WO2024040908A1 - 一种多孔球形三元前驱体及其制备方法、三元正极材料、正极极片和电池 - Google Patents

一种多孔球形三元前驱体及其制备方法、三元正极材料、正极极片和电池 Download PDF

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WO2024040908A1
WO2024040908A1 PCT/CN2023/079086 CN2023079086W WO2024040908A1 WO 2024040908 A1 WO2024040908 A1 WO 2024040908A1 CN 2023079086 W CN2023079086 W CN 2023079086W WO 2024040908 A1 WO2024040908 A1 WO 2024040908A1
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porous spherical
ternary precursor
secondary particles
precursor
reaction kettle
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French (fr)
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蒋伟
刘更好
李伟权
阮丁山
李和敏
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the field of battery technology, and specifically, to a porous spherical ternary precursor and a preparation method thereof, a ternary positive electrode material, a positive electrode sheet and a battery.
  • ternary materials have become a hot research topic, in which ternary precursors play an important role.
  • the cathode material almost completely inherits all the physical and chemical indicators of the precursor.
  • Various parameters of the precursor such as specific surface area, tap density, particle size distribution, etc., directly affect the electrochemical performance of the battery.
  • a larger specific surface area can greatly increase the contact area between the material and the electrolyte, and a higher tap density can maintain The cycle stability of the battery and the improvement of volumetric energy density.
  • the specific surface area and tapping are two important parameters of the ternary precursor, and the two are often in opposition. That is, the primary particles of the highly tapped precursor are relatively tight and it is difficult to obtain a higher specific surface area. The primary particles with a high specific surface area are relatively small. Loose and difficult to have high vibration.
  • the purpose of the present invention is to provide a porous spherical ternary precursor and a preparation method thereof, which can realize the organic unity of large specific surface area and high vibration while ensuring the cycle performance of the battery, and significantly improve the electrochemical performance of the battery.
  • the present invention also aims to provide a ternary positive electrode material, a positive electrode sheet and a battery, all of which are prepared by the above-mentioned porous spherical ternary precursor.
  • the present invention provides a method for preparing a porous spherical ternary precursor, including:
  • the intermediate precursor is post-processed to obtain a porous spherical ternary precursor.
  • the target particle size of the secondary particles is 10.1 ⁇ D50 ⁇ 10.5 ⁇ m
  • the steps of gradually reducing the pH in the reaction kettle to 11-11.5 and simultaneously gradually reducing the stirring speed include:
  • the pH should be adjusted to 11.5-12.5 and the stirring speed should be adjusted to 450-550rpm.
  • the pH should be adjusted to 11.5-11.8 and the stirring speed should be adjusted to 450-550rpm.
  • the speed should be adjusted to 300-450rpm; when the secondary particles are 7.5 ⁇ D50 ⁇ 10.1 ⁇ m, the pH should be adjusted to 11-11.5, and the stirring speed should be adjusted to 250-300rpm.
  • the metal solution before the metal solution is mixed with the alkali solution, it also includes adding an M-containing compound to the metal solution;
  • the M-containing compound is one of molybdenum trioxide, tungsten trioxide, and zirconium sulfate;
  • 610-700g of M-containing compound needs to be added to every 800-900L of metal solution.
  • the specific surface area of the porous spherical ternary precursor is 13-15m 2 /g;
  • the tap density of the porous spherical ternary precursor is 2.05-2.30g/cm 3 ;
  • the sulfur content of the porous spherical ternary precursor is 1500-1800ppm;
  • the nickel salt is any one of nickel sulfate hexahydrate and nickel chloride;
  • the cobalt salt is any one of cobalt sulfate heptahydrate and cobalt chloride;
  • the manganese salt is manganese sulfate monohydrate.
  • the flow rate of the metal solution into the reaction kettle is 20-40L/h; the flow rate of the alkali solution into the reaction kettle is 8-18L/h.
  • the concentration of the metal solution is 1.6-2.2 mol/L.
  • the ammonia concentration is 1.8-3.2g/L.
  • the alkali solution is sodium hydroxide solution; preferably, the concentration of the sodium hydroxide solution is 6-12 mol/L.
  • the stirring speed for forming primary particles is maintained at 450-550 rpm.
