WO2023201486A1 - 电极活性材料前驱体、其制备方法、电极活性材料及电池 - Google Patents
电极活性材料前驱体、其制备方法、电极活性材料及电池 Download PDFInfo
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- WO2023201486A1 WO2023201486A1 PCT/CN2022/087489 CN2022087489W WO2023201486A1 WO 2023201486 A1 WO2023201486 A1 WO 2023201486A1 CN 2022087489 W CN2022087489 W CN 2022087489W WO 2023201486 A1 WO2023201486 A1 WO 2023201486A1
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- Prior art keywords
- electrode active
- active material
- carbon
- oxide particles
- material precursor
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- 239000007772 electrode material Substances 0.000 title claims abstract description 180
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 324
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- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
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- 239000003513 alkali Substances 0.000 claims description 3
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- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
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- 239000012153 distilled water Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 150000001340 alkali metals Chemical class 0.000 description 2
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- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 2
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- 238000004134 energy conservation Methods 0.000 description 2
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
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- 238000007561 laser diffraction method Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
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- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
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- 229910052792 caesium Inorganic materials 0.000 description 1
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- 229910052730 francium Inorganic materials 0.000 description 1
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- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/36—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
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G49/02—Oxides; Hydroxides
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present application relates to the technical field of lithium batteries, and in particular to an electrode active material precursor, its preparation method, electrode active material and battery.
- Electrode active materials cannot meet the energy density and specific capacity requirements of new generation batteries.
- the electrode active material is often subjected to carbon coating post-processing to optimize the transmission of electrons in the electrode active material.
- existing treatment methods cannot effectively improve battery performance.
- This application aims to solve at least one of the technical problems existing in the prior art.
- one purpose of this application is to propose an electrode active material precursor for preparing electrode active materials, so as to solve the problem that electrode active materials require carbon coating post-processing.
- An embodiment of the first aspect of the present application provides an electrode active material precursor, including carbon composite oxide particles, and the oxide satisfies the formula (1): M a O b (1); wherein the M element is selected from the relative atomic mass One or more transition metal elements less than 65, which can be selected from Ni, Co, Fe, Mn, Zn, Mg, Ca, Cu, Mn, Sn, Mo, Ru, Ir, V, Nb, Cr One or more, a>0, b>0, the powder resistivity of the carbon composite oxide particles is less than 100 ⁇ cm.
- the electrode active material precursor includes carbon composite oxide particles, in which the carbon element has high uniformity and good dispersion, so that the carbon composite oxide particles have lower powder resistivity. , avoids the need for carbon coating post-processing for electrode active materials prepared using it as a precursor, solves the adverse effects caused by the above conventional carbon coating post-processing, improves the stability of electrode active materials, and reduces manufacturing costs. At the same time, due to the low powder resistivity of carbon composite oxide particles and good carbon dispersion, the coating integrity of the carbon layer in the electrode active material prepared with it as a precursor is high, and the powder resistivity of the electrode active material is low. Thereby increasing the battery capacity.
- the growth and agglomeration of the electrode active material can be inhibited, and the size of the electrode active material can be limited to the submicron to nanometer level, so that the electrode active material can be charged during charging.
- the ion transport path is short, the kinetics are high, the stability is good, and the charging capacity is higher.
- the atomic mass of the transition metal elements in the carbon composite oxide particles is relatively small, which makes the prepared electrode active material have a higher charging capacity, and the residual material after discharge is lighter, accounting for a smaller weight of the entire pole piece, and can Further increase the proportion of electrode active materials and energy density of the battery.
- the carbon composite oxide particles have a powder resistivity of less than 10 ⁇ cm, optionally less than 1 ⁇ cm. Reducing the powder resistivity of carbon composite oxide particles can further reduce the resistivity of the electrode active material prepared by it and increase the charging capacity.
- the mass content of carbon element in the carbon composite oxide particles is 10% to 40%, optionally 20% to 30%. Controlling the mass content of carbon element in the carbon composite oxide particles within an appropriate range can obtain carbon composite oxide particles with uniform particle size distribution and high carbon element dispersion through uniform carbon composite, and can also reduce the oxidation of the carbon composite.
- the resistivity of the material particles and the powder of electrode active materials prepared with it as a precursor can be improved to increase the battery capacity.
- the median diameter Dv50 of the carbon composite oxide particles is 10 to 200 nm, optionally 20 to 100 nm. Controlling the median particle size Dv50 of carbon composite oxide particles within a suitable range is beneficial to controlling the particle size of electrode active materials prepared using it as a precursor, which is beneficial to the preparation of powders with low resistivity, suitable median particle size Dv50, and high charging Gram capacity electrode active material.
- An embodiment of the second aspect of the present application provides a method for preparing an electrode active material precursor.
- the method includes the following steps: dispersing a carbon source in an aqueous solution containing M ions to obtain a mixed solution; regulating the pH value of the mixed solution to alkaline , to obtain an alkaline mixed solution; a precipitation reaction occurs in the alkaline mixed solution to obtain a precipitate; the precipitate is separated and washed to obtain a precursor; the precursor is dehydrated and dried to prepare an electrode active material precursor; the electrode active material precursor includes carbon composite Oxide particles, the oxide satisfies formula (1): M a O b (1); wherein, the M element is selected from one or more transition metal elements with a relative atomic mass less than 65, and can be selected from Ni, Co , one or more of Fe, Mn, Zn, Mg, Ca, Cu, Mn, Sn, Mo, Ru, Ir, V, Nb, Cr, a>0, b>0, carbon composite oxide particles
- the preparation method is simple and easy to implement, suitable for the preparation of various carbon composite oxide particles, and has the characteristics of low cost and easy promotion and use.
- a carbon source is added during the reaction as a nucleation site for precipitates, which can not only inhibit the agglomeration of precipitates, but also improve the composite effect of carbon and oxides, reduce the resistivity of carbon composite oxide particles, and prepare
- the carbon composite oxide particles have the characteristics of uniform particle size distribution, high dispersion, small powder resistivity, and high carbon content.
- the pH value of the alkaline mixed solution is in the range of 9-13, optionally in the range of 10-12. Controlling the pH value of the alkaline mixed solution within a suitable range is beneficial to the preparation of carbon composite oxide particles with low powder resistivity and a suitable median particle size Dv50.
- reaction time of the precipitation reaction is in the range of 4 to 15 hours, and optionally in the range of 6 to 12 hours. Controlling the reaction time of the precipitation reaction within a suitable range is beneficial to the preparation of carbon composite oxide particles with low powder resistivity and suitable median particle size Dv50.
- the reaction temperature of the precipitation reaction is in the range of 30-80°C, optionally in the range of 40-60°C. Controlling the reaction temperature of the precipitation reaction within a suitable range is beneficial to the preparation of electrode active material precursors with low powder resistivity and suitable median particle size Dv50. Moreover, the preparation method disclosed in this application has a low reaction temperature, which is different from the traditional preparation method that requires reaction at a higher temperature, thereby reducing energy consumption, saving costs, and is conducive to popularization and application.
- a weak alkaline solution is added to the mixed solution before adjusting the pH value of the mixed solution to be alkaline.
- the hydroxide in the weakly alkaline solution slowly ionizes out of the solution, which can control the nucleation process of the precipitate, increase the nucleation rate of M ions on the carbon source, and prevent the precipitate from rapidly growing and precipitating, causing it to be adsorbed on the carbon source.
- the M ions have sufficient time to disperse and nucleate, which improves the dispersibility of the carbon composite oxide particles, facilitates the control of the particle size of the carbon composite oxide, and is conducive to the preparation of carbon composites with low powder resistivity and suitable median particle size Dv50 oxide particles.
- the weak base solution is selected from one or more of ammonia water, ammonium bicarbonate aqueous solution, ammonium carbonate aqueous solution, sodium carbonate aqueous solution, and sodium bicarbonate aqueous solution.
- ammonia water ammonium bicarbonate aqueous solution
- ammonium carbonate aqueous solution sodium carbonate aqueous solution
- sodium bicarbonate aqueous solution sodium bicarbonate aqueous solution.
- the carbon source is selected from one or more of carbon black, acetylene black, Ketjen black, carbon nanotubes, graphene, graphite, carbon fiber, and carbon microspheres. This further expands the applicability of the method.
- the aqueous solution containing M ions is prepared by dissolving one or more of sulfate, nitrate, oxalate, and halide containing M element in water.
- the easy availability of raw materials further increases the versatility of the method.
