LU101838B1 - Lithium-rich Manganese-based Electrode Material and Preparation Method - Google Patents
Lithium-rich Manganese-based Electrode Material and Preparation Method Download PDFInfo
- Publication number
- LU101838B1 LU101838B1 LU101838A LU101838A LU101838B1 LU 101838 B1 LU101838 B1 LU 101838B1 LU 101838 A LU101838 A LU 101838A LU 101838 A LU101838 A LU 101838A LU 101838 B1 LU101838 B1 LU 101838B1
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- Luxembourg
- Prior art keywords
- lithium
- rich manganese
- niobium
- carboxylic acid
- acid derivative
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 68
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 61
- 239000011572 manganese Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000007772 electrode material Substances 0.000 title description 6
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000010955 niobium Substances 0.000 claims abstract description 48
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 28
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000007774 positive electrode material Substances 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 12
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 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
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229910015118 LiMO Inorganic materials 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229910003327 LiNbO3 Inorganic materials 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910016104 LiNi1 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- ZKZDFIWYUXIKTP-UHFFFAOYSA-N [Li].[Nb].CCO Chemical compound [Li].[Nb].CCO ZKZDFIWYUXIKTP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- -1 niobium carboxylic acid derivative Chemical class 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
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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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A preparation method of a lithium-rich manganese-based positive electrode material, including the following steps of: (1) dissolving a carboxylic acid derivative of niobium in deionized water to prepare a solution with a pH value of 1~3; (2) mixing a lithium-rich manganese-based material with the solution of the carboxylic acid derivative of niobium, and stirring and heating the mixture to a temperature of 55-80°C, preferably 60-65°C, to form a suspension; (3) adding a lithium source, a complexing agent and a dispersant into the suspension according to a molar ratio of 1:1-3:0.01-0.5, performing heating at a temperature of 60-100°C for 2-1 Oh to form a lithium-rich manganese-based material coated with a Li-Nb precursor; and (4) calcinating the lithium-rich manganese-based material, which is obtained in Step (3) and coated with Li-Nb precursor, at a temperature of 500-900°C for 5-15h to obtain a manganese-based positive electrode material. By using the mild acidity of the solution of the carboxylic acid derivative of niobium, this method constructs Li+/H+ structure defects at the surface of the lithium-rich manganese-based material, and constructs an "Nb-doped/LiNbO3-coated" dual-shell surface reconstruction layer via the addition of the lithium source and the high-temperature solid-phase reaction, thereby significantly improving the electrochemical performance of the lithium-rich manganese-based material.
Description
SUNPT20058LU 05.06.2020 lu101838 Specification Lithium-rich Manganese-based Electrode Material and Preparation Method Technical Field The present invention relates to a method of surface modification on a lithium-rich manganese-based positive electrode material and an electrode prepared by this method, belonging to the technical field of lithium batteries. Background Due to a discharge specific capacity of 250 mAh-g' and its low cost, lithium-rich manganese base (xLizMnOQs-(1-x)LiMO,) is hopeful to be the next-generation positive electrode material for the electric vehicle power batteries. Nevertheless, its application is limited by its inherent disadvantages, which include: (1) comparatively low coulomb efficiency caused by irreversible phase transition during the first cycle; (2) dissolution of transition metal ions when being charged to a high voltage; (3) voltage attenuation during a long period cycle; (4) poor ratio and cycling performance. To solve these problems, researchers proposed some solutions, such as bulk phase doping, surface coating and so on. The main doped elements include APY, Mg”, Ti**, etc, which mainly play a role of stabilizing the laminated structure of bulk phase materials and suppressing cation mixing; coating materials mainly include metal oxide, lithium conducting layer, polymer conducting layer and so on.
In recent years, Nb°* has been applied, as a new type of doped ions, to the modification of laminated positive electrode materials, wherein Nb mainly plays the role of stabilizing the structure of laminated materials and accelerating ion diffusion; as a lithium fast ion conductor, LiNbO; has also been applied to the coating modification of various positive electrode materials such as LiCoO2, LiNipsMn;sOa, LiNi1/3C01/3Mn1/0;, etc, which can isolate the active material from the organic electrolyte, function as a physical protective layer, suppress surface side reaction, as well as promote the transmission of lithium ions by using its ion conductivity as high as 10° S-cm™.