  • the nucleation reaction time to form primary particles is 3-7 hours.
  • the preset time is 10-40 minutes.
  • reaction bottom liquid is obtained by adding ammonia water while stirring in heated clear water;
  • the heating temperature range of clean water is 55-75°C;
  • the stirring speed is maintained at 450-550 rpm.
  • the present invention provides a porous spherical ternary precursor, which is prepared by the method for preparing a porous spherical ternary precursor in any one of the preceding embodiments.
  • the present invention provides a ternary cathode material, including a porous spherical ternary precursor prepared by the method for preparing a porous spherical ternary precursor in any one of the preceding embodiments; or, comprising a porous spherical ternary precursor according to the preceding embodiment.
  • a ternary cathode material including a porous spherical ternary precursor prepared by the method for preparing a porous spherical ternary precursor in any one of the preceding embodiments; or, comprising a porous spherical ternary precursor according to the preceding embodiment.
  • Spherical ternary precursor Spherical ternary precursor.
  • the present invention provides a positive electrode sheet, including the positive electrode material of the aforementioned embodiment.
  • the present invention provides a battery including the positive electrode sheet of the aforementioned embodiment.
  • the invention provides a method for preparing a porous spherical ternary precursor.
  • the pH in the reaction kettle is gradually reduced to 11-11.5, and the stirring speed is gradually reduced simultaneously.
  • the pH in the reaction kettle is rapidly raised to 11.5-12.5 and maintained for a preset time to obtain the intermediate precursor;
  • the intermediate precursor is post-processed to obtain a porous spherical ternary precursor.
  • This method can ensure that the primary particles are uniform in thickness and roughly in the shape of a short and thin "toothpick sphere", which is not only conducive to ensuring the formation of a porous structure during the formation of secondary particles to ensure the specific surface area of the entire precursor, but also is beneficial to Ensure tap density to improve the electrochemical performance of the battery;
  • This method can ensure that the particles agglomerate and grow to the target particle size, and can suppress the generation of small particles, so that the shape and structure of the particles with the target particle size are stable porous spherical shapes, so as to ensure the cycle performance of the battery. At the same time, it achieves the organic unity of large specific surface area and high vibration;
  • This method can not only ensure the stability of the secondary particle morphology and structure, reduce the breakage and cracking of the secondary particles to ensure the electrochemical performance of the battery, but also increase the particle size distribution of the entire secondary particles so that each size
  • the particle size distribution is more uniform to ensure the uniformity and stability of the secondary particle structure and morphology of the porous spherical structure, so as to further achieve the organic unity of large specific surface area and high vibration while ensuring the cycle performance of the battery;
  • This method can reduce the sulfur content in the precursor, making the sulfur removal operation simpler and more convenient, thereby reducing the cost of sulfur removal.
  • the preparation method of the porous spherical ternary precursor provided by the embodiments of the present invention can ensure the cycleability of the battery. Under the premise of high energy efficiency, the organic unity of large specific surface area and high vibration is achieved to fully improve the electrochemical performance of the battery.
  • Embodiments of the present invention also provide a ternary positive electrode material, a positive electrode sheet and a battery, all of which are prepared by the above-mentioned porous spherical ternary precursor. Therefore, it also has the advantage of improving the electrochemical performance of the battery.
  • Figure 1 is an SEM morphology image of a porous spherical ternary precursor provided by an embodiment of the present invention
  • Figure 2 is a slice morphology diagram of a porous spherical ternary precursor provided by an embodiment of the present invention.
  • Figure 1 is an SEM morphology diagram of a porous spherical ternary precursor provided by an embodiment of the present invention
  • Figure 2 is a slice morphology diagram of a porous spherical ternary precursor provided by an embodiment of the present invention.
  • embodiments of the present invention provide a porous spherical ternary precursor, which is prepared by the following method:
  • S2 Continue granulation to agglomerate the primary particles to form secondary particles.