- the precursor is dried at 100-200°C for 6-20 hours to obtain an electrode active material precursor. Controlling the drying temperature and time is beneficial to the preparation of carbon composite oxide particles with low powder resistivity and suitable median particle size Dv50.
- the third embodiment of the present application provides an electrode active material prepared by using the electrode active material precursor of the above embodiment as a raw material.
- the electrode active material prepared by the electrode active material precursor has optimized powder resistivity and particle size, the carbon coating layer is uniform and complete, and the electrode active material has high electronic conductivity, charging capacity and stability, thereby further improving the battery performance. Capacity, the electrode active material does not need to undergo carbon coating post-processing, saving manufacturing costs.
- An embodiment of a fourth aspect of the present application provides a battery including the electrode active material of the above embodiment. This battery has high capacity.
- Figure 1 is a scanning electron microscope (SEM) photo of Fe 2 O 3 @C provided in Example 3;
- Figure 2 is a transmission electron microscope (TEM) photo of Fe 2 O 3 @C provided in Example 3;
- Figure 3 is an X-ray diffraction (XRD) pattern of Fe 2 O 3 @C provided in Example 3;
- Figure 4 is a transmission electron microscope (TEM) photo of Li 5 FeO 4 @C provided in Example 25;
- Figure 5 is an X-ray diffraction (XRD) pattern of Li 5 FeO 4 @C provided for Example 25;
- Figure 6 is a first charging curve of Li 5 FeO 4 @C provided for Example 25.
- an embodiment means that a particular feature, structure or characteristic described in connection with the embodiment can be included in at least one embodiment of the present application.
- the appearances of this phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those skilled in the art understand, both explicitly and implicitly, that the embodiments described herein may be combined with other embodiments.
- multiple refers to more than two (including two).
- multiple groups refers to two or more groups (including two groups), and “multiple pieces” refers to It is more than two pieces (including two pieces).
- electrode active materials are often mixed with carbon materials for carbon coating post-processing to increase the battery capacity.
- lithium-rich metal oxides are often subjected to carbon coating post-processing to solve the problem of poor stability and poor stability of lithium-rich metal oxides. The problem of poor dynamics.
- the carbon coating post-processing has the following shortcomings: first, the coating integrity of the carbon coating post-processing is poor and random; secondly, in the process of carbon coating post-processing of lithium-rich metal oxides The intermediate pole can easily cause a phase change on the surface, causing the active lithium inside the material to escape and generate lithium carbonate as a by-product on the surface, which in turn reduces the charging capacity of lithium-rich metal oxides; in addition, the post-processing of carbon coating has strict requirements on the production environment.
- the first embodiment of the present application proposes an electrode active material precursor, including carbon composite oxide particles, and the oxide satisfies formula (1): M a O b (1); wherein, the M element One or more transition metal elements with a relative atomic mass less than 65 can be selected from Ni, Co, Fe, Mn, Zn, Mg, Ca, Cu, Mn, Sn, Mo, Ru, Ir, V, One or more of Nb and Cr, a>0, b>0, and the powder resistivity of carbon composite oxide particles is less than 100 ⁇ cm.
- Electrode active material precursors refer to raw materials that can be used to prepare electrode active materials.
- the upper limit value of the powder resistivity of the carbon composite oxide particles may be selected from the group consisting of 50 ⁇ cm, 40 ⁇ cm, 30 ⁇ cm, and 20 ⁇ cm.
- the term "powder resistivity” refers to a parameter used to characterize the conductive properties of the material itself, which is different from the resistivity of the pole piece.
- the powder resistivity is measured using a tester such as a four-probe meter based on "Carbon Composite Lithium Iron Phosphate Cathode Material for Lithium-Ion Batteries” GB/T 30835-2014.
- the carbon composite oxide particles are composite materials including carbon and oxide particles. It can be understood that carbon and oxide particles can be compounded in any way, such as physical mixing, chemical compounding, etc. Specifically, carbon and oxide particles can be composited through stirring, grinding, ultrasound, in-situ growth, grafting, coating, etc.
- M a O b is selected from one or more of the following: M 1 O, M 2 O 2 , M 3 2 O 5 , M 4 2 O 3 , M 5 O.
- M 1 includes one or more of Ni, Co, Fe, Mn, Zn, Mg, Ca, and Cu
- M 2 includes one or more of Mn, Sn, Mo, Ru, and Ir
- M 3 Including one or more of V, Nb, Cr, and Mo
- M 4 includes one or more of Fe, Cr, V, and Mo.
- M 5 includes one or more of Co, V, Cr, and Mo. kind.
- Transition metal elements refer to a series of metal elements in the d zone and ds zone of the periodic table of elements.
- the d zone elements include elements from groups IIIB to VIIB and VIII of the periodic table, and the ds zone includes elements from groups IB to IIB of the periodic table.
- the electrode active material precursor provided in this application includes carbon composite oxide particles, in which the carbon element has high uniformity and good dispersion, so that the carbon composite oxide particles have lower powder resistivity, which avoids the use of carbon composite oxide particles.
- the electrode active material prepared from the precursor requires carbon coating post-processing, which solves the adverse effects caused by the above-mentioned conventional carbon coating post-processing, improves the stability of the electrode active material, and reduces manufacturing costs.
- the coating integrity of the carbon layer in the electrode active material prepared with it as a precursor is high, and the powder resistivity of the electrode active material is low. Thereby increasing the battery capacity.
- the growth and agglomeration of the electrode active material can be inhibited, and the size of the electrode active material can be limited to the submicron to nanometer level, so that the electrode active material can be charged during charging.
- the ion transport path is short, the kinetics are high, the stability is good, and the charging capacity is higher.
- the atomic mass of the transition metal elements in the carbon composite oxide particles is relatively small, which makes the prepared electrode active material have a higher charging capacity, and the residual material after discharge is lighter, accounting for a smaller weight of the entire pole piece, and can Further increase the proportion of electrode active materials and energy density of the battery.
- the powder resistivity of the carbon composite oxide particles is less than 10 ⁇ cm, optionally less than 1 ⁇ cm, and the upper limit of the powder resistivity can be selected from 9 ⁇ cm, 8 ⁇ cm, 7 ⁇ cm , 6 ⁇ cm, 5 ⁇ cm, 4.25 ⁇ cm, 3.58 ⁇ cm, 2.78 ⁇ cm, 2.28 ⁇ cm, 2.15 ⁇ cm, 1.38 ⁇ cm, 1.02 ⁇ cm, 0.98 ⁇ cm, 0.95 ⁇ cm, 0.56 ⁇ cm, 0.42 ⁇ cm, 0.31 ⁇ cm, 0.3 ⁇ cm, 0.28 ⁇ cm, 0.26 ⁇ cm, 0.25 ⁇ cm, 0.24 ⁇ cm, 0.23 ⁇ cm, 0.22 ⁇ cm, 0.21 ⁇ cm, 0.19 ⁇ cm. Reducing the powder resistivity of the carbon composite oxide particles can reduce the resistivity of the electrode active material prepared therefrom and increase the charging capacity of the electrode active material.
- the mass content of carbon element in the carbon composite oxide particles is 10% to 40%, optionally 20% to 30%. In some embodiments, the mass content of carbon element in the carbon composite oxide particles may be selected from the group consisting of 10%, 18%, 20%, 22%, 23%, 24%, 25%, 30% and 40%.
- a carbon content analyzer is used to test the mass content of carbon element in the carbon composite oxide particles.
- the mass content of carbon element in the carbon composite oxide particles can be adjusted by changing the quality of the carbon source added during the process of preparing the carbon composite oxide.
- the mass content of carbon element in the carbon composite oxide particles is too high, it will easily lead to a reduction in the proportion of oxides in the carbon composite oxide particles, the carbon material will agglomerate itself, and the composite effect will be poor. Controlling the mass content of carbon element in the carbon composite oxide particles within an appropriate range can obtain carbon composite oxide particles with uniform particle size distribution and high carbon element dispersion through uniform carbon composite, and can also reduce the oxidation of the carbon composite.
- the resistivity of the material particles and the powder of electrode active materials prepared with it as a precursor can be improved to increase the battery capacity.
- the median diameter Dv50 of the carbon composite oxide particles is 10 to 200 nm, optionally 20 to 100 nm. In some embodiments, the median diameter Dv50 of the carbon composite oxide particles may be selected from 20 nm, 30 nm, 40 nm, 45 nm, 47 nm, 58 nm, 60 nm, 61 nm, 62 nm, 65 nm, 68 nm, 70 nm, 75 nm, 80 nm, 83 nm , 94nm, 100nm, 110nm and 200nm.
