CN112794378A - Lithium-rich manganese-based doped positive electrode material and preparation method and application thereof - Google Patents
Lithium-rich manganese-based doped positive electrode material and preparation method and application thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 110
- 239000011572 manganese Substances 0.000 title claims abstract description 100
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 99
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 75
- 238000002156 mixing Methods 0.000 claims abstract description 60
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 50
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims description 80
- 239000002245 particle Substances 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000010405 anode material Substances 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 72
- 238000006243 chemical reaction Methods 0.000 description 37
- 239000000203 mixture Substances 0.000 description 25
- 239000008139 complexing agent Substances 0.000 description 24
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 19
- 229910052808 lithium carbonate Inorganic materials 0.000 description 19
- 239000013078 crystal Substances 0.000 description 17
- 239000010406 cathode material Substances 0.000 description 16
- 238000000975 co-precipitation Methods 0.000 description 14
- 239000012670 alkaline solution Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 229910017053 inorganic salt Inorganic materials 0.000 description 12
- 229940099596 manganese sulfate Drugs 0.000 description 12
- 239000011702 manganese sulphate Substances 0.000 description 12
- 235000007079 manganese sulphate Nutrition 0.000 description 12
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 12
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 12
- 239000012266 salt solution Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/002—Compounds containing, besides ruthenium, rhodium, palladium, osmium, iridium, or platinum, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- 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
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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
- H01M4/52—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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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 lithium-rich manganese-based doped anode material and a preparation method and application thereof. The method for preparing the lithium-rich manganese-based doped positive electrode material comprises the following steps: providing a precursor of a doped lithium-rich manganese-based positive electrode material and a lithium salt; mixing the doped lithium-rich manganese-based positive electrode material precursor with a part of the lithium salt and carrying out first calcination treatment to obtain a positive electrode material precursor; and mixing the positive electrode material precursor with the rest part of the lithium salt and carrying out second calcination treatment to obtain the doped lithium-rich manganese-based positive electrode material. According to the method, the lithium salt is calcined with the precursor step by step, so that generation of impure phases in the material can be effectively inhibited, and the performance of the product is improved.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a lithium-rich manganese-based doped positive electrode material and a preparation method and application thereof.
Background
The single crystal or single crystal-like particle cathode material has better performance than the polycrystalline particle cathode material, and has been accepted by the industry and scientific research community. The lithium-rich manganese-based layered cathode material is considered as a next-generation high-specific-volume lithium ion battery cathode material, and the preparation of single crystal particles of the lithium-rich manganese-based layered cathode material, particularly the preparation of multi-element doped single crystal lithium-rich manganese-based layered cathode material, is one of key core technologies in the field.
In the prior art, for the preparation of the crystal lithium-rich manganese-based layered cathode material, a process of adding a lithium salt once and then carrying out high-temperature treatment in two sections is adopted.
Chinese patent CN109537054A discloses a high-rate doped lithium-rich manganese-based anode material single crystal and a preparation method thereof, wherein the patent adopts a coprecipitation method to obtain a doped precursor, and then lithium salt and an auxiliary agent are mixed to obtain a material after one-time high-temperature treatment. However, the introduction of the flux greatly complicates the material preparation process and the production cost, and the flux removal process also affects the performance of the lithium manganese-based layered cathode material, causing unnecessary side reactions, thereby causing deterioration in the electrochemical performance of the cathode material.
Chinese patent CN110391417A discloses a preparation method of a mono-like crystal doped lithium-rich manganese-based anode material, which adopts oxalate as a raw material and utilizes a sol-gel method to obtain the material after one-time high-temperature treatment. The material prepared by the method has poor consistency due to uneven element dispersion, and influences on actual performance.
In summary, the existing lithium-rich manganese-based doped positive electrode material and the preparation method thereof still need to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a lithium-rich manganese-based doped positive electrode material, and a preparation method and application thereof. The method for preparing the lithium-rich manganese-based doped anode material can effectively inhibit the generation of impure phases in the material by calcining the lithium salt and the precursor step by step, thereby improving the performance of the product.
In one aspect of the invention, the invention provides a method for preparing a doped lithium-rich manganese-based positive electrode material. According to an embodiment of the invention, the method comprises: providing a precursor of a doped lithium-rich manganese-based positive electrode material and a lithium salt; mixing the doped lithium-rich manganese-based positive electrode material precursor with a part of the lithium salt and carrying out first calcination treatment to obtain a positive electrode material precursor; and mixing the positive electrode material precursor with the rest part of the lithium salt and carrying out second calcination treatment to obtain the doped lithium-rich manganese-based positive electrode material.
