LU101837A1 - Method for Modifying High-nickel Positive Electrode Material - Google Patents
Method for Modifying High-nickel Positive Electrode Material Download PDFInfo
- Publication number
- LU101837A1 LU101837A1 LU101837A LU101837A LU101837A1 LU 101837 A1 LU101837 A1 LU 101837A1 LU 101837 A LU101837 A LU 101837A LU 101837 A LU101837 A LU 101837A LU 101837 A1 LU101837 A1 LU 101837A1
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- LU
- Luxembourg
- Prior art keywords
- niobium
- carboxylic acid
- acid derivative
- nickel
- laminated material
- Prior art date
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 31
- 239000010955 niobium Substances 0.000 claims abstract description 31
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 19
- 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 28
- 239000002648 laminated material Substances 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 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 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 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 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- IBXOPEGTOZQGQO-UHFFFAOYSA-N [Li].[Nb] Chemical compound [Li].[Nb] IBXOPEGTOZQGQO-UHFFFAOYSA-N 0.000 claims description 3
- -1 carboxylic acid niobium salt Chemical class 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910013716 LiNi Inorganic materials 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 28
- 230000001351 cycling effect Effects 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000002002 slurry Substances 0.000 description 15
- 239000012467 final product Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 210000005056 cell body Anatomy 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 101100004392 Arabidopsis thaliana BHLH147 gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000012093 Myrtus ugni Nutrition 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 244000061461 Tema Species 0.000 description 1
- 241000949477 Toona ciliata Species 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A method for modifying a high-nickel positive electrode material, wherein a high-nickel laminated positive electrode material is processed by using a carboxylic acid derivative of niobium such that lithium residue on the surface of the material reacts with the carboxylic acid derivative of niobium and generates Li(NbO(C2O4)2)nH2O, and then different surface reconstruction layers are formed on the surface of the material after high temperature heat treatment, as a result, the cycling performance and discharge performance of the material are significantly improved.
Description
SUNPT20057LU 05.06.2020 lu101837 Specification Method for Modifying High-nickel Positive Electrode Material Technical Field The invention relates to a method for performing surface coating for a high-nickel positive electrode material and an electrode prepared by using the method, belonging to the technical field of lithium batteries.
Background During the preparation of high-nickel electrode materials, excessive lithium is usually required for suppressing cation mixing and lithium volatilization. However, the addition of excessive lithium causes the following problems: 1) after the product is sintered, excessive lithium remains on the surface, and can easily react with H2O and CO; in the air, forming LiOH and Li2CO; residues; 2) in the mixing process of preparing the electrode, Lithium residue reacts with the adhesive solvent N-methyl pyrrolidone, which causes “gel” phenomenon and makes mixing difficult; 3) when the battery is operated for a long period of time, the lithium residue can react with the organic electrolyte, which generates COz, N2, Oz and other gases and causes “flatulence” of batteries; and 4) LiOH and Li2CO;3 are electrochemically inert materials with very low ion conductivity, which hinders the transmission of ions and electrons and affects the ratio performance of the materials. Therefore, when preparing high-nickel laminated materials, measures need to be taken to reduce the amount of residual lithium on the surface. “Water washing--secondary heating” is a common method for removing lithium residues in the prior art. However, when being washed by a large amount of water, the surface structure of the material will be damaged, which reduces capacity and cycling stability.
On the other hand, since Ni*" in high-nickel electrode materials is very unstable, Ni**—Ni°* reaction may easily occur between the high-nickel electrode material and the organic electrolyte at high temperature and high voltage; moreover, Ni** and Li” have similar ionic radius, so the migration from the transition metal status to Li status may easily occur, which results in “cation mixing”. In order to suppress the reaction between active materials and the organic electrolyte, the method of coating with inert materials, such as AlLO3, MgO, AIF3, etc., is usually adopted, but the ion conductivities of these materials 1
SUNPT20057LU 05.06.2020 | lu101837 are very low, which affects the ratio performance of the materials. Another treatment is to coat with lithium conductive materials, such as LisPO4, LizTiO3, Lis VO4, etc. This method can isolate the organic electrolyte from the active surface, but requires the addition of a lithium source, which cannot reduce the content of residual lithium on the surface.
Therefore, the high-nickel positive electrode material needs to reduce the residual lithium content and provide a physical protective layer; meanwhile, the surface layer has a high ion conductivity.
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 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 spinel-type lithium manganese-based composite oxide (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 rate 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.