- the median diameter Dv50 of the carbon composite oxide particles is a meaning known in the art.
- the median particle size Dv50 also known as the average particle size, represents the particle size corresponding to when the cumulative volume distribution percentage of the material reaches 50%.
- Methods and instruments known in the art can be used for determination. For example, you can refer to the GB/T 19077-2016 particle size distribution laser diffraction method and use a laser particle size analyzer to measure it.
- the particle size of the carbon composite oxide particles is too small, the specific surface area will be too large and the specific surface energy will be too high. In the process of preparing electrode active materials, the carbon composite oxide particles themselves will agglomerate and their dispersion will be reduced. If the particle size of the carbon composite oxide particles is too large, the composite effect of the carbon and oxide particles will be reduced. Controlling the median particle size Dv50 of carbon composite oxide particles within a suitable range is beneficial to controlling the particle size of electrode active materials prepared using it as a precursor, which is beneficial to the preparation of powders with low resistivity, suitable median particle size Dv50, and high charging Gram capacity electrode active material.
- An embodiment of the second aspect of the present application provides a method for preparing the above-mentioned electrode active material precursor.
- the method includes the following steps: dispersing the carbon source in an aqueous solution containing M ions to obtain a mixed solution, and regulating the pH value of the mixed solution to an alkaline level. properties to obtain an alkaline mixed solution.
- the alkaline mixed solution undergoes a precipitation reaction to obtain a precipitate.
- the precipitate is separated and washed to obtain a precursor.
- the precursor is dehydrated and dried to prepare an electrode active material precursor;
- the electrode active material precursor includes carbon Composite oxide particles, the oxide satisfies formula (1): M a O b (1); wherein, the M element is selected from one or more transition metal elements with a relative atomic mass less than 65, and can be selected from Ni, One or more of Co, Fe, Mn, Zn, Mg, Ca, Cu, Mn, Sn, Mo, Ru, Ir, V, Nb, Cr, a>0, b>0, carbon composite oxide
- the powder resistivity of the particles is less than 100 ⁇ cm.
- an aqueous solution of M ions is prepared by dissolving a salt bearing M ions in water.
- the concentration of M element in the mixed solution is 0.5-10 mol/L.
- the carbon source in the mixed liquid is dispersed through various dispersion methods, such as ultrasound, stirring, and other dispersion methods.
- the carbon source is dispersed in an aqueous solution containing M ions, so that the M ions are uniformly adsorbed on the carbon source.
- the carbon source can act as a matrix in the subsequent precipitation reaction process, and the M ions serve as nucleation reactants and are evenly dispersed on the matrix to avoid The generated precipitates aggregate and grow, inhibiting the growth of oxide particles.
- the pH value of the mixed solution is adjusted by adjusting the flow rate and flow rate of the strong alkaline solution.
- the strong alkaline solution can be selected from one or more of sodium hydroxide and potassium hydroxide.
- the hydroxyl radicals in strong alkaline solutions can be quickly ionized from the solution and used to control the growth process of the precipitate.
- the concentration of the strong alkaline solution is 1 to 10 mol/L.
- the strong alkaline solution is added to the mixed solution after the mixed solution has been stirred for a period of time.
- the strong alkali solution is added to the mixed solution after the mixed solution is stirred for 0.1 to 2 hours.
- the strong alkaline solution is added to the mixed solution after the mixed solution is stirred for 1 hour.
- the strong alkaline solution and the mixed liquid are added into the reaction kettle in parallel flow, and the flow rate of the strong alkaline solution is 0.01-0.5 times that of the mixed liquid.
- the strong alkaline solution and the mixed liquid are added into the reaction kettle in parallel flow, and the flow rate of the strong alkaline solution is 0.1 times that of the mixed liquid.
- the dispersion of M ions and carbon source is improved by stirring the mixed solution, assisting the adsorption of M ions on the carbon source, preventing the rapid growth of carbon composite oxide particles, and helping to prepare high dispersion , carbon composite oxide particles with uniform particle size.
- the precipitation reaction is performed under stirring conditions. In some embodiments, the stirring intensity is 100 to 500 rpm. In some embodiments, after the reaction is completed, the precipitate is subjected to suction filtration or centrifugation to separate the precipitate. In some embodiments, the precipitate is washed by repeatedly rinsing it with distilled water or absolute ethanol several times. In some embodiments, carbon composite oxide particles can be obtained by drying the washed product in an oven.
- Precipitation reaction refers to a reaction in which the target product in the solution is precipitated in the form of a solid phase.
- M ions are precipitated in an alkaline mixed solution to obtain a precipitate.
- the preparation method is simple and easy to implement, suitable for the preparation of various carbon composite oxide particles, and has the characteristics of low cost and easy promotion and use.
- a carbon source is added during the reaction as a nucleation site for precipitates, which can not only inhibit the agglomeration of precipitates, but also improve the composite effect of carbon and oxides, reduce the resistivity of carbon composite oxide particles, and prepare
- the carbon composite oxide particles have the characteristics of uniform particle size distribution, high dispersion, small powder resistivity, and high carbon content.
- the pH value of the alkaline mixed solution is in the range of 9-13, optionally in the range of 10-12. In some embodiments, the pH value of the alkaline mixed solution can be selected from any one of 8, 9, 10, 11, 11.6, 11.8, 12, and 13.
- Adjusting the pH value of the alkaline mixture can control the nucleation and growth process of the precipitate. If the pH value of the alkaline mixed solution is too high, the time required for the precipitation reaction is extremely short, the precipitation process is difficult to control, and large particles of precipitation agglomerates are easily formed. If the pH value of the alkaline mixed solution is too low, the aqueous solution containing M ions will not easily form a precipitate. Controlling the pH value of the alkaline mixed solution within a suitable range is beneficial to the preparation of carbon composite oxide particles with low powder resistivity and a suitable median particle size Dv50.
- the reaction time of the precipitation reaction is in the range of 4 to 15 hours, optionally in the range of 6 to 12 hours. In some embodiments, the reaction time of the precipitation reaction can be selected from any one of 4h, 6h, 8h, 12h, and 15h.
- Regulating the reaction time of the precipitation reaction can control the nucleation and growth process of the precipitate. If the reaction time is too short, it will easily lead to incomplete nucleation and growth of the precipitate and poor crystallinity of the material. If the reaction time is too long, the precipitate will continue to grow after nucleation, causing the precipitate particles to be too large. Controlling the reaction time of the precipitation reaction within a suitable range is beneficial to the preparation of carbon composite oxide particles with low powder resistivity and suitable median particle size Dv50.
- the reaction temperature of the precipitation reaction is in the range of 30-80°C, optionally in the range of 40-60°C. In some embodiments, the reaction temperature of the precipitation reaction can be selected from any one of 40°C, 50°C, 60°C, and 80°C.
- Controlling the reaction temperature of the precipitation reaction can control the nucleation and growth process of the precipitate. If the reaction temperature is too low, it will easily lead to incomplete nucleation and growth of the precipitate and poor crystallinity of the material. If the reaction temperature is too high, it will easily cause the precipitate to nucleate and grow too fast to form large particles of precipitate. Controlling the reaction temperature of the precipitation reaction within a suitable range is beneficial to the preparation of electrode active material precursors with low powder resistivity and suitable median particle size Dv50. Moreover, the preparation method disclosed in this application has a low reaction temperature, which is different from the traditional preparation method of electrode active materials or their precursors that require reaction at a higher temperature, thereby reducing energy consumption and saving costs, which is conducive to popularization and application.
- a weak alkaline solution is added to the mixed solution before adjusting the pH value of the mixed solution to alkaline.
- the hydroxide in the weakly alkaline solution slowly ionizes out of the solution, which can control the nucleation process of the precipitate, increase the nucleation rate of M ions on the carbon source, and prevent the precipitate from rapidly growing and precipitating, causing it to be adsorbed on the carbon source.
- the M ions have sufficient time to disperse and nucleate, which improves the dispersibility of the carbon composite oxide particles, facilitates the control of the particle size of the carbon composite oxide, and is conducive to the preparation of carbon composites with low powder resistivity and suitable median particle size Dv50 oxide particles.
- the weak base solution is added to the mixed solution after the mixed solution has been stirred for a period of time. In some embodiments, the weak base solution is added to the mixed solution after the mixed solution is stirred for 0.5 h. Stirring the mixed liquid for a period of time improves the dispersion of M ions and carbon source, assists the adsorption of M ions on the carbon source, and helps to prepare electrode active material precursors with high dispersion and uniform particle size.