According to the method for preparing the lithium-rich manganese-based positive electrode material in the embodiment of the invention, firstly, the precursor doped with the lithium-rich manganese-based positive electrode material is mixed with part of lithium salt and calcined to obtain the positive electrode material precursor which can be used as a seed crystal, and then, the obtained positive electrode material precursor is mixed with the rest part of lithium salt and calcined. The lithium salt is calcined step by step with the precursor, so that the generation of an impure phase (a compound of lithium-doping element-oxygen) in the material can be effectively inhibited, and the high-purity single crystal doping lithium-rich manganese-based layered anode material is obtained, thereby improving the performance of the product.
In addition, the method for preparing the doped lithium-rich manganese-based cathode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the average particle size of the doped lithium-rich manganese-based positive electrode material precursor is 1-5 μm.
In some embodiments of the invention, the molar ratio of the doped lithium-rich manganese-based positive electrode material precursor to the lithium salt is 1 (1.4-1.7).
In some embodiments of the present invention, the portion of the lithium salt is 80% to 95% of the total amount of the lithium salt.
In some embodiments of the invention, the first calcination treatment comprises: and mixing the precursor of the lithium-rich manganese-based positive electrode material with a part of the lithium salt, heating to 500-600 ℃ at a heating rate of 5-15 ℃/min, keeping the temperature for 4-6 h, heating to 850-950 ℃ at a heating rate of 5-15 ℃/min, and keeping the temperature for 10-14 h to obtain the precursor of the positive electrode material.
In some embodiments of the invention, the second calcination treatment comprises: and mixing the precursor of the positive electrode material with the rest part of the lithium salt, heating to 750-850 ℃ at the heating rate of 5-15 ℃/min, and keeping the temperature for 10-14 h to obtain the doped lithium-rich manganese-based positive electrode material.
In some embodiments of the present invention, the doping element in the doped lithium-rich manganese-based positive electrode material precursor is at least one selected from Al, La, Mg, Na, Nb, Ni, Ru, Ti, Zr.
In some embodiments of the invention, the content of the doping element is 2-8 mol% of the precursor of the doped lithium-rich manganese-based positive electrode material.
In some embodiments of the present invention, before mixing the positive electrode material precursor with the remaining portion of the lithium salt and performing the second calcination treatment, further comprises: and grinding the precursor of the positive electrode material until the average particle size is 3-4 mu m.
In another aspect of the invention, the invention provides a lithium-rich manganese-based doped positive electrode material. According to the embodiment of the invention, the lithium-rich manganese-based doped cathode material is prepared by the method for preparing the lithium-rich manganese-based doped cathode material of the embodiment. Therefore, the single crystal of the lithium-rich manganese-based doped anode material is high in purity, and the performance of the doped element can be better exerted, so that the lithium-rich manganese-based doped anode material can obtain better performance.
In yet another aspect of the present invention, a lithium battery is provided. According to an embodiment of the invention, the lithium battery comprises the doped lithium-rich manganese-based positive electrode material of the embodiment. Therefore, the lithium battery has better electrical property.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow chart of a method for preparing a doped lithium-rich manganese-based cathode material according to one embodiment of the invention;
FIG. 2 is an XRD spectrum of the doped lithium-rich manganese-based positive electrode material prepared in examples 1 to 6;
fig. 3 is a graph showing the cycle test results of the button cell made of the lithium-rich manganese-based doped positive electrode material prepared in examples 1 to 6.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, the invention provides a method for preparing a doped lithium-rich manganese-based positive electrode material. According to an embodiment of the invention, the method comprises: providing a precursor of a doped lithium-rich manganese-based positive electrode material and a lithium salt; mixing the precursor of the lithium-rich manganese-based positive electrode material with a part of lithium salt and carrying out first calcination treatment to obtain a precursor of the positive electrode material; and mixing the precursor of the positive electrode material with the rest part of the lithium salt and carrying out second calcination treatment to obtain the doped lithium-rich manganese-based positive electrode material.