CN102244231A provides a method for cladding surfaces of an anode active material and/or the anode and methods for manufacturing the anode and a battery, wherein gas-phase precursors are used to pass into a reactor alternately, and, via chemical adsorption and chemical reaction, a deposited film is 1
SUNPT20058LU 05.06.2020 lu101838 formed on the substrate, which is to be deposited and located in the reactor, as a result, the cycling performance and specific capacity of the lithium-ion battery are significantly improved, and electrode materials are more stable.
CN103339062A relates to a lithium niobate/spinel-type lithium manganese-based composite oxide (LNO/LMO) used as a positive electrode active material for lithium batteries, wherein the crystallite size of LMO is 250~350nm, the distortion is at most 0.085, and the specific surface area growth ratio is at most 10.0% when it is placed in water with a temperature of 25°C and a pH value of 7 to go through an ultrasonic dispersion with an ultrasonic intensity of 40W for 600 seconds, as a result, LMO is capable of preventing output power decrease following repeated charging and discharging at high temperature.
The present invention adopts a “niobium-containing mild carboxylic acidity treatment--post-heating” method, and adds a certain amount of lithium source to combine Nb surface gradient doping and LiNbO; surface coating; this patent uses a “sol-gel” process to reduce the thickness of the coating layer to a nanometer scale and further improve its uniformity.
Summary of the Invention A carboxylic acid derivative of niobium is a soluble Nb source, and its aqueous solution is mildly acidic, the pH value of which is 1-3 when the mass concentration is 0.1-1g/10mL. The present invention treats the surface of lithium-rich manganese-based (LMR) material by using the solution of the carboxylic acid derivative of niobium, which has a mild acidity, wherein: firstly, structural defects are formed on the surface of the material through Li*/H" ion exchange reaction, and then high temperature sintering is performed. After these steps, Nb element can partially enter the lithium-rich manganese-based material, thereby enhancing the structural stability of the lithium-rich manganese-based (LMR) material and suppressing voltage attenuation. In the present invention, Li source is added to the niobium carboxylic acid derivative suspension of LMR so as to form a LiNbOs fast ion conductive layer on the surface of the lithium-rich manganese-based material (LMR), and also to function as a physical protective layer, thereby improving the ratio and cycling stability of the material. In the coating process, complexing agents and dispersants can also be added so as to form a uniform nano-scale coating layer on the material surface.
The present invention provides a method of preparing a lithium-rich manganese-based positive electrode material, including the following steps of: (1) dissolving a carboxylic acid derivative of niobium in deionized water to prepare a solution of the 2
SUNPT20058LU 05.06.2020 lu101838 carboxylic acid derivative of niobium with a pH value of 1~3; (2) mixing a lithium-rich manganese-based material with the solution of the carboxylic acid derivative of niobium, and stirring and heating the mixture to a temperature of 55-80°C, preferably 60-65°C, to form a suspension; (3) adding a lithium source, a complexing agent and a dispersant into the suspension according to a molar ratio of 1:1-3:0.01-0.5, performing heating at a temperature of 60-100°C for 2-10h to form a lithium-rich manganese-based material coated with a Li-Nb precursor; and (4) calcinating the lithium-rich manganese-based material, which is obtained in Step (3) and coated with Li-Nb precursor, at a temperature of 500-900°C for 5-15h to obtain a manganese-based positive electrode material.
Said lithium-rich manganese-based material is xLixMnOs-(1-x)LiMO,, wherein x is 0.01-0.99, preferably 0.1-0.5.
Said Li source is one or more of lithium hydroxide, lithium carbonate, lithium nitrate, and lithium oxalate.
The addition amount of said carboxylic acid derivative of niobium in Step (2) is 0.1-9wt% of the mass of LMR material, preferably 0.5~5.