- the weak alkaline solution and the mixed liquid are added into the reaction kettle in parallel flow, and the flow rate of the weak alkaline solution is 0.1-0.7 times the flow rate of the mixed liquid, preferably 0.2-0.6 times, and more preferably 0.4 times. Controlling the nucleation speed by controlling the flow rate of the weakly alkaline solution is beneficial to the preparation of carbon composite oxide particles with high dispersion and uniform particle size.
- the weak base solution is selected from one or more of ammonia water, ammonium bicarbonate aqueous solution, ammonium carbonate aqueous solution, sodium carbonate aqueous solution, and sodium bicarbonate aqueous solution.
- the concentration of the weak base solution is preferably 2 to 8 mol/L.
- the carbon source is selected from one or more of carbon black, acetylene black, Ketjen black, carbon nanotubes, graphene, graphite, carbon fiber, and carbon microspheres. It can be understood that any carbon material can be used as a carbon source, further expanding the applicable scope of this method.
- an aqueous solution containing M ions is prepared by dissolving one or more of sulfate, nitrate, oxalate, and halide containing M elements in water.
- the precursor is dried at 100-200°C for 6-20 hours to obtain an electrode active material precursor. If the drying temperature or time is too low, the moisture in the precursor may be incompletely removed. If the drying temperature is too high or the time is too long, the carbon composite oxide particles may agglomerate and grow. Controlling the drying temperature and time is beneficial to the preparation of carbon composite oxide particles with low powder resistivity and suitable median particle size Dv50.
- a third embodiment of the present application provides an electrode active material prepared by using the electrode active material precursor in any of the above embodiments as a raw material.
- the electrode active material prepared from the electrode active material precursor has optimized powder resistivity and particle size, the carbon coating layer is uniform and complete, and the electrode active material has high electronic conductivity, charging capacity and stability, which can further improve the battery. capacity, the electrode active material does not need to undergo carbon coating post-processing, saving manufacturing costs.
- An embodiment of the fourth aspect of the present application provides an electrode active material.
- the electrode active material includes carbon-coated metal oxide particles, and the metal oxide particles satisfy formula (2): Ac M d O e (2); wherein, The A element is selected from one or more alkali metal elements or alkaline earth metal elements, and the M element is selected from one or more transition metal elements with a relative atomic mass less than 65, c>0, d>0, e>0 .
- Alkali metal elements refer to the six metal elements in Group IA in the periodic table of elements except hydrogen (H), namely lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), Francium (Fr).
- Alkaline earth metal elements refer to Group IIA elements in the periodic table of elements, including six elements: beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).
- Transition metal elements refer to a series of metal elements in the d zone and ds zone of the periodic table of elements.
- the d zone elements include elements from groups IIIB to VIIB and VIII of the periodic table, and the ds zone includes elements from groups IB to IIB of the periodic table.
- the atomic mass of the transition metal element in the electrode active material provided by this embodiment is relatively small.
- the carbon-coated metal oxide particles have a higher charging capacity when containing the same number of A ions, and the residual material after discharge is lighter.
- the weight of the entire pole piece is small, which can increase the proportion of electrode active materials and energy density of the battery.
- the A element is selected from one or more of Li, Na, K, Mg, and Ca.
- the above-mentioned metal oxides have high charge capacity and high energy density, and the raw materials are abundant and easily available. They are suitable for use in various batteries and have excellent application prospects.
- the metal oxide is selected from one of Li 2 M 1 O 2 , Li 2 M 2 O 3 , Li 3 M 3 O 4 , Li 5 M 4 O 4 , Li 6 M 5 O 4 or Several, among which, M 1 is selected from one or more of Ni, Co, Fe, Mn, and Cu, M 2 is selected from one or more of Mn, Sn, Mo, Ru, and Ir, and M 3 includes One or more of V, Nb, Cr, and Mo. M 4 is selected from one or more of Fe, Cr, V, and Mo. M 5 includes one or more of Co, V, Cr, and Mo. kind.
- the morphology, composition, structure, surface valence state and electrochemical performance of the electrode active material can be adjusted by regulating the type and proportion of the M element in the metal oxide.
- the M element has abundant valence states, and the valence states of the M element in the metal oxide are all lower than its own highest oxidation valence state.
- the above-mentioned metal oxides have high charge capacity, high energy density and excellent application prospects.
- the metal oxide is selected from one or more of Li 2 NiO 2 , Li 2 CuO 2 , Li 2 MnO 3 , Li 3 VO 4 , Li 5 FeO 4 , and Li 6 CoO 4 .
- the above-mentioned lithium-rich metal oxide preparation method is mature, has high charging capacity and high energy density, can meet the needs of the next generation of rechargeable lithium batteries for large-scale grid storage and electric vehicles, and has high application prospects.
- the molar ratio of the A element to the M element is c:d ⁇ 2, based on the total number of moles of elements of the electrode active material.
- the number of A atoms in the above-mentioned metal oxides is greater than that of M atoms, which makes the electrode active material have a higher charging capacity.
- the electrode active material has a carbon content of 2 to 20 wt%, optionally 5 to 15 wt%, based on the total weight of the electrode active material. In some embodiments, the electrode active material has a carbon content of 2 to 20 wt%, optionally 5 to 15 wt%, based on the total weight of the carbon-coated metal oxide. Appropriate content of carbon coating enables the electrode active material to have low powder resistivity, high material stability and electronic conductivity, and excellent carbon coating effect, which is beneficial to increasing battery capacity.
- the electrode active material includes a doping element.
- the ratio of the solubility product constants of the hydroxide of the doping element and the hydroxide of the M element is between 10 -5 and 10 5 .
- the doping element can be selected from Mg, Zn, Al, Ti.
- the electrode active material includes doping elements, which can further improve the stability of the electrode active material.
- the solubility product refers to the dissolution equilibrium constant of the precipitate, expressed as K sp , and the size of the solubility product reflects the dissolving ability of the poorly soluble electrolyte.
- the ratio of the solubility product constants of the hydroxide of the doping element and the hydroxide of the M element is between 10 -5 and 10 5 to avoid the difference in the solubility products of the hydroxide of the doping element and the hydroxide of the M element. If it is too large, it will lead to uneven doping or even individual precipitation of doping elements, which will help maximize the effectiveness of doping elements and improve the charging capacity and energy density of electrode active materials.
- the carbon-coated metal oxide particles have a powder resistivity of less than 1000 ⁇ cm, optionally less than 350 ⁇ cm, optionally less than 10 ⁇ cm, and further optionally less than 5 ⁇ cm. In some embodiments, the carbon-coated metal oxide particles may optionally have a powder resistivity of less than 100 ⁇ cm, optionally less than 50 ⁇ cm.
- the carbon-coated metal oxide particles may have powder resistivities of 1.24 ⁇ cm, 2.12 ⁇ cm, 2.83 ⁇ cm, 3.18 ⁇ cm, 6.54 ⁇ cm, 10.13 ⁇ cm , 17.24 ⁇ cm, 21.34 ⁇ cm, 25.36 ⁇ cm, 32.41 ⁇ cm, 35.76 ⁇ cm, 45.32 ⁇ cm, 48.35 ⁇ cm, 50.13 ⁇ cm, 56.21 ⁇ cm, 60.28 ⁇ cm , 81.22 ⁇ cm, 89.13 ⁇ cm, 236.11 ⁇ cm and 313.87 ⁇ cm.
- the carbon-coated metal oxide particles provided by this embodiment have low powder resistivity, higher material stability and electronic conductivity, and good carbon coating effect, which is beneficial to increasing battery capacity.
- the median diameter Dv50 of the carbon-coated metal oxide particles is in the range of 100 to 900 nm, optionally in the range of 300 to 700 nm. In some embodiments, the median diameter Dv50 of the carbon-coated metal oxide particles is in the range of 100 to 800 nm, optionally in the range of 400 to 900 nm, optionally in the range of 200 to 600 nm.
- the carbon-coated metal oxide particles provided by this application have a suitable median particle size, a short ion transmission path during the charging process, high kinetics, a higher charging capacity, and a suitable specific surface area, making it less likely to occur. Reunion leads to a reduction in its charging capacity.
- An embodiment of the fifth aspect of the present application provides a method for preparing an electrode active material.