The method for preparing the doped lithium-rich manganese-based positive electrode material according to the embodiment of the invention is further described in detail below. Referring to fig. 1, the method includes:
s100: providing a precursor of a doped lithium-rich manganese-based positive electrode material and a lithium salt
According to some embodiments of the present invention, the source and specific type of the doped lithium-rich manganese-based positive electrode material precursor are not particularly limited, and may be prepared by a metal salt co-precipitation method, for example. The composition of the precursor of the lithium-rich manganese-based positive electrode material can be expressed as aLi2Mn(OH)2·(1-a)LiM(OH)2Wherein, 0<a<1 and M is a doping element.
According to some embodiments of the present invention, the doping element doped in the lithium-rich manganese-based positive electrode material precursor may be at least one selected from Al, La, Mg, Na, Nb, Ni, Ru, Ti, Zr. The content of the doping elements can be 2-8 mol% of the precursor of the lithium-rich manganese-based positive electrode material. The inventor finds that by controlling the content of the doping element in the above range, the structural stability of the material can be effectively improved, the migration process of Ni ions can be inhibited, the crystal structure transformation can be suppressed, and finally, lower voltage attenuation can be obtained.
According to some embodiments of the present invention, the average particle size of the doped lithium-rich manganese-based positive electrode material precursor may be 1 to 5 μm, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, and the like. Therefore, the material with excellent rate performance can be obtained, and the compaction density of the electrode plate can be considered at the same time.
In addition, according to some embodiments of the present invention, the precursor of the doped lithium-rich manganese-based positive electrode material used in the present invention is preferably a precursor with a flower-like porous structure, so that the performance of the prepared positive electrode material product is better.
In addition, specific kinds of the above lithium salt are not particularly limited, and lithium salts commonly used in the art, for example, lithium carbonate, lithium hydroxide, lithium nitrate, and the like, may be used.
S200: first calcination treatment
According to some embodiments of the present invention, the molar ratio of the doped lithium-rich manganese-based positive electrode material precursor to the lithium salt is 1 (1.4-1.7), such as 1:1.4, 1:1.45, 1:1.5, 1:1.55, 1:1.6, 1:1.65, 1:1.7, and the like. The inventor finds that by controlling the molar ratio of the precursor of the lithium-rich manganese-based positive electrode material to the lithium salt, a high-performance material with less crystal defects and higher crystallinity can be obtained. If the precursor of the lithium-rich manganese-based positive electrode material is doped with too low lithium salt, impure phases such as spinel phase and spinel-like phase can appear, so that the specific capacity, the cycling stability and the like of the material are reduced; if the precursor of the lithium-rich manganese-based positive electrode material and the lithium salt are too high, an impurity phase of a rock salt phase can appear, so that the specific capacity, the cycling stability and the like of the material are sharply reduced.
According to some embodiments of the present invention, the lithium salt mixed with the precursor in the first calcination process may be 80% to 95%, for example, 80%, 82%, 85%, 88%, 90%, 92%, 95%, etc., of the total amount of the lithium salt. The inventors found that by controlling the amount of the lithium salt mixed with the precursor in the first calcination treatment to be within the above range, the requirement of the precursor for the lithium salt can be preferentially met, so that the doping element is prevented from reacting with the lithium salt to generate a lithium-containing compound, and the doping element cannot enter a doping position in a crystal lattice, but coexists with the lithium-rich manganese-based positive electrode material in a separate phase. If the lithium salt dosage is too low, the first calcined product has an impure phase similar to spinel phase, and the final generation of the lithium-rich manganese-based positive electrode material is influenced; if the lithium salt is used in an excessive amount, the first calcined product has rock salt and other impure phases, and the generation of the final lithium-rich manganese-based cathode material is affected.
According to some embodiments of the invention, the first calcination treatment comprises: mixing the lithium-rich manganese-based positive electrode material precursor with a part of lithium salt, heating to 500-600 ℃ at a heating rate of 5-15 ℃/min, keeping the temperature for 4-6 h, heating to 850-950 ℃ at a heating rate of 5-15 ℃/min, and keeping the temperature for 10-14 h to obtain the positive electrode material precursor. Specifically, in the first stage, the heating rate can be 5 ℃/min, 8 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min and the like, the target temperature can be 500 ℃, 525 ℃, 550 ℃, 575 ℃, 600 ℃ and the like, and the constant temperature time can be 4h, 4.5h, 5h, 5.5h, 6h and the like. In the second stage, the heating rate can be 5 ℃/min, 8 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min and the like, the target temperature can be 850 ℃, 875 ℃, 900 ℃, 925 ℃, 950 ℃ and the like, and the constant temperature time can be 10h, 11h, 12h, 13h, 14h and the like. By carrying out the first calcination treatment under the above conditions, the requirement of the precursor for the lithium salt can be preferentially met, so that the condition that the doping element cannot enter the doping position in the crystal lattice due to the generation of a lithium-containing compound by the reaction of the doping element and the lithium salt is avoided, and the separately existing phase and the lithium-rich manganese-based positive electrode material coexist.