Summary of the Invention The present invention provides a surface modification method, which uses a carboxylic acid derivative of niobium as a reactant so as to convert and utilize the surface lithium residue, to regulate the reaction heat treatment temperature, and to generate a surface reconstruction layer on the surface of the high-nickel laminated material, thereby reducing the content of lithium residue and enhancing the ratio and cycling stability of the material.
In the present invention, a carboxylic acid derivative of niobium is used for treating the high-nickel | laminated positive electrode material so that the lithium residue on the material surface reacts with the carboxylic acid derivative of niobium, and then forms a surface reconstruction layer on the material surface after high temperature heat treatment, thereby improving the performance of the material. It is found by the inventor that, when the heat treatment temperature is 500-750°C, the structure of the surface | > |
SUNPT20057LU 05.06.2020 1 14101837 reconstruction layer changes with the temperature and physical protective layers with different phases are generated. Therefore, heat treatment temperature may be appropriately chosen according to the performance necessities.
The present invention provides a method of preparing a high-nickel positive electrode material, including the following steps of: (1) mixing a high-nickel laminated material with a dispersant, and stirring intensely to prepare a | suspension of the high-nickel laminated material; (2) dissolving a carboxylic acid derivative of niobium into deionized water so as to prepare an aqueous solution of carboxylic acid derivative of niobium; (3) mixing the suspension of the high-nickel laminated material with the aqueous solution of carboxylic acid derivative of niobium, and adding a complexing agent, wherein the mass ratio between the high-nickel laminated material and the carboxylic acid derivative of niobium is 20-100; a ratio of the amount of the substance between the complexing agent and the carboxylic acid derivative of niobium is 1-5; (4) heating and vigorously stirring the mixture obtained in Step (3) at 90-150°C till the solvent is completely volatilized so as to obtain a solid powder of a high-nickel laminated material coated with a carboxylic acid lithium niobium precursor; (5) performing a heat treatment for the solid powder of high-nickel laminated material coated with carboxylic acid lithium niobium in an oxidizing atmosphere so as to obtain a surface-modified high-nickel laminated material; and (6) crushing and sifting the surface-modified material so as to obtain the high-nickel positive electrode material.
The molecular formula of said high-nickel laminated material is LINi1->Mx, wherein M is one of Co, Mn and Al, and x is 0.01-0.4, preferably x is 0.1-0.4.
The carboxylic acid derivative of niobium is a carboxylic acid salt of niobium with a small carbon atom number, preferably a monobasic or dibasic carboxylic acid niobium salt having 1-5 carbon atoms, and more preferably niobium oxalate or ammonium niobium oxalate.
The dispersant is one or more of water, ethanol, ethylene glycol, propylene glycol, propanol, and butanol.
The complexing agent is one or more of citric acid, tartaric acid, EDTA and ammonia water.
3 |
SUNPT20057LU 05.06.2020 lu101837 The mixing method may be one of the following: directly mixing the active material suspension and the carboxylic acid derivative of niobium, slowly adding the active material suspension to the solution of | the carboxylic acid derivative of niobium by means of a metering pump, and slowly adding the solution of the carboxylic acid derivative of niobium to the active material suspension by means of a metering pump.
In Step (1), a mass ratio of the high-nickel laminated material to the dispersant is 0.01-0.5, preferably 0.1-0.3.
In Step (2), a mass ratio of the carboxylic acid derivative of niobium to the deionized water is
0.01-0.3, preferably 0.05-0.2.
Step (4) is carried out at 0.01-0.5MPa, preferably 0.5-0.3MPa.
In Step (5), the oxidizing atmosphere is an oxygen or air atmosphere, the heat treatment temperature is 450-900°C, and the heat treatment time is 1-12h; the preferable heat treatment temperature is 500-800°C, and the treatment time is 4-8h.
The other aspect of the present invention also discloses a high-nickel positive electrode material prepared by said method and its application to batteries.
Beneficial Effects of the Invention: According to the present invention, a high-nickel laminated positive electrode material is processed by using the carboxylic acid derivative of niobium such that lithium residue on the surface of the material reacts with the carboxylic acid derivative of niobium, and then different surface reconstruction layers are formed on the surface of the material after high temperature heat treatment, as a result, the cycling performance and discharge performance of the material are significantly improved.
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 4
| SUNPT20057LU 05.06.2020 14101837 Mix 10g of LiNio.6Coo.2Mno.202 (NCM-1) with a certain amount of absolute ethanol to prepare slurry of active material.