- the method includes: providing carbon composite oxide particles, and the oxide satisfies formula (1): M a O b (1); wherein the M element is selected from The M element is selected from one or more transition metal elements with a relative atomic mass less than 65, a>0, b>0; and the carbon composite metal oxide particles and the A source are sintered to obtain a carbon-coated Metal oxide particles, the metal oxide satisfies formula (2): A c M d O e (2); wherein, the A element is selected from one or more of alkali metal elements or alkaline earth metal elements, and the M element is selected from the relative One or more transition metal elements with an atomic mass less than 65, c>0, d>0, e>0.
- the carbon composite oxide particles are composite materials including carbon and oxide particles. It can be understood that carbon and oxide particles can be compounded in any way, such as physical mixing, chemical compounding, etc. Specifically, carbon and oxide particles can be composited through stirring, grinding, ultrasound, in-situ growth, grafting, etc.
- M a O b is selected from one or more of the following: M 1 O, M 2 O 2 , M 3 2 O 5 , M 4 2 O 3 , M 5 O.
- M 1 includes one or more of Ni, Co, Fe, Mn, Zn, Mg, Ca, and Cu
- M 2 includes one or more of Mn, Sn, Mo, Ru, and Ir
- M 3 Including one or more of V, Nb, Cr, and Mo
- M 4 includes one or more of Fe, Cr, V, and Mo.
- M 5 includes one or more of Co, V, Cr, and Mo. kind.
- the A source is a raw material containing any one or more alkali metals or alkaline earth metals, and can be selected from lithium hydroxide, lithium carbonate, lithium oxide, lithium oxalate, lithium acetate, sodium hydroxide, sodium carbonate, One or more of sodium oxide, sodium oxalate, and sodium acetate.
- the carbon composite metal oxide particles and the A source are evenly mixed to achieve uniform sintering.
- the carbon composite metal oxide particles and the A source can be mixed uniformly by any method, such as mechanical stirring, ball milling, chemical mixing, etc. to improve the uniformity of mixing.
- the sintering process is performed in an atmosphere including an inert gas to increase the purity of the sintered product.
- the atmosphere may be one or more of nitrogen, argon, and hydrogen/argon mixture.
- the inert gas can be any inert gas, such as nitrogen, argon, etc.
- the carbon composite metal oxide particles and the A source are sintered, and then the sintered product is crushed and/or screened to obtain carbon-coated metal oxide particles.
- the carbon-coated metal oxide particles prepared by the above method have high external carbon layer coating integrity and low powder resistivity of the material; in addition, the surface carbon layer in the carbon composite oxide particles can be effectively utilized to inhibit the sintering process.
- the growth and agglomeration of metal oxide particles in the medium limits the particle size of metal oxide particles to the submicron to nanometer level, making the carbon-coated metal oxide particles have a short ion transmission path during the charging process, high kinetics, and charging The gram capacity is higher; at the same time, the carbon coating post-processing of the carbon-coated metal oxide particles is avoided, which effectively improves the stability of the carbon-coated metal oxide particles and saves manufacturing costs.
- the carbon composite oxide particles have a powder resistivity of less than 100 ⁇ cm, optionally less than 10 ⁇ cm.
- Carbon composite oxide particles have low powder resistivity, which proves that the carbon element composite has high uniformity and good dispersion, so that the electrode active material prepared with it as a precursor does not require carbon coating post-processing, solving the problem of conventional carbon coating. It can eliminate the adverse effects caused by post-coating treatment, improve the stability of electrode active materials, and reduce manufacturing costs.
- the carbon layer in the carbon-coated metal oxide particles prepared as a precursor has high coating integrity, and the carbon-coated metal oxide particles have high coating integrity.
- Metal oxide particles have low powder resistivity, thereby increasing battery capacity.
- the median diameter Dv50 of the carbon composite oxide particles is in the range of 10 to 200 nm, optionally in the range of 20 to 100 nm. Controlling the median particle size of the carbon composite oxide particles within an appropriate range is beneficial to controlling the particle size of the prepared carbon-coated metal oxide, reducing the powder resistivity of the carbon-coated metal oxide, and increasing its charging capacity. .
- the carbon content in the carbon composite oxide particles ranges from 10 wt% to 40 wt%, optionally from 20 wt% to 30 wt%, based on the total weight of the carbon composite oxide particles. Controlling the carbon content in the carbon composite oxide particles within an appropriate range is beneficial to reducing the powder resistivity of the carbon-coated metal oxide particles and improving their charging capacity.
- the temperature of the sintering treatment is in the range of 500-700°C, optionally in the range of 550-650°C; and/or the time of the sintering treatment is in the range of 4-20h, optionally in the range of 8-12h .
- the temperature of the sintering process can be selected from the group consisting of 550°C, 590°C, 600°C, 610°C, 620°C, and 650°C.
- the sintering treatment may be selected from 8 h, 10 h, and 12 h.
- the temperature of the sintering process is too low or the time of the sintering process is too short, it will easily lead to poor crystallinity of the carbon-coated metal oxide particles, incomplete phase presentation, and low charging capacity. If the sintering temperature is too high or the sintering treatment time is too long, the median diameter Dv50 of the carbon-coated metal oxide particles will be too large, the delithiation path will be increased, the kinetics will be reduced, and the charging capacity will be low. Controlling the temperature and/or time of the sintering process within a suitable range is beneficial to the preparation of carbon-coated metal oxide particles with low powder resistivity, suitable median particle size Dv50 and high charging gram capacity.
- the A source is selected from one or more oxides, salts, and hydroxides of alkali metals or alkaline earth metals.
- the A source is selected from one or more oxides, salts, and hydroxides of alkali metals or alkaline earth metals.
- one or more of lithium oxide, sodium oxide, and magnesium oxide is selected from one or more oxides, salts, and hydroxides of alkali metals or alkaline earth metals.
- lithium oxide, sodium oxide, and magnesium oxide is selected from one or more oxides, salts, and hydroxides of alkali metals or alkaline earth metals.
- This method has a wide range of applications and can synthesize a variety of carbon-coated metal oxide particles as needed.
- the A source is selected from one or more of lithium hydroxide, lithium carbonate, lithium oxide, lithium oxalate, and lithium acetate, and the lithium element in the A source is compounded with carbon in the oxide particles.
- the molar ratio of elements is in the range of 5.5 to 1.
- the molar ratio of the lithium element in the A source to the M element in the carbon composite oxide particles is in the range of 5.2 to 1.
- the lithium-rich metal oxides prepared by this method exhibit low powder resistivity and high charge capacity.
- carbon composite oxide particles are prepared by liquid phase precipitation.
- the liquid phase precipitation method includes a precipitation reaction, which is a reaction in which the target product in the solution is precipitated in the form of a solid phase. This method is simple, low-cost, and easy to be promoted and applied in large areas.
- An embodiment of the sixth aspect of the present application provides a pole piece, including a current collector and an electrode active material layer disposed on at least one surface of the current collector.
- the electrode active material layer includes the electrode active material in any embodiment.
- the pole piece enables the battery to have a high capacity.
- An embodiment of the seventh aspect of the present application provides a battery, including the electrode active material or pole piece in any embodiment. This battery has high capacity.
- the following examples provide an electrode active material precursor.
- Fe 2 O 3 as an example, the Fe(OH) 3 precursor is obtained through hydrolysis and precipitation, and is dehydrated and dried to obtain Fe 2 O 3 @C.
- the specific preparation method is as follows:
- Configure solution A Prepare an ammonium bicarbonate solution with a concentration of 5mol/L.
- Configure solution B Prepare a sodium hydroxide solution with a concentration of 2mol/L. Add the mixed solution into the reaction kettle. Solution A starts to be added to the reaction kettle 0.5h after the addition of the mixed solution. Solution B starts to be added to the reaction kettle 1h after the addition of the mixed solution to obtain an alkaline mixed solution. The flow rate of solution A The flow rate of solution B is 0.4 times the flow rate of the mixed liquid. The flow rate of solution B is 0.1 times the flow rate of the mixed liquid.
- the pH value of the alkaline mixed liquid is 9. The alkaline mixed liquid undergoes a precipitation reaction when the stirring intensity is 300 rpm. The precipitation reaction is The reaction temperature was 50°C, and the reaction time of the precipitation reaction was 8 hours.