S300: second calcination treatment
According to some embodiments of the invention, the second calcination treatment comprises: and mixing the precursor of the positive electrode material with the rest part of the lithium salt, heating to 750-850 ℃ at the heating rate of 5-15 ℃/min, and keeping the temperature for 10-14 h to obtain the lithium-rich manganese-based doped positive electrode material. Specifically, the temperature rate can be 5 ℃/min, 8 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min and the like, the target temperature can be 750 ℃, 775 ℃, 800 ℃, 825 ℃, 850 ℃ and the like, and the constant temperature time can be 10h, 11h, 12h, 13h, 14h and the like. By performing the second calcination treatment under the above-described conditions, the growth of primary crystal grains can be promoted, and a material with high crystallinity can be obtained.
In addition, according to some embodiments of the present invention, before mixing the positive electrode material precursor with the remaining portion of the lithium salt and performing the second calcination treatment, the positive electrode material precursor may be ground to an average particle size of 3 to 4 μm. The inventors have found in their studies that by grinding the positive electrode material precursor to the above-mentioned particle size and then performing the second calcination treatment, sufficient mixing and contact between the reactants can be ensured, and a material having excellent properties can be more easily obtained.
In another aspect of the invention, the invention provides a lithium-rich manganese-based doped positive electrode material. According to the embodiment of the invention, the lithium-rich manganese-based doped cathode material is prepared by the method for preparing the lithium-rich manganese-based doped cathode material of the embodiment. Therefore, the single crystal of the lithium-rich manganese-based doped anode material is high in purity, and the performance of the doped element can be better exerted, so that the lithium-rich manganese-based doped anode material can obtain better performance.
In addition, it should be noted that all the features and advantages described above for the method for preparing the lithium-rich manganese-based doped positive electrode material are also applicable to the lithium-rich manganese-based doped positive electrode material, and are not described in detail herein.
In yet another aspect of the present invention, a lithium battery is provided. According to an embodiment of the invention, the lithium battery comprises the doped lithium-rich manganese-based positive electrode material of the embodiment. Therefore, the lithium battery has better electrical property.
In addition, it should be noted that the lithium battery has all the features and advantages described above for the doped lithium-rich manganese-based positive electrode material, and thus, the description thereof is omitted.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1) Mixing nickel sulfate, manganese sulfate and ruthenium chloride according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.20, the reaction temperature is 55 ℃, the reaction time is 22 hours, the stirring speed is 450r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) mixing the sample C with lithium carbonate according to a molar ratio of 1:1.47, heating the mixture from room temperature to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5 hours, and then heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10 hours to obtain a sample D;
(5) and crushing and sieving the sample D, mixing the sample D with lithium carbonate according to the molar ratio of 1:0.08, heating to 800 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Comparative example 1
(1) Mixing nickel sulfate, manganese sulfate and ruthenium chloride according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.2, the reaction temperature is 55 ℃, the reaction time is 22 hours, the stirring speed is 450r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) and uniformly mixing the sample C and lithium carbonate according to the mass ratio of 1:1.55, heating the mixture from room temperature to 550 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 5 hours, heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Example 2
(1) Mixing nickel sulfate, manganese sulfate and lanthanum chloride according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.2, the reaction temperature is 55 ℃, the reaction time is 22 hours, the stirring speed is 400r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) mixing the sample C with lithium carbonate according to a molar ratio of 1:1.47, heating the mixture from room temperature to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5 hours, and then heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10 hours to obtain a sample D;
(5) and crushing and sieving the sample D, mixing the sample D with lithium carbonate according to the molar ratio of 1:0.08, heating to 800 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Comparative example 2
(1) Mixing nickel sulfate, manganese sulfate and lanthanum chloride according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.2, the reaction temperature is 55 ℃, the reaction time is 22 hours, the stirring speed is 400r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) and uniformly mixing the sample C and lithium carbonate according to the mass ratio of 1:1.55, heating the mixture from room temperature to 550 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 5 hours, heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Example 3