Said complexing agent is one or more of citric acid, EDTA, ascorbic acid and maleic acid; said dispersant is one or more of ethylene glycol, glycerin, propylene glycol, polyvinyl alcohol, dimethyl ether and acetone.
Said carboxylic acid derivative of niobium is a mono- or dibasic carboxylic acid derivative, of which a carbon atom number of niobium is 2-5, preferably niobium oxalate or ammonium niobium oxalate.
Said mixing in Step (2) is one of the following ways: slowly pumping the solution of the carboxylic acid derivative of niobium into the suspension of the lithium-rich manganese-based material; slowly pouring a powder of the lithium-rich manganese-based material into the solution of the carboxylic acid derivative of niobium; and directly mixing the solution of the carboxylic acid derivative of niobium with the suspension of the lithium-rich manganese-based material.
Preferably, Step (4) is carried out in an oxidizing atmosphere in the presence of oxygen or air.
Preferably, the product obtained in Step (4) is crushed to 200-400 mesh to obtain the final product.
The other aspect of the present invention also discloses a lithium-rich manganese-based positive electrode material prepared by said method and its application to batteries.
3
SUNPT20058LU 05.06.2020 lu101838 Beneficial effects of the Invention: By using the mild acidity of the solution of the carboxylic acid derivative of niobium and through Li*/H' ion exchange reaction, the present invention first constructs Li'/H” structural defects on the surface of the lithium-rich manganese-based material; by means of high-temperature solid-phase reaction, Nb is solid-dissolved into the surface of the material, and exchange again with H” therein, thereby forming a lithium-rich manganese-based material doped on the surface of Nb. During the sintering process, undoped Nb reacts with the added lithium source and Li” separated out of the surface layer to form a LiNbO; fast ionic conductor phase on the material surface (the ion conductivity reaches 107° Sem). In this way, after the three stages of “processing of a carboxylic acid derivative of niobium --addition of Li source--high-temperature sintering”, the “Nb-doped/LiNbO3 coated” double-shell surface reconstruction layer can be formed on the surface of the lithium-rich manganese-based material, thereby improving the electrochemical properties of the lithium-rich manganese-based material. The addition of the complexing agent and the dispersant is beneficial to the forming of nanometer coating with uniform thickness.
Description of the Drawing Fig. 1 is a schematic diagram showing the preparation process of the electrode material. Embodiments With reference to the drawing of the description and the Examples, the present invention will be further limited as follows.
Example 1 A method of preparing a lithium-rich manganese-based material, including the following steps of: (1) dissolving niobium oxalate in deionized water to prepare a solution with a pH value of 1; (2) mixing a lithium-rich manganese-based material with the solution of ammonium niobium oxalate, and stirring and heating the mixture to a temperature of 60°C to form a suspension; the addition amount of ammonium niobium oxalate is 2wt% of the mass of LMR (0.5LixMn0O3-0.5LiNi13Co13Mni302) material; (3) adding lithium nitrate, EDTA and dimethyl ether into the suspension according to a molar ratio of 4
SUNPT20058LU 05.06.2020 lut01838 1:1:0.1, performing heating at a temperature of 60°C for 10h to form a lithium-rich manganese-based material coated with a Li-Nb precursor; and (4) calcinating the lithium-rich manganese-based material coated with Li-Nb precursor at a temperature of 900°C for 5h, and crushing the calcined manganese-based positive electrode material to 200 mesh.
Example 2 A method of preparing a lithium-rich manganese-based positive electrode material, including the following steps of: (1) dissolving ammonium niobium oxalate in deionized water to prepare a solution with a pH value of 2; (2) mixing a lithium-rich manganese-based material with the solution of ammonium niobium oxalate, and stirring and heating the mixture to a temperature of 80°C to form a suspension; the addition amount of ammonium niobium oxalate is 1wt% of the mass of LMR (0.5Li2MnO3-0.SLiNi1/3C013Mn1502) material; (3) adding a lithium source, a complexing agent and a dispersant into the suspension according to a molar ratio of 1:2:0.3, performing heating at a temperature of 95°C for 2h to form a lithium-rich manganese-based material coated with a Li-Nb precursor; and (4) calcinating the lithium-rich manganese-based material, which is obtained in Step (3) and coated with Li-Nb precursor, at a temperature of 600°C for 12h, and crushing the calcined manganese-based positive electrode material to 300 mesh.