- the precipitate is filtered or centrifuged, and the precipitate is washed several times with distilled water or absolute ethanol to obtain the precursor.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 1. The difference is that the pH value of the alkaline mixed solution in Example 1 is set to 10, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 1. The difference is that the pH value of the alkaline mixed solution in Example 1 is set to 11, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 3. The difference is that the pH value of the alkaline mixed solution in Example 3 is set to 12, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 3. The difference is that the pH value of the alkaline mixed solution in Example 3 is set to 13, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 3. The difference is that the reaction time of the precipitation reaction in Example 3 is set to 4 hours, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 3. The difference is that the reaction time of the precipitation reaction in Example 3 is set to 6 hours, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 3. The difference is that the reaction time of the precipitation reaction in Example 3 is set to 12 hours, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 3. The difference is that the reaction time of the precipitation reaction in Example 3 is set to 15 hours, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 3. The difference is that the reaction temperature of the precipitation reaction in Example 3 is set to 30°C, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 3. The difference is that the reaction temperature of the precipitation reaction in Example 3 is set to 40°C, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 3. The difference is that the reaction temperature of the precipitation reaction in Example 3 is set to 60°C, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 3. The difference is that the reaction temperature of the precipitation reaction in Example 3 is set to 80°C, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor.
- the preparation method is roughly the same as that in Example 3. The difference is that the amount of carbon black added in Example 3 is reduced so that the mass content of carbon element in the generated product is 10%. .
- This embodiment provides an electrode active material precursor.
- the preparation method is roughly the same as that in Example 3. The difference is that the amount of carbon black added in Example 3 is reduced so that the mass content of carbon element in the generated product is 20%. , other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor.
- the preparation method is roughly the same as that in Example 3. The difference is that the amount of carbon black added in Example 3 is increased so that the mass content of carbon element in the generated product is 30%. , other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor.
- the preparation method is roughly the same as that in Example 3. The difference is that the amount of carbon black added in Example 3 is increased so that the mass content of carbon element in the generated product is 40%. , other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, and its preparation method is roughly the same as that in Example 3. The difference is that in Example 3, the carbon source is replaced from carbon black to carbon nanotubes (CNTs), and the carbon nanotubes added are The quality of the tube is such that the mass content of carbon in the product is 20%, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor.
- the preparation method is roughly the same as that in Example 3. The difference is that in Example 3, the carbon source is replaced from carbon black to graphite (Gr). The quality of the graphite added is such that the The mass content of carbon element in the product is 18%, and other operating procedures remain unchanged.
- This embodiment provides an electrode active material precursor, the preparation method of which is roughly the same as that of Example 3, except that the metal salt FeSO 4 ⁇ 7H 2 O in Example 3 is replaced with NiSO 4 ⁇ 6H 2 O,
- the pH value of the alkaline mixed solution is set to 11.8, the reaction time of the precipitation reaction is set to 8 hours, the reaction temperature is changed to 55°C, the mass of carbon black added makes the mass content of carbon element in the generated product 23%, and other operating procedures remain the same. constant.
- This embodiment provides an electrode active material precursor, the preparation method of which is roughly the same as that of Example 3, except that the metal salt FeSO 4 ⁇ 7H 2 O in Example 3 is replaced with CuSO 4 ⁇ 5H 2 O,
- the pH value of the alkaline mixed solution is set to 11.6
- the reaction time of the precipitation reaction is set to 6 hours
- the reaction temperature is set to 45°C
- the mass of carbon black added makes the mass content of carbon element in the generated product 22%, and other operating procedures remain the same. constant.
- This embodiment provides an electrode active material precursor.
- the preparation method is roughly the same as that in Example 3. The difference is that the metal salt FeSO 4 ⁇ 7H 2 O in Example 3 is replaced with CoSO 4 ⁇ 7H 2 O.
- the pH value of the alkaline mixed solution is set to 12
- the reaction time of the precipitation reaction is set to 10h
- the reaction temperature is set to 60°C
- the mass of carbon black added makes the mass content of carbon element in the generated product 24%, and other operating procedures remain the same. constant.
- This embodiment provides an electrode active material precursor.
- the preparation method is roughly the same as that in Example 3. The difference is that the pH value of the alkaline mixed solution in Example 3 is set to 8, and the mass of carbon black added is such that The mass content of carbon element in the generated product is 45%, and other operating procedures remain unchanged.
- This comparative example provides an electrode active material precursor, and its preparation method is roughly the same as that of Comparative Example 1. The difference is that the pH value of the alkaline mixed solution in Comparative Example 1 is set to 14, and the reaction time of the precipitation reaction is set to 2h, the mass content of carbon element in the generated product is 5%, and other operating procedures remain unchanged.
- This comparative example provides an electrode active material precursor, and its preparation method is roughly the same as that of Comparative Example 1. The difference is that the pH value of the alkaline mixed solution in Comparative Example 1 is set to 11, and the reaction time of the precipitation reaction is set to 2h, the reaction temperature of the precipitation reaction is set to 90°C, the mass content of carbon element in the generated product is 16%, and other operating procedures remain unchanged.
- This comparative example provides an electrode active material precursor, and its preparation method is roughly the same as that of Comparative Example 1. The difference is that the pH value of the alkaline mixed solution in Comparative Example 1 is set to 11, and the reaction time of the precipitation reaction is set to 20h, the reaction temperature of the precipitation reaction is set to 25°C, the mass content of carbon element in the generated product is 35%, and other operating procedures remain unchanged.
- This comparative example provides an electrode active material precursor, and its preparation method is roughly the same as that of Comparative Example 1. The difference is that no carbon black is added in Comparative Example 1, and the pH value of the alkaline mixed solution in Comparative Example 1 is Set to 11, the reaction time of the precipitation reaction is set to 8h, the reaction temperature of the precipitation reaction is changed to 50°C, and other operating procedures remain unchanged.
- This comparative example provides an electrode active material precursor. Its preparation method is roughly the same as that of Comparative Example 1. The difference is that the Fe 2 O 3 and carbon black in Comparative Example 5 are ball milled with a carbon mass ratio of 25%. Comparative Example 6 was prepared by mixing, the ball milling speed was 200 rpm, and the ball milling was performed for 6 hours. The obtained product was recorded as Fe 2 O 3 /C.
- This embodiment provides an electrode active material, taking Li 5 FeO 4 @C as an example.
- the specific preparation method is as follows:
- Fe 2 O 3 @C with a carbon content of 25% is selected as the electrode active material precursor.
- the Dv50 of Fe 2 O 3 @C is 10 nm, and the powder resistivity is 1.02 ⁇ cm.
- lithium hydroxide (LiOH ⁇ H 2 O) as the A source add it to the mechanical fusion machine at a metal molar ratio of Li:Fe of 5.1:1, and mix through mechanical fusion at a speed of 300 rpm and a mixing time of 6 hours.
- the mixed raw materials are heated under nitrogen at 3°C/min to a sintering temperature of 600°C, the sintering time is 10h, and then the temperature is naturally cooled to obtain the product.
- Crushing and classification After crushing, classifying and sieving the product, carbon-coated metal oxide particles (Li 5 FeO 4 @C) can be obtained.
- This embodiment provides an electrode active material, the preparation method of which is roughly the same as that of Example 23, except that the Dv50 of Fe 2 O 3 @C in Example 23 is changed to 20 nm, and the powder resistivity is 0.56 ⁇ cm,.
- This embodiment provides an electrode active material, the preparation method of which is roughly the same as that of Example 23, except that the Dv50 of Fe 2 O 3 @C in Example 23 is changed to 60 nm, and the powder resistivity is 0.22 ⁇ cm,.
- This embodiment provides an electrode active material, the preparation method of which is roughly the same as that of Example 25, except that the Dv50 of Fe 2 O 3 @C in Example 25 is changed to 100 nm, and the powder resistivity is 3.58 ⁇ cm.
- This embodiment provides an electrode active material, the preparation method of which is roughly the same as that of Example 25, except that the Dv50 of Fe 2 O 3 @C in Example 25 is changed to 200 nm, and the powder resistivity is 8.32 ⁇ cm.
- This embodiment provides an electrode active material.
- the preparation method is roughly the same as that in Example 25. The difference is that the Fe 2 O 3 @C carbon content in Example 25 is changed to 10%, and the powder resistivity is 15.34 ⁇ . ⁇ cm,.
- This embodiment provides an electrode active material.
- the preparation method is roughly the same as that in Example 25. The difference is that the Fe 2 O 3 @C carbon content in Example 25 is changed to 20%, and the powder resistivity is 10.13 ⁇ . ⁇ cm.
- This embodiment provides an electrode active material, the preparation method of which is roughly the same as that of Example 25, except that the Fe 2 O 3 @C carbon content in Example 25 is changed to 30%, and the powder resistivity is 0.48 ⁇ . ⁇ cm.