(1) Mixing nickel sulfate, manganese sulfate and magnesium nitrate according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.0, the reaction temperature is 50 ℃, the reaction time is 23 hours, the stirring speed is 350r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) mixing the sample C with lithium carbonate according to a molar ratio of 1:1.47, heating the mixture from room temperature to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5 hours, and then heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10 hours to obtain a sample D;
(5) and crushing and sieving the sample D, mixing the sample D with lithium carbonate according to the molar ratio of 1:0.08, heating to 800 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Comparative example 3
(1) Mixing nickel sulfate, manganese sulfate and magnesium nitrate according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.0, the reaction temperature is 50 ℃, the reaction time is 23 hours, the stirring speed is 350r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) and uniformly mixing the sample C and lithium carbonate according to the mass ratio of 1:1.55, heating the mixture from room temperature to 550 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 5 hours, heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Example 4
(1) Mixing nickel sulfate, manganese sulfate and aluminum nitrate according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.1, the reaction temperature is 50 ℃, the reaction time is 23 hours, the stirring speed is 400r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) mixing the sample C with lithium carbonate according to a molar ratio of 1:1.47, heating the mixture from room temperature to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5 hours, and then heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10 hours to obtain a sample D;
(5) and crushing and sieving the sample D, mixing the sample D with lithium carbonate according to the molar ratio of 1:0.08, heating to 800 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Comparative example 4
(1) Mixing nickel sulfate, manganese sulfate and aluminum nitrate according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.2, the reaction temperature is 50 ℃, the reaction time is 23 hours, the stirring speed is 400r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) and uniformly mixing the sample C and lithium carbonate according to the mass ratio of 1:1.55, heating the mixture from room temperature to 550 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 5 hours, heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Example 5
(1) Mixing nickel sulfate, manganese sulfate and zirconium nitrate according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.2, the reaction temperature is 55 ℃, the reaction time is 22 hours, the stirring speed is 450r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) mixing the sample C with lithium carbonate according to a molar ratio of 1:1.47, heating the mixture from room temperature to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5 hours, and then heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10 hours to obtain a sample D;
(5) and crushing and sieving the sample D, mixing the sample D with lithium carbonate according to the molar ratio of 1:0.08, heating to 800 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Comparative example 5
(1) Mixing nickel sulfate, manganese sulfate and zirconium nitrate according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.2, the reaction temperature is 55 ℃, the reaction time is 22 hours, the stirring speed is 450r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) and uniformly mixing the sample C and lithium carbonate according to the mass ratio of 1:1.55, heating the mixture from room temperature to 550 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 5 hours, heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Example 6
(1) Mixing nickel sulfate, manganese sulfate and chromium nitrate according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.2, the reaction temperature is 50 ℃, the reaction time is 22 hours, the stirring speed is 400r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) mixing the sample C with lithium carbonate according to a molar ratio of 1:1.47, heating the mixture from room temperature to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5 hours, and then heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10 hours to obtain a sample D;
(5) and crushing and sieving the sample D, mixing the sample D with lithium carbonate according to the molar ratio of 1:0.08, heating to 800 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Comparative example 6
(1) Mixing nickel sulfate, manganese sulfate and chromium nitrate according to a molar ratio of 25:70:5 to prepare an inorganic salt solution A with a total metal ion concentration of 2 mol/L;
(2) mixing sodium hydroxide and a complexing agent to form an alkaline solution B, wherein the concentration of the sodium hydroxide is 170g/L, and the concentration of the complexing agent is 15 g/L;
(3) adopting a coprecipitation reaction kettle, controlling the reaction conditions that the pH value is 10.2, the reaction temperature is 50 ℃, the reaction time is 22 hours, the stirring speed is 400r/min, filtering to obtain a precursor with the particle size of 3-5 mu m, washing to remove residues such as sulfate radicals and the like, and drying to obtain a sample C;
(4) and uniformly mixing the sample C and lithium carbonate according to the mass ratio of 1:1.55, heating the mixture from room temperature to 550 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 5 hours, heating the mixture to 900 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 12 hours to obtain the lithium-rich manganese-based doped anode material.