Dissolve 0.1g of niobium oxalate (NO) in 10mL of deionized water to prepare an aqueous solution of niobium oxalate.
Slowly and dropwise add the aqueous solution of niobium oxalate to the slurry of NCM-1, and add a small amount of citric acid, and then continuously stir and heat the mixture and keep the temperature of the slurry at 60°C.
After adding the solution of niobium oxalate dropwise, raise the temperature to 80°C, and continue stirring the mixture till the solvent is completely | volatilized.
After volatilization of the solvent, dry the obtained powder at 100°C for 4h, and then perform heat treatment at 500°C for 5h in an oxygen atmosphere so as to obtain the final product NCM-NO-1. The residual lithium contents of unmodified product and NO modified products are shown in Table 1; the contrast of ratio performances of the products before and after modification are shown in Table 2; and the contrast of cycling performances of the products before and after modification are shown in Table 3. Table 1 [oem | corm | ae pam] Table 2 Toews [em | mw | cme | moms Table 3 Specific discharge capacity | Specific discharge capacity | Capacity retention ratio of the first cycle mAh-g" of 100 cycles, mAh-g" of 100 cycles, % Example 2
—
SUNPT20057LU 05.06.2020 lu101837 Mix 10g of LiNio.6Coo.2Mno.202 (NCM-1) with a certain amount of absolute ethanol to prepare slurry. Dissolve 0.2g of ammonium niobium oxalate (ANO) in 15mL of deionized water to prepare an aqueous solution of ammonium niobium oxalate. Slowly and dropwise add the ANO aqueous solution to the slurry of NCM-1, and add a certain amount of EDTA, and then continuously stir and heat the mixture and keep the reaction temperature of the slurry at 60°C. After adding the solution of ammonium niobium oxalate (ANO) dropwise, raise the temperature to 80°C, and continue stirring the mixture till the solvent is completely volatilized. Dry the powder at 100°C for 4h, and then perform heat treatment at 700°C for 5h in an oxygen atmosphere so as to obtain the final product NCM-ANO-2. The residual lithium contents of unmodified product and ANO modified products are shown in Table 4, and the contrast of electrical properties of the products before and after modification are shown in Tables 5 and 6..
Table 4 con | taco | tem rs Table 5 Tale m [emer | cme | mine | cma Table 6 Specific capacity of the first | Specific capacity of 100 Specific capacity retention cycle, mAh-g! cycles, mAh:g" ratio, % Example 3 Mix 10g of LiNio.gCoo.1Mno.102(NCM-2) with a certain amount of absolute ethanol to prepare slurry. Dissolve 0.2g of niobium oxalate (NO) in 10mL of deionized water to prepare an NO aqueous solution. 6
SUNPT20057LU 05.06.2020 lu101837 Slowly and dropwise add an NO aqueous solution to the slurry of NCM-2, and add a small amount of citric acid, and then continuously stir and heat the mixture and keep the temperature of the slurry at 60°C.
After adding the NO solution dropwise, maintain the temperature at 60°C, and continue stirring the mixture till the solvent is completely volatilized.
Perform vacuum drying for the powder at 120°C for 4h in a vacuum drying oven, and then perform heat treatment at 700°C for 5h in an oxygen atmosphere so as to obtain the final product NCM-NO-3. The residual lithium contents of unmodified product and NO modified products, as well as the contrast of their electrical properties are shown in Tables 7-9. | Table 7 [ote | toon | roman Table 8 oem [cm | mare | Somane | 106 mare | Table 9 Specific capacity of the Specific capacity of 100 Capacity retention ratio of first cycle, mAh-g"! cycles, mAh-g"! 100 cycles, % Example 4 Dissolve 10g of ammonium niobium oxalate (ANO) in 10mL of water and heat the solution to 60°C.
Slowly pour 10g of LiNio.sCo0.1sA10.0s02 (NCM-3) powder into the ANO solution, add a small amount of EDTA, continuously stir for 30min, and then intensely stir at 80°C till the solvent is completely volatilized.
After volatilization of the solvent, transfer the powder into a vacuum drying oven to dry it at 120°C for 4h, and then perform high-temperature heat treatment at 750°C for 6h in an oxygen atmosphere 7
SUNPT20057LU 05.06.2020 lu101837 so as to obtain the final product NCM-ANO-4. The residual lithium contents of unmodified product and ANO modified products, as well as the contrast of their electrical properties are shown in Tables 10-12. Table 10 ecm [me | sme | sea | mie | Table 11 Specific capacity of the first Specific capacity of 100 Capacity retention ratio cycle, mAh-g"! cycles, mAh-g" of 100 cycles, % Table 12 | em ppm 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.