Comparative Example 1 (1) Dissolving lithium ethoxide and niobium ethoxide in a certain amount of ethanol solution; (2) dispersing a lithium-rich manganese-based material in said solution, and stirring the solution intensely; (3) heating the dispersed solution at a temperature of 80°C till the solvent is completely evaporated, thereby obtaining a lithium-rich manganese-based material coated with ethanol niobium lithium; and (4) drying the product obtained in Step (3) at a temperature of 500°C, obtaining the lithium-rich manganese-based material coated with LINbO3, and crushing and sifting under 200 mesh the calcined manganese-based positive electrode material. Comparative Example 2 | -
SUNPT20058LU 05.06.2020 lu101838 A method of preparing a lithium-rich manganese-based positive electrode material, including the following steps of: (1) dissolving niobium oxalate in deionized water to prepare a solution with a pH value of 1; (2) mixing a lithium-rich manganese-based material with the solution of ammonium niobium oxalate, and stirring and heating the mixture to a temperature of 60°C to form a suspension; the addition amount of ammonium niobium oxalate is 2wt% of the mass of LMR (0.5Li2MnO30.5LiNi1/3C01/3Mn1502) material; (3) stirring and heating the suspension obtained in Step (2) to 60°C till the solvent is completely evaporated; and (4) calcinating the dried product obtained in Step (3) for 5h, and crushing the calcined lithium-rich manganese-based positive electrode material to 200 mesh.
Comparative Example 3 | (1) Dissolving ammonium niobium oxalate in deionized water to prepare a solution with a pH value of 1; (2) mixing a lithium-rich manganese-based material with the solution of ammonium niobium oxalate, and stirring and heating the mixture to a temperature of 60°C to form a suspension; the addition amount of the ammonium niobium oxalate is 1wt% of the mass of LMR (0.5Li2MnO3-0.5LiNi13Co13Mn;30) material; (3) adding a complexing agent and a dispersant into the suspension according to a molar ratio of 2:0.3, performing heating at a temperature of 95°C for 2h to form a lithium-rich manganese-based material coated with Nb; and (4) calcinating the lithium-rich manganese-based material coated with Nb at a temperature of 900°C for 5h, and crushing the calcined manganese-based positive electrode material to 200 mesh.
The positive electrode materials prepared according to Examples 1-2 and Comparative Examples 1-3 will be mixed with conductive carbon black and polyvinylidene fluoride at a ratio of 8:1:1 by weight, and the mixture will be uniformly blended with N-methyl-2-pyrrolidone into a positive electrode slurry. The positive electrode slurry will be uniformly spread on an aluminum foil with a thickness of 0.02mm, and will be dried by using a hot air circulation at 80~150°C. After drying, a pressure of 300 tons will be used for rolling, and the required positive electrode for lithium batteries will be obtained after compaction. .
Performance tests were carried out on the products of Examples 1-2 and Comparative Examples 1-3, 6
SUNPT20058LU 05.06.2020 lu101838 and the results are as follows: First-cycle Coulomb | 1C Capacity retention | IC Discharge medium efficiency, % ratio after 100 voltage after 100 cycles, V cycles , % Comparative Examples 1-3 use neutral niobium solutions for loading treatment; no lithium source, no complexing agent and no dispersant are added; no electrode material prepared with lithium source is added. According to the comparison between the embodiments of the present invention and the comparative examples, the electrode material prepared by the method of the present invention has a better capacity retention ratio after multiple cycles, the discharge voltage reduce is very small and coulomb efficiency is significantly enhanced, which indicate great improvement.
The above examples exemplarily illustrate the technical effects and the implementation process of the present invention only. However, one skilled in the art should understand that any changes in form and details, which are made on such a basis and do not exceed the scope of protection of the claims, belong to the scope of protection of the present invention.
