, the pretreatment in the step (3) is mechanical crushing, the mechanical crushing mode comprises any one or combination of at least two of ball milling, extrusion or impact, and the mechanical crushing time is 6-8 hours.
Further, the roasting reaction in the step (3) is carried out in an oxygen sintering furnace.
Further, the cooling process in the step (3) is furnace cooling, and the cooling is carried out until the temperature is less than 100 ℃.
Further, the drying temperature in the step (4) is 80-120 ℃; the drying time is 2-5 h.
The ternary positive electrode material NCM811 of the lithium ion battery is of a large crystal structure, and the size of the ternary positive electrode material NCM is 1-2 mu m.
Compared with the prior art, the invention has the following beneficial effects:
(1) when the molten salt is used as a reaction medium, the final electrochemical performance of a product is greatly influenced by temperature, and a material with high crystallinity is difficult to obtain at too low temperature, so that the corresponding cycle stability is determined; too high a temperature tends to cause the material to become dense, which may result in poor material utilization. According to the invention, the NCM811 cathode material with submicron size is prepared by regulating and controlling the roasting temperature and the type and the amount of nickel, cobalt and manganese, so that the prepared material crystal has better integrity and uniformity, and further the first reversible specific capacity of the lithium battery prepared from the material prepared by the invention is over 171mAh/g under the multiplying power of 0.2C, and the capacity is kept over 95% after 1C multiplying power cycling test for 50 times at room temperature;
(2) the invention takes the fused salt as the reaction medium, can ensure that the reactants have larger diffusion rate, thereby ensuring nucleation uniformity and finally showing that the consistency of the material is good; meanwhile, the consistency of products in different batches can be ensured by taking the molten salt as a reaction medium;
(3) the NCM811 cathode material prepared by the invention has the advantages of uniform average particle size, excellent cycle performance, simple preparation method and process, low production cost, energy conservation and high efficiency.
Drawings
FIG. 1 is an XRD pattern of a positive electrode material of NCM811 obtained in example 1 of the present invention;
FIG. 2 is an SEM photograph of the positive electrode material of NCM811 obtained in example 1 of the present invention;
FIG. 3 is a graph showing the first reversible specific capacity at 0.2C rate of a battery made of the NCM811 cathode material obtained in example 1 of the present invention;
FIG. 4 is a graph of cycle performance of a battery made of the NCM811 cathode material obtained in example 3 of the present invention at 0.2C rate cycle test for 50 weeks.
Fig. 5 is a graph of coulombic efficiency at 0.2C rate cycle test for 50 weeks for a battery made of the NCM811 cathode material obtained in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.
Example 1:
this example provides a molten salt method for preparing LiNi0.8Co0.1Mn0.1O2A method of making a positive electrode material, the method comprisingThe method comprises the following steps:
(1) mixing 74.2g of nickel hydroxide, 7.5g of cobaltous oxide and 8.7g of manganese dioxide (the molar ratio of Ni, Co and Mn is 8:1:1) to obtain a mixture A;
(2) 171g of lithium nitrate, 63.8g of lithium hydroxide monohydrate and 234g of sodium chloride were mixed to obtain a mixture B;
(3) mixing the mixture A obtained in the step (1) and the mixture B obtained in the step (2), adding the mixture into a ball milling tank for grinding for 5 hours, placing the grinding material into a sintering furnace under the atmosphere of oxygen, calcining for 3 hours at the temperature of 300 ℃, calcining for 3 hours at the temperature of 700 ℃, calcining for 6 hours at the temperature of 900 ℃, and cooling to room temperature along with the furnace temperature after the reaction is finished to obtain a block-shaped object;
(4) and (4) putting the blocky object in the step (3) into a ball mill, grinding the blocky object into powder, adding water to wash the blocky object for three times, filtering the powder, and drying the filtered powder for 2 hours at the temperature of 100 ℃ by using a drying oven to obtain the NCM811 cathode material.
Example 2:
(1) mixing 216g of nickel sulfate hexahydrate, 28.1g of cobalt sulfate and 15.1g of manganese sulfate (the molar ratio of Ni to Co to Mn is 8:1:1) to obtain a mixture A;
(2) 170g of lithium nitrate, 63.8g of lithium hydroxide monohydrate and 298g of potassium chloride are mixed to obtain a mixture B;
(3) mixing the mixture A obtained in the step (1) and the mixture B obtained in the step (2), adding the mixture into a ball milling tank for grinding for 6 hours, placing the grinding material into a sintering furnace under the atmosphere of oxygen, preserving heat for 3 hours at the temperature of 330 ℃, preserving heat for 3 hours at the temperature of 720 ℃, preserving heat for 6 hours at the temperature of 850 ℃, and cooling the mixture to room temperature along with the furnace temperature after the reaction is finished to obtain a block-shaped object;
(4) and (4) putting the blocky object in the step (3) into a ball mill, grinding the blocky object into powder, adding water to wash the blocky object for three times, filtering the powder, and drying the filtered powder for 2 hours at 120 ℃ to obtain the NCM811 cathode material.