Comparative Example 1 Mix LiNi0.6C00.2Mn0.202 (NCM-1) with 1wt% of Al203 through ball mill, and perform heat treatment at 750°C under O2 atmosphere for 6h, thereby obtaining AlOs;-modified high-nickel ternary NCM-1 material NCM-1-Al). Table 13 PT wou | coum | ren pr 8
SUNPT20057LU 05.06.2020 lu101837 Table 14 Towne | Cm | mare | Cons’ [06 mai Table 15 1C Capacity of the first | 1C Capacity after 100 1C Capacity retention ratio after cycle, mAh-g" cycles, mAh:g" 100 cycles, % Comparative Example 2 Mix 10g of LiNiosCo002Mng 202 (NCM-1) with a certain amount of absolute ethanol to prepare slurry of active material.
Dissolve 0.1g of niobium oxalate (NO) in 10mL of deionized water to prepare an aqueous solution of niobium oxalate.
Slowly and dropwise add the NO aqueous solution to the slurry of NCM-1, and add a small amount of citric acid, and then continuously stir and heat the mixture and keep the temperature of the slurry at 60°C.
After adding the NO solution dropwise, raise the temperature to 80°C, and continue stirring the mixture till the solvent is completely volatilized.
After volatilization of the solvent, dry the obtained powder at 100°C for 4h, and then perform heat treatment at 400°C for 5h in an oxygen atmosphere so as to obtain the final product NCM-NO-1-400. The residual lithium contents of unmodified product and NO modified products, as well as the contrast of their electrical properties are shown in Tables 16-18. Table 16 CT] woe | coum ora 9
SUNPT20057LU 05.06.2020 lu101837 Table 17 1C Capacity ofthe | 1C Capacity of 100 | 1C Cycling retention ratio first cycle mAh-g' | cycles mAhg! of 100 cycles, % Table 18 Totem [ Cons | ames | soma | 106 man | Comparative Example 3 Mix 10g of LiNio.6Coo.2Mno.202 (NCM-1) with a certain amount of absolute ethanol to prepare slurry of active material.
Dissolve 0.1g of niobium oxalate (NO) in 10mL of deionized water to prepare an aqueous solution of niobium oxalate.
Slowly and dropwise add the NO aqueous solution to the slurry of NCM622, and add a small amount of citric acid, and then continuously stir and heat the mixture and keep the temperature of the slurry at 60°C.
After adding the NO solution dropwise, raise the temperature to 80°C, and continue stirring the mixture till the solvent is completely volatilized.
After volatilization of the solvent, dry the obtained powder at 100°C for 4h, and then perform heat treatment at 900°C for 5h in an oxygen atmosphere so as to obtain the final product NCM-NO-1-900. The residual lithium contents of unmodified product and NO modified products, as well as the contrast of their electrical properties are shown in Tables 19-21. Table 19 PT om | tom [toto Table 20 Tecan | te ca ai | camer
SUNPT20057LU 05.06.2020 lu101837 amos | eat | motifs Table 21 CT Toc tema [oma | soma [man Comparative Example 1 shows that the ratio performance and cycling stability, especially the ratio performance, of NO modified products are better than those of Al,O3 modified products; baased on the contrast between Example 1 and Comparative Examples 2 and 3, NCM-1, which is modified by 1wt% of NO, has better lithium residue removal and electrochemical performance when the treatment temperature ia 500°C, because, when the heat treatment temperature is low, the formed Li-Nb oxide precursor cannot be completely decomposed, and, when the heat treatment temperature is high, the thickness of the surface Li3NbO; phase is large, which can effectively remove lithium residue and significantly improve cycling stability but has little effect on ratio performance enhancement. 11
Claims (9)
1.A method of preparing a high-nickel positive electrode material, including the following steps of: (1) mixing a high-nickel laminated material with a dispersant, and stirring intensely to prepare a suspension of the high-nickel laminated material; (2) dissolving a carboxylic acid derivative of niobium into deionized water so as to prepare an aqueous solution of carboxylic acid derivative of niobium; (3) mixing the suspension of the high-nickel laminated material with the aqueous solution of carboxylic acid derivative of niobium, and adding a complexing agent, wherein the mass ratio between the high-nickel laminated material and the carboxylic acid derivative of niobium is 20-100; a ratio of the amount of the substance between the complexing agent and the carboxylic acid derivative of niobium is 1-5; (4) heating and vigorously stirring the mixture obtained in Step (3) at 90-150°C till the solvent is completely volatilized so as to obtain a solid powder of a high-nickel laminated material coated with a carboxylic acid lithtum niobium precursor; (5) performing a heat treatment for the solid powder of high-nickel laminated material coated with carboxylic acid lithium niobium in an oxidizing atmosphere so as to obtain a surface-modified high-nickel laminated material; and (6) crushing and sifting the surface-modified material so as to obtain the high-nickel positive electrode material.