7 | | | | ee ——————————————————————————
Claims (10)
1. A method of preparing a lithium-rich manganese-based positive electrode material, including the following steps of: (1) dissolving a carboxylic acid derivative of niobium in deionized water to prepare a solution of the carboxylic acid derivative of niobium with a pH value of 1~3; (2) mixing a lithium-rich manganese-based material with the solution of the carboxylic acid derivative of niobium, and stirring and heating the mixture to a temperature of 55-80°C, preferably 60-65°C, to form a suspension; (3) adding a lithium source, a complexing agent and a dispersant into the suspension according to a molar ratio of 1:1-3:0.01-0.5, performing heating at a temperature of 60-100°C for 2-10h to form a lithium-rich manganese-based material coated with a Li-Nb precursor; and (4) calcinating the lithium-rich manganese-based material, which is obtained in Step (3) | and coated with Li-Nb precursor, at a temperature of 500-900°C for 5-15h to obtain a manganese-based positive electrode material.
2. The method according to claim 1, wherein the lithium-rich manganese-based material is xLizMnOj3-(1-x)LiMO», wherein x is 0.01-0.99, preferably 0.1-0.5; the Li source is one or more of lithium hydroxide, lithium carbonate, lithium nitrate, and lithium oxalate.
3. The method according to claim 1, wherein the carboxylic acid derivative of niobium is a mono- or dibasic carboxylic acid derivative, of which a carbon atom number of niobium is 2-5, preferably niobium oxalate or ammonium niobium oxalate.
4. The method according to claim 1, wherein the addition amount of said carboxylic acid derivative of niobium in Step (2) is 0.1-9wt% of the mass of LMR material, preferably 0.5~5.
5. The method according to claim 1, wherein the complexing agent is one or more of citric acid, EDTA, ascorbic acid and maleic acid; the dispersant is one or more of ethylene glycol, glycerin, propylene glycol, polyvinyl alcohol, dimethyl ether and acetone.
6. The method according to claim 1, wherein the mixing in Step (2) is one of the following ways: slowly pumping the solution of the carboxylic acid derivative of niobium into the suspension of the lithium-rich manganese-based material; slowly pouring a powder of the lithium-rich manganese-based material into the solution of the carboxylic acid derivative 1
SUNPT20058LU 05.06.2020 lu101838 of niobium; and directly mixing the solution of the carboxylic acid derivative of niobium with the suspension of the lithium-rich manganese-based material.
7. The method according to claim 1, wherein Step (4) is carried out in an oxidizing atmosphere in the presence of oxygen or air.
8. The method according to claim 1, wherein the product obtained in Step (4) is crushed to 200-400 mesh to obtain the final product.
9.A lithium-rich manganese-based positive electrode material prepared by the method of any of the claims 1-8.
10. Application of the lithium-rich manganese-based positive electrode material prepared by the method of any of the claims 1-8 to batteries.
2
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| CN113611862A (en) * | 2021-07-29 | 2021-11-05 | 广州大学 | Preparation method of lithium niobate-coated positive electrode material, lithium niobate-coated positive electrode material and application |
| CN114678522A (en) * | 2022-04-25 | 2022-06-28 | 西安理工大学 | Modification method and material application of manganese vacancies regulated lithium-rich manganese-based cathode materials |
| CN117441240A (en) * | 2023-09-13 | 2024-01-23 | 广东邦普循环科技有限公司 | Lithium-rich manganese-based cathode materials, preparation methods and applications |
| CN118053991A (en) * | 2023-12-27 | 2024-05-17 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | A lithium-rich manganese-based positive electrode material coated with lithium niobate and a preparation method thereof |
| CN120072912B (en) * | 2025-04-28 | 2025-07-08 | 长三角物理研究中心有限公司 | A lithium-rich manganese-based positive electrode material co-coated with molybdenum disulfide and lithium lanthanum niobium oxide and a preparation method thereof |
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| WO2012118117A1 (en) | 2011-03-02 | 2012-09-07 | 三井金属鉱業株式会社 | Spinel-type lithium manganese-based composite oxide |
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