Example 3:
the embodiment provides a method for preparing an NCM811 cathode material by a molten salt method, which comprises the following steps:
(1) 77.91 Nickel hydroxide, 8.7g manganese dioxide and 7.6g cobaltous oxide (molar ratio of Ni, Co and Mn 8:1:1) were mixed to give mixture A;
(2) 275g of lithium nitrate and 233g of sodium chloride were mixed to obtain a mixture B;
(3) mixing the mixture A obtained in the step (1) and the mixture B obtained in the step (2), adding the mixture into a ball milling tank for grinding for 7 hours, placing the grinding material into a sintering furnace under the atmosphere of oxygen, preserving heat for 1 hour at the temperature of 300 ℃, preserving heat for 2 hours at the temperature of 750 ℃, preserving heat for 6 hours at the temperature of 850 ℃, and cooling to room temperature along with the furnace temperature after the reaction is finished to obtain a block-shaped object;
(4) and (4) putting the blocky object in the step (3) into a ball mill, grinding the blocky object into powder, adding water to wash the blocky object for three times, filtering the powder, and drying the filtered powder for 3 hours at the temperature of 80 ℃ to obtain the NCM811 cathode material.
Example 4:
example 4 provides a method for preparing an NCM811 cathode material by a molten salt method, which is the same as in example 1 of the preparation process uniformity except that only lithium hydroxide is used as a material in step (2).
Example 5:
example 5 provides a method for preparing an NCM811 cathode material by a molten salt method, which uses the same materials as in example 1 except that the calcination temperature in step (3) is 320-750-850 ℃.
Mixing the NCM811 positive electrode material prepared in the examples 1-5, conductive carbon black and PVDF binder according to the mass ratio of 90:4:6, preparing uniform slurry by taking NMP as a solvent, then coating the uniform slurry on an aluminum foil in a scraping manner, and carrying out vacuum drying at 120 ℃ to obtain a positive electrode piece, wherein the negative electrode piece is a lithium piece; the test cell was placed in a glove box filled with argon gas, and a charge and discharge test was performed at a constant current, and the test results are shown in table 1.
Wherein, the XRD pattern of the sample obtained in example 1 is shown in figure 1, and the SEM photograph of the sample is shown in figure 2. The battery prepared by the sample obtained in the example 1 has the first reversible specific capacity of 171mAh/g at 4.3V, as shown in figure 3; the capacity of the sample obtained in example 3 was maintained above 95% at room temperature by 1C-cycle testing for 50 weeks, as shown in fig. 4 and 5.
Table 1: performance test Table for batteries made from the materials obtained in examples 1 to 5
The results of the embodiments 1 to 5 are combined to show that the molten salt is used as the reaction medium, so that the invention can ensure that the reactants have a larger diffusion rate, thereby ensuring the nucleation uniformity and finally showing that the consistency of the material is good; meanwhile, the molten salt is used as a reaction medium, so that the consistency of products in different batches can be ensured.
According to the invention, molten salt is used as a reaction medium, and the NCM811 cathode material with good cycle performance and high rate performance is prepared by regulating and controlling the reaction temperature and the type and the amount of nickel, cobalt and manganese, so that the integrity and the uniformity of material crystal grains are ensured, and the diffusion requirement of lithium ions can be met, thereby enabling the initial reversible specific capacity of the full battery prepared from the material prepared by the invention to be more than 171mAh/g at 4.3V and the capacity to be kept more than 95% at room temperature after 1C rate cycle test for 50 weeks.
Example 6:
this example provides a molten salt method for preparing LiNi0.8Co0.1Mn0.1O2A method of positive electrode material, the method comprising the steps of:
(1) mixing 74.2g of nickel hydroxide, 7.5g of cobaltous oxide and 8.7g of manganese dioxide (the molar ratio of Ni, Co and Mn is 8:1:1) to obtain a mixture A;
(2) 171g of lithium nitrate, 63.8g of lithium hydroxide monohydrate, 234g of sodium chloride and 37.2g of potassium chloride were mixed to obtain a mixture B;
(3) mixing the mixture A obtained in the step (1) and the mixture B obtained in the step (2), adding the mixture into a ball milling tank for grinding for 8 hours, placing the grinding material into a sintering furnace under the atmosphere of oxygen, calcining for 2 hours at the temperature of 320 ℃, calcining for 2.5 hours at the temperature of 700 ℃, calcining for 9 hours at the temperature of 880 ℃, and cooling to room temperature along with the furnace temperature after the reaction is finished to obtain a block-shaped object;
(4) and (4) putting the blocky objects in the step (3) into a ball mill, grinding the blocky objects into powder, adding water to wash the blocky objects for three times, filtering the powder, and drying the filtered powder for 5 hours at the temperature of 100 ℃ by using a drying oven to obtain the NCM811 cathode material.