Test example
XRD characterization is carried out on the doped lithium-rich manganese-based positive electrode materials prepared in the embodiments 1-6, and the results are shown in FIG. 2. As can be seen from FIG. 2, the lithium-rich manganese-based doped positive electrode material prepared by the embodiment of the invention has high crystal purity and no impure phase and impurity peak.
The lithium-rich manganese-based doped positive electrode materials prepared in examples 1 to 6 were prepared into button cells, and cycle performance tests were performed, and the results are shown in fig. 3. As can be seen from fig. 3, the button cell prepared from the doped lithium-rich manganese-based positive electrode material crystal prepared in the embodiment of the invention has excellent cycle performance.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for preparing a lithium-rich manganese-based doped positive electrode material is characterized by comprising the following steps:
providing a precursor of a doped lithium-rich manganese-based positive electrode material and a lithium salt;
mixing the doped lithium-rich manganese-based positive electrode material precursor with a part of the lithium salt and carrying out first calcination treatment to obtain a positive electrode material precursor;
and mixing the positive electrode material precursor with the rest part of the lithium salt and carrying out second calcination treatment to obtain the doped lithium-rich manganese-based positive electrode material.
2. The method according to claim 1, wherein the average particle size of the doped lithium-rich manganese-based positive electrode material precursor is 1-5 μm.
3. The method according to claim 1, wherein the molar ratio of the doped lithium-rich manganese-based positive electrode material precursor to the lithium salt is 1 (1.4-1.7).
4. The method of claim 1, wherein the portion of the lithium salt is 80% to 95% of the total amount of the lithium salt.
5. The method according to claim 1, characterized in that said first calcination treatment comprises: and mixing the precursor of the lithium-rich manganese-based positive electrode material with a part of the lithium salt, heating to 500-600 ℃ at a heating rate of 5-15 ℃/min, keeping the temperature for 4-6 h, heating to 850-950 ℃ at a heating rate of 5-15 ℃/min, and keeping the temperature for 10-14 h to obtain the precursor of the positive electrode material.
6. The method according to claim 1, characterized in that said second calcination treatment comprises: and mixing the precursor of the positive electrode material with the rest part of the lithium salt, heating to 750-850 ℃ at the heating rate of 5-15 ℃/min, and keeping the temperature for 10-14 h to obtain the doped lithium-rich manganese-based positive electrode material.
7. The method according to claim 1, wherein the doping element in the doped lithium-rich manganese-based positive electrode material precursor is selected from at least one of Al, La, Mg, Na, Nb, Ni, Ru, Ti, Zr;
optionally, the content of the doping element is 2-8 mol% of the precursor of the lithium-rich manganese-based doped positive electrode material.
8. The method according to any one of claims 1 to 7, further comprising, before mixing the positive electrode material precursor with the remaining part of the lithium salt and performing the second calcination treatment: and grinding the precursor of the positive electrode material until the average particle size is 3-4 mu m.
9. A lithium-rich manganese-based doped positive electrode material, which is characterized by being prepared by the method of claims 1-8.
10. A lithium battery comprising the doped lithium-rich manganese-based positive electrode material of claim 9.
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| CN116143200A (en) * | 2023-04-23 | 2023-05-23 | 宜宾锂宝新材料有限公司 | High-compaction micron monocrystal lithium-rich manganese-based positive electrode material, preparation method and lithium battery |
Citations (2)
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| CN111170377A (en) * | 2020-01-19 | 2020-05-19 | 昆明理工大学 | Preparation method of lithium-rich manganese-based positive electrode material |
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| CN109728262A (en) * | 2018-11-30 | 2019-05-07 | 高点(深圳)科技有限公司 | Anode material for lithium-ion batteries and its preparation method and application |
| CN111170377A (en) * | 2020-01-19 | 2020-05-19 | 昆明理工大学 | Preparation method of lithium-rich manganese-based positive electrode material |
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| CN114684874A (en) * | 2022-03-08 | 2022-07-01 | 宜宾光原锂电材料有限公司 | Doped high-rate 5-series monocrystal precursor and preparation method thereof |
| CN114684874B (en) * | 2022-03-08 | 2023-08-08 | 宜宾光原锂电材料有限公司 | Doped high-magnification 5-series single crystal precursor and preparation method thereof |
| CN116143200A (en) * | 2023-04-23 | 2023-05-23 | 宜宾锂宝新材料有限公司 | High-compaction micron monocrystal lithium-rich manganese-based positive electrode material, preparation method and lithium battery |
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