- This embodiment provides an electrode active material, the preparation method of which is roughly the same as that of Example 25, except that the Fe 2 O 3 @C carbon content in Example 25 is changed to 40%, and the powder resistivity is 0.71 ⁇ . ⁇ cm.
- This embodiment provides an electrode active material, the preparation method of which is substantially the same as that of Embodiment 25, except that the sintering temperature in Embodiment 25 is changed to 500°C.
- This embodiment provides an electrode active material, the preparation method of which is substantially the same as that of Embodiment 25, except that the sintering temperature in Embodiment 25 is changed to 550°C.
- This embodiment provides an electrode active material, the preparation method of which is substantially the same as that of Embodiment 25, except that the sintering temperature in Embodiment 25 is changed to 650°C.
- This embodiment provides an electrode active material, the preparation method of which is substantially the same as that of Embodiment 25, except that the sintering temperature in Embodiment 25 is changed to 700°C.
- This embodiment provides an electrode active material, the preparation method of which is substantially the same as that of Embodiment 25, except that the sintering time in Embodiment 25 is changed to 4 hours.
- This embodiment provides an electrode active material, the preparation method of which is substantially the same as that of Embodiment 25, except that the sintering time in Embodiment 25 is changed to 8 hours.
- This embodiment provides an electrode active material, the preparation method of which is substantially the same as that of Embodiment 25, except that the sintering time in Embodiment 25 is changed to 12 hours.
- This embodiment provides an electrode active material, the preparation method of which is substantially the same as that of Embodiment 25, except that the sintering time in Embodiment 25 is changed to 20 hours.
- This embodiment provides an electrode active material, the preparation method of which is roughly the same as that of Embodiment 25, except that the carbon source in Embodiment 25 is replaced from carbon black to carbon nanotubes, and the precursor Fe 2 O 3 @CNTs
- the powder resistivity is 0.24 ⁇ cm.
- This embodiment provides an electrode active material, the preparation method of which is roughly the same as that of Embodiment 25, except that the carbon source in Embodiment 25 is replaced from carbon black to graphite, and the powder of the precursor Fe 2 O 3 @Gr The resistivity is 0.23 ⁇ cm.
- This embodiment provides an electrode active material.
- the preparation method is roughly the same as that in Example 25. The difference is that the Fe 2 O 3 @C in Example 25 is changed to NiO@C, and the Dv50 of NiO@C is 58 nm. , the powder resistivity was 0.21 ⁇ cm, the NiO@C carbon content was changed to 23%, and the sintering temperature was changed to 620°C.
- This embodiment provides an electrode active material.
- the preparation method is roughly the same as that in Example 25. The difference is that Fe 2 O 3 @C in Example 25 is changed to CuO@C, and the Dv50 of CuO@C is 62 nm. , the powder resistivity was 0.25 ⁇ cm, the carbon content of CuO@C was changed to 22%, and the sintering temperature was changed to 590°C.
- This embodiment provides an electrode active material, the preparation method of which is roughly the same as that of Example 25, except that Fe 2 O 3 @C in Example 25 is changed to Co 3 O 4 @C, Co 3 O 4
- the Dv50 of @C is 61 nm
- the powder resistivity is 0.19 ⁇ cm
- the carbon content of Co 3 O 4 @C is changed to 24%
- the sintering temperature is changed to 610°C.
- This comparative example provides an electrode active material, taking Li 5 FeO 4 @C as an example.
- the specific preparation method is as follows:
- Fe 2 O 3 @C with a carbon content of 1% is selected as the electrode active material precursor.
- the Dv50 of Fe 2 O 3 @C is 320 nm, and the powder resistivity is 25.16 ⁇ cm.
- lithium hydroxide (LiOH ⁇ H 2 O) as the A source add it to the mechanical fusion machine at a metal molar ratio of Li:Fe of 5.1:1, and mix through mechanical fusion at a speed of 300 rpm and a mixing time of 6 hours.
- the mixed raw materials are heated under nitrogen at 3°C/min to a sintering temperature of 600°C, the sintering time is 10h, and then the temperature is naturally cooled to obtain the product.
- Crushing and classification After crushing, classifying and sieving the product, carbon-coated metal oxide particles (Li 5 FeO 4 @C) can be obtained.
- This comparative example provides an electrode active material, and its preparation method is roughly the same as that of Comparative Example 7. The difference is that the Dv50 of Fe 2 O 3 @C in Comparative Example 7 is changed to 420 nm, and the powder resistivity is 36.78 ⁇ cm. , the carbon content in Fe 2 O 3 @C is 5%, the sintering temperature is changed to 750°C, and other operating procedures remain unchanged.
- This comparative example provides an electrode active material. Its preparation method is roughly the same as that of Comparative Example 7. The difference is that the Dv50 of Fe 2 O 3 @C in Comparative Example 7 is changed to 250 nm, and the powder resistivity is 18.36 ⁇ cm. , the carbon content in Fe 2 O 3 @C is 25%, the sintering temperature is changed to 450°C, the sintering time is changed to 2h, and other operating procedures remain unchanged.
- This comparative example provides an electrode active material. Its preparation method is roughly the same as that of Comparative Example 7. The difference is that the Dv50 of Fe 2 O 3 @C in Comparative Example 7 is changed to 350 nm, and the powder resistivity is 28.74 ⁇ cm. , the carbon content in Fe 2 O 3 @C is 50%, the sintering temperature is changed to 800°C, the sintering time is changed to 22h, and other operating procedures remain unchanged.
- This comparative example provides an electrode active material. Its preparation method is roughly the same as that of Comparative Example 7. The difference is that Fe 2 O 3 is prepared through the steps of Comparative Example 5. The Dv50 of Fe 2 O 3 is 2500nm, and the powder resistivity is 68201.39 ⁇ cm, using Fe 2 O 3 as the electrode active material precursor. The other operating procedures are consistent with Comparative Example 7, and Li 5 FeO 4 is directly used as the electrode active material.
- This comparative example provides an electrode active material, and its preparation method is roughly the same as that of Comparative Example 7.
- Fe 2 O 3 /C is prepared through the steps of Comparative Example 6, and the mass of carbon black is the mass of Fe 2 O 3 25%, the Dv50 of Fe 2 O 3 /C is 2600 nm, and the powder resistivity is 2310.23 ⁇ cm.
- Li 5 FeO 4 is prepared by sintering using the process of Comparative Example 7. Other operating procedures remain unchanged. Change.
- Median particle size Dv50 Measured using the UK Malvern Mastersizer 2000E laser particle size analyzer with reference to the GB/T 19077-2016 particle size distribution laser diffraction method.
- Carbon content test Use carbon content analyzer C content analyzer, equipment model HCS-140, and use high-frequency induction furnace post-combustion infrared absorption method (conventional method) GBT20123-2006 to test the carbon content in the powder based on the determination of the total carbon and sulfur content of steel. .
- Powder resistivity test Dry the powder of carbon composite oxide particles or carbon-coated metal oxide particles, weigh an appropriate amount of powder, and then use a powder resistivity tester, equipment model ST2722 digital four-probe meter, according to "Carbon composite lithium iron phosphate cathode material for lithium-ion batteries" GB/T 30835-2014 measures the powder resistivity of the sample.
- First charging gram capacity test of carbon-coated metal oxide particles Disperse the carbon-coated metal oxide particles, conductive agent carbon black, and binder polyvinylidene fluoride (PVDF) in a mass ratio of 80:10:10 into the solvent N-methylpyrrolidone (NMP), stir thoroughly and mix evenly to obtain a positive electrode slurry.
- the positive electrode slurry is coated on one surface of the positive electrode current collector aluminum foil, and after drying and cold pressing, a positive electrode sheet is obtained.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- controlling the pH value of the alkaline mixed solution can adjust the powder resistivity and median particle size of the carbon composite oxide particles.
- An appropriate pH value of the alkaline mixed solution is beneficial to the preparation of carbon composite oxide particles with low powder resistivity and suitable median particle size.
- controlling the reaction temperature or reaction time of the precipitation reaction can adjust the powder resistivity and median particle size of the carbon composite oxide particles. Appropriate reaction temperature and reaction time of the precipitation reaction are beneficial to preparing carbon composite oxide particles with low powder resistivity and suitable median particle size.
- controlling the carbon content of the carbon composite oxide particles can adjust the powder resistivity and median particle size of the carbon composite oxide particles.