Example 7:
this example provides a molten salt method for preparing LiNi0.8Co0.1Mn0.1O2A method of positive electrode material, the method comprising the steps of:
(1) mixing 74.2g of nickel hydroxide, 7.5g of cobaltous oxide and 8.7g of manganese dioxide (the molar ratio of Ni, Co and Mn is 8:1:1) to obtain a mixture A;
(2) 171g of lithium nitrate, 63.8g of lithium hydroxide monohydrate and 180.8g of potassium chloride were mixed to give a mixture B;
(3) mixing the mixture A obtained in the step (1) and the mixture B obtained in the step (2), adding the mixture into a ball milling tank for grinding for 8 hours, placing the grinding material into a sintering furnace under the atmosphere of oxygen, calcining for 2 hours at the temperature of 320 ℃, calcining for 2.5 hours at the temperature of 700 ℃, calcining for 7 hours at the temperature of 870 ℃, and cooling to room temperature along with the furnace temperature after the reaction is finished to obtain a block-shaped object;
(4) and (4) putting the blocky objects in the step (3) into a ball mill, grinding the blocky objects into powder, adding water to wash the blocky objects for three times, filtering the powder, and drying the filtered powder for 5 hours at the temperature of 100 ℃ by using a drying oven to obtain the NCM811 cathode material.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. A method for preparing a ternary cathode material NCM811 of a lithium ion battery by a molten salt method is characterized by comprising the following steps:
(1) according to the mole ratio of nickel, cobalt and manganese elements of 8:1:1, respectively taking a nickel source, a cobalt source and a manganese source, and mixing to obtain a mixture A;
(2) taking a lithium source according to 4 times of the sum of the molar weight of the nickel source, the molar weight of the cobalt source and the molar weight of the manganese source, taking molten salt according to 2-3 times of the sum of the mass of the nickel source, the molar weight of the cobalt source and the molar weight of the manganese source, and mixing the lithium source and the molten salt to obtain a mixture B;
(3) mixing the mixture A obtained in the step (1) and the mixture B obtained in the step (2), roasting at the temperature of 300-320 ℃ for 1-3h, then roasting at the temperature of 700-750 ℃ for 2-3h, and finally roasting at the temperature of 850-900 ℃ for 6-9h after pretreatment, and cooling after the roasting reaction is finished to obtain a block-shaped object;
(4) and (4) grinding, washing and drying the block-shaped object obtained in the step (3) to obtain the ternary cathode material NCM811 of the lithium ion battery.
2. The method for preparing the ternary cathode material NCM811 of the lithium ion battery by the molten salt method according to claim 1, wherein the method comprises the following steps: in the step (1), the nickel source is nickel hydroxide or nickel sulfate, the cobalt source is cobaltous oxide or cobalt sulfate, and the manganese source is manganese dioxide or manganese sulfate.
3. The method for preparing the ternary cathode material NCM811 of the lithium ion battery by the molten salt method according to claim 1, wherein the method comprises the following steps: the lithium source in the step (2) is lithium nitrate and lithium hydroxide.
4. The method for preparing the ternary cathode material NCM811 of the lithium ion battery by the molten salt method according to claim 3, wherein the method comprises the following steps: the lithium source in the step (2) comprises 38% of LiOH and 62% of LiNO by mol ratio3。
5. The method for preparing the ternary cathode material NCM811 of the lithium ion battery by the molten salt method according to claim 1, wherein the method comprises the following steps: the molten salt in the step (2) is sodium chloride, potassium chloride or a combination of the sodium chloride and the potassium chloride.
6. The method for preparing the ternary cathode material NCM811 of the lithium ion battery by the molten salt method according to claim 1, wherein the method comprises the following steps: the pretreatment in the step (3) is mechanical crushing, the mechanical crushing mode comprises any one or combination of at least two of ball milling, extrusion or impact, and the mechanical crushing time is 6-8 h.
7. The method for preparing the ternary cathode material NCM811 of the lithium ion battery by the molten salt method according to claim 1, wherein the method comprises the following steps: and (4) carrying out the roasting reaction in the step (3) in an oxygen sintering furnace.
8. The method for preparing the ternary cathode material NCM811 of the lithium ion battery by the molten salt method according to claim 1, wherein the method comprises the following steps: the cooling process in the step (3) is furnace cooling, and the cooling is carried out until the temperature is less than 100 ℃.
9. The method for preparing the ternary cathode material NCM811 of the lithium ion battery by the molten salt method according to claim 1, wherein the method comprises the following steps: the drying temperature in the step (4) is 80-120 ℃; the drying time is 2-5 h.
10. The lithium ion battery ternary cathode material NCM811 prepared by the method of any one of claims 1 to 9 has a large crystal structure, and the size of the lithium ion battery ternary cathode material NCM is 1-2 μm.
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