2. The method according to claim 1, wherein the molecular formula of said high-nickel laminated material in step 1) is LiNi;.xMx, wherein M is one of Co, Mn and Al, and x is 0.01-0.4, preferably x is 0.1-0.3.
3. The method according to claim 1, wherein the dispersant is one or more of water, ethanol, ethylene glycol, propylene glycol, propanol, and butanol; the complexing agent is one or more of citric acid, tartaric acid, EDTA and ammonia water.
4. The method according to claim 1, wherein the carboxylic acid derivative of niobium is a carboxylic acid salt of niobium with a small carbon atom number, preferably a monobasic or dibasic carboxylic acid niobium salt having 1-5 carbon atoms, and more preferably niobium oxalate or ammonium niobium oxalate.
1
SUNPT20057LU 05.06.2020 | lu101837
5. The method according to claim 1, wherein the mixing method may be one of the following: directly mixing the active material suspension and the carboxylic acid derivative of niobium, slowly adding the active material suspension to the solution of the carboxylic acid derivative of niobium by means of a metering pump, and slowly adding the solution of the carboxylic acid derivative of niobium to the active material suspension by means of a metering pump.
6. The method according to claim 1, wherein in Step (1), a mass ratio of the high-nickel laminated material to the dispersant is 0.01-0.5, preferably 0.1-0.3.
7. The method according to claim 1, wherein in Step (2), a mass ratio of the | carboxylic acid derivative of niobium to the deionized water is 0.01-0.3, preferably
0.05-0.2.
8. The method according to claim 1, wherein Step (4) is carried out at 0.01-0.1MPa, preferably 0.05-0.1MPa.
9. The method according to claim 1, wherein in Step (5), the oxidizing atmosphere is an oxygen or air atmosphere, the heat treatment temperature is 450-900°C, and the heat treatment time is 1-12h; the preferable heat treatment temperature is 500-800°C, and the treatment time is 4-8h.
A high-nickel positive electrode material prepared by the method according any of the claims 1-9.
2
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| CN102244231A (en) | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
| CN103339062A (en) | 2011-03-02 | 2013-10-02 | 三井金属矿业株式会社 | Spinel-type lithium-manganese composite oxide |
| JP5928445B2 (en) * | 2011-03-07 | 2016-06-01 | 旭硝子株式会社 | Cathode active material for lithium ion secondary battery and method for producing the same |
| US20180323435A1 (en) * | 2017-05-08 | 2018-11-08 | Hyundai Motor Company | Cathode material for all-solid state battery including coating layer for preventing diffusion and method for preparing the same |
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| JP6302385B2 (en) * | 2013-11-08 | 2018-03-28 | 株式会社東芝 | Method for producing negative electrode active material for non-aqueous electrolyte secondary battery |
| CN107768634A (en) * | 2017-10-17 | 2018-03-06 | 贵州理工学院 | A kind of ion doping and Surface coating modify anode material for lithium-ion batteries and preparation method thereof jointly |
| CN108899539A (en) * | 2018-06-28 | 2018-11-27 | 上海电力学院 | A kind of nickelic ternary lithium ion anode material and preparation method thereof |
| CN109244446B (en) * | 2018-08-04 | 2021-08-20 | 浙江金鹰瓦力新能源科技有限公司 | Modified nickel-cobalt-manganese ternary cathode material and preparation method thereof |
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| CN102244231A (en) | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
| CN103339062A (en) | 2011-03-02 | 2013-10-02 | 三井金属矿业株式会社 | Spinel-type lithium-manganese composite oxide |
| JP5928445B2 (en) * | 2011-03-07 | 2016-06-01 | 旭硝子株式会社 | Cathode active material for lithium ion secondary battery and method for producing the same |
| US20180323435A1 (en) * | 2017-05-08 | 2018-11-08 | Hyundai Motor Company | Cathode material for all-solid state battery including coating layer for preventing diffusion and method for preparing the same |
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