- the median diameter Dv50 and powder resistivity of carbon composite oxide particles first decreased and then increased as the carbon content increased.
- the morphology of the carbon-coated metal oxide particles was tested using a transmission electron microscope TEM.
- the test results are shown in Figure 4. It can be seen from the contrast between light and dark in the figure that the active material particles are evenly coated in carbon, and the particle size is at the nanometer level. Obvious agglomeration occurred, and the carbon-coated metal oxide particles prepared by the method of Example 25 were tested with X-ray diffraction XRD. The test results are shown in Figure 5. It can be seen from the crystal form comparison that the synthesized product is carbon-coated and rich. Lithium iron oxide, recorded as Li 5 FeO4@C, is used as the electrode material. The first charging curve of the battery assembled is shown in Figure 6, and the first charging gram capacity of the battery is calculated based on this.
- adjusting the median particle diameter Dv50 of the carbon composite oxide particles can adjust the powder resistivity and median particle size of the carbon-coated metal oxide particles.
- An appropriate median particle diameter Dv50 of the carbon composite oxide particles is beneficial to the preparation of carbon-coated metal oxide particles with low powder resistivity, appropriate median particle size, and high charge capacity.
- adjusting the carbon content of the carbon composite oxide particles can adjust the powder resistivity and median particle size of the carbon-coated metal oxide particles.
- the appropriate carbon content in the carbon composite oxide particles is beneficial to the preparation of carbon-coated metal oxide particles with low powder resistivity and suitable median particle size, thereby increasing the gram capacity of the battery.
- controlling the sintering temperature and time can adjust the powder resistivity and median particle size of the carbon-coated metal oxide particles.
- the method for preparing carbon-coated metal oxide particles disclosed in this application is suitable for preparing Li 2 NiO 2 @C, Li 2 CuO 2 @C, Li 6 CoO 4 @C, etc. electrode active material, and the prepared products all have low powder resistivity, suitable median particle size, and high charging capacity, indicating that the preparation method is versatile.
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Abstract
Description
Claims (15)
- 一种电极活性材料前驱体,包括碳复合的氧化物颗粒,其特征在于,所述氧化物满足式(1):M aO b (1)其中,M元素选自相对原子质量小于65的过渡金属元素中的一种或几种,可选自Ni、Co、Fe、Mn、Zn、Mg、Ca、Cu、Mn、Sn、Mo、Ru、Ir、V、Nb、Cr中的一种或几种,a>0,b>0,所述碳复合的氧化物颗粒的粉末电阻率小于100Ω·cm。
- 根据权利要求1所述的电极活性材料前驱体,其特征在于,所述碳复合的氧化物颗粒的粉末电阻率小于10Ω·cm,可选为小于1Ω·cm。
- 根据权利要求1所述的电极活性材料前驱体,其特征在于,碳元素在所述碳复合的氧化物颗粒中的质量含量为10%~40%,可选为20%~30%。
- 根据权利要求1所述的电极活性材料前驱体,其特征在于,所述碳复合的氧化物颗粒的中值粒径Dv50为10~200nm,可选为20~100nm。
- 一种制备电极活性材料前驱体的方法,其特征在于,所述方法包括以下步骤:将碳源分散于含有M离子的水溶液中,得到混合液;调控所述混合液的pH值至碱性,得到碱性混合液;所述碱性混合液发生沉淀反应,获得沉淀物;分离、清洗所述沉淀物,得到前体;将所述前体脱水干燥制备得到电极活性材料前驱体;所述电极活性材料前驱体包括碳复合的氧化物颗粒,所述氧化物满足式(1):M aO b (1)其中,M元素选自相对原子质量小于65的过渡金属元素中的一种或几种,可选自Ni、Co、Fe、Mn、Zn、Mg、Ca、Cu、Mn、Sn、Mo、Ru、Ir、V、Nb、Cr中的一种或几种,a>0,b>0,所述碳复合的氧化物颗粒的粉末电阻率小于100Ω·cm。
- 根据权利要求5所述的制备电极活性材料前驱体的方法,其特征在于,所述碱性混合液的pH值在9~13范围内,可选为10~12范围内。
- 根据权利要求5所述的制备电极活性材料前驱体的方法,其特征在于,所述沉淀反应的反应时间在4~15h范围内,可选为6~12h范围内。
- 根据权利要求5所述的制备电极活性材料前驱体的方法,其特征在于,所述沉淀反应的反应温度在30~80℃范围内,可选为40~60℃范围内。
- 根据权利要求5所述的制备电极活性材料前驱体的方法,其特征在于,在调控所述混合液的pH值至碱性前,在所述混合液中加入弱碱溶液。
- 根据权利要求9所述的制备电极活性材料前驱体的方法,其特征在于,所述弱碱溶液选自氨水、碳酸氢铵水溶液、碳酸铵水溶液、碳酸钠水溶液、碳酸氢钠水溶液中的一种或多种。
- 根据权利要求5所述的制备电极活性材料前驱体的方法,其特征在于,所述碳源选自炭黑、乙炔黑、科琴黑、碳纳米管、石墨烯、石墨、碳纤维、碳微球中的一种或多种。
- 根据权利要求5所述的制备电极活性材料前驱体的方法,其特征在于,所述含有M离子的水溶液通过将包含有M元素的硫酸盐、硝酸盐、草酸盐、卤化物中的一种或多种溶解于水中制备而得。
- 根据权利要求5所述的制备电极活性材料前驱体的方法,其特征在于,将所述前体在100~200℃之间烘干6~20h得到所述电极活性材料前驱体。
- 一种电极活性材料,其特征在于,以权利要求1-4中任一项所述的电极活性材料前驱体为原材料制备而得。
- 一种电池,其特征在于,包括如权利要求14中所述的电极活性材料。
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JP2023569616A JP2024517471A (ja) | 2022-04-18 | 2022-04-18 | 電極活物質の前駆体、その調製方法、電極活物質及び電池 |
EP22936737.0A EP4310949A1 (en) | 2022-04-18 | 2022-04-18 | Electrode active material precursor and preparation method therefor, electrode active material and battery |
CN202280055511.6A CN117769771A (zh) | 2022-04-18 | 2022-04-18 | 电极活性材料前驱体、其制备方法、电极活性材料及电池 |
PCT/CN2022/087489 WO2023201486A1 (zh) | 2022-04-18 | 2022-04-18 | 电极活性材料前驱体、其制备方法、电极活性材料及电池 |
KR1020237038877A KR20230170730A (ko) | 2022-04-18 | 2022-04-18 | 전극 활물질 전구체, 이의 제조 방법, 전극 활물질 및 전지 |
US18/387,477 US20240079551A1 (en) | 2022-04-18 | 2023-11-07 | Electrode active material precursor, method for preparing the same, electrode active material, and battery |
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CN102646817A (zh) * | 2011-02-16 | 2012-08-22 | 中国科学院金属研究所 | 锂离子电池用石墨烯/金属氧化物复合负极材料及制备 |
WO2017082338A1 (ja) * | 2015-11-13 | 2017-05-18 | 戸田工業株式会社 | 鉄酸化物-炭素複合体粒子粉末及びその製造方法 |
CN112271292A (zh) * | 2020-10-30 | 2021-01-26 | 格林美(江苏)钴业股份有限公司 | 一种石墨烯包覆四氧化三钴复合材料的制备方法 |
CN112490415A (zh) * | 2019-09-12 | 2021-03-12 | 湖南杉杉能源科技股份有限公司 | 一种锂离子正极材料补锂添加剂及其制备方法 |
CN113550141A (zh) * | 2021-07-22 | 2021-10-26 | 山东科技大学 | 一种碳纤维负载铁氧化物的方法、多孔碳纤维负载铁氧化物的复合材料与应用 |
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- 2022-04-18 CN CN202280055511.6A patent/CN117769771A/zh active Pending
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- 2022-04-18 EP EP22936737.0A patent/EP4310949A1/en active Pending
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CN101154728A (zh) * | 2007-09-07 | 2008-04-02 | 清华大学 | 一种锂离子电池正极材料超细LiFePO4/C的制备方法 |
CN102646817A (zh) * | 2011-02-16 | 2012-08-22 | 中国科学院金属研究所 | 锂离子电池用石墨烯/金属氧化物复合负极材料及制备 |
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CN113550141A (zh) * | 2021-07-22 | 2021-10-26 | 山东科技大学 | 一种碳纤维负载铁氧化物的方法、多孔碳纤维负载铁氧化物的复合材料与应用 |
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