  • the secondary particles growing to the target particle size gradually reduce the pH in the reaction kettle to 11-11.5, and simultaneously gradually reduce the stirring speed so that The secondary particles gradually grow into porous spherical shapes, and after the secondary particles grow to the target particle size, the pH in the reactor is rapidly raised to 11.5-12.5 and maintained for a preset time to obtain the intermediate precursor;
  • step S1 during the process of granulating to form primary particles, the pH is controlled between 11.5 and 12.5, so that the thickness and shape of the primary particles formed by granulation are relatively uniform and roughly appear "thin and short""Toothpick spherical shape" is also similar to a short and thin ellipsoid, which can ensure the formation of porous morphology through the spherical structure during the secondary particle agglomeration process to ensure the specific surface area, and can also ensure the tap density through the thin and short structure, so as to simultaneously Increase the specific surface area and tap density of particles in the medium particle stage.
  • step S2 by gradually reducing the pH during the formation of secondary particles by controlling the pH, the pH can be gradually reduced from 11.5-12.5 to 11-11.5, which can ensure that the particles can agglomerate and grow to the target particle size, and can suppress small particles.
  • Particle generation makes the shape and structure of the particles of the target particle size into a stable porous spherical shape, so as to achieve the organic unity of large specific surface area and high vibration while ensuring the cycle performance of the battery; at the same time, the formation of secondary particles is gradually reduced through control
  • the stirring rate during the process can further ensure the stability of the secondary particle morphology and structure, reduce the breakage and cracking of the secondary particles, and ensure the electrochemical performance of the battery.
  • the particle size of the secondary particles can be controlled to maintain the particle size of the secondary particles at the target particle size, and small particles can be formed by increasing the pH.
  • the particle structure is used to increase the particle size distribution of the entire secondary particles and make the particle size distribution of each size more uniform to ensure the uniformity and stability of the secondary particle structure and morphology of the porous spherical structure to further ensure the cycle of the battery. While achieving high performance, it achieves the organic unity of large specific surface area and high vibration.
  • a more regular spherical structure is formed through control, so that during the battery charge and discharge process, the electrolyte infiltrates the various positions of the electrode piece prepared from the precursor more regularly and uniformly, reducing the charge and discharge process.
  • the generation of side reactions ensures the cycle performance of the battery and extends the service life of the battery.
  • the sulfur content in the precursor can be reduced accordingly, making the sulfur removal operation simpler and more convenient, thereby reducing the cost of sulfur removal.
  • post-processing includes centrifugation, drying, batch mixing, sieving and demagnetization in sequence to ensure that the porous spherical ternary precursor can be used to prepare cathode materials, cathode pole sheets and batteries.
  • the preparation method of the porous spherical ternary precursor provided by the embodiments of the present invention can realize the organic unity of large specific surface area and high vibration on the premise of ensuring the cycle performance of the battery, so as to fully improve the electrochemical performance of the battery.
  • the specific surface area of the porous spherical ternary precursor can be increased to 13-15m2 /g, and the tap density of the porous spherical ternary precursor can be increased to 2.05-2.30g/ cm3 ; the content of the porous spherical ternary precursor can be increased to 13-15m2/g.
  • the sulfur content can be reduced to 1500-1800ppm.
  • the alkali solution is a sodium hydroxide solution
  • the compound containing M is mixed with the metal solution.
  • the M-containing compound is one of molybdenum trioxide, tungsten trioxide, and zirconium sulfate.
  • metal elements molybdenum, tungsten, zirconium
  • each 800-900L of metal solution usually requires 610-700g of M-containing compound.
  • the nickel salt can be selected from nickel sulfate hexahydrate or nickel chloride; the cobalt salt can be selected from cobalt sulfate heptahydrate or cobalt chloride; and the manganese salt can be manganese sulfate monohydrate.
  • the usage ratio of nickel salt, cobalt salt and manganese salt is roughly (94-98):(1-3):(1-3). For example, 97:2:1 can be selected.
  • the concentration of the metal solution is 1.6-2.2mol/L; the concentration of ammonia solution is 1.8-3.2g/L; and the concentration of the sodium hydroxide solution is 6-12mol /L.
  • the concentration of each component of the mixed solution the corresponding pH value can be matched to prepare a thin and short "toothpick sphere", which is also similar to a short and ellipsoid-shaped primary particle, so that the secondary particles can be reunited.
  • porous morphology is ensured through the spherical structure to ensure the specific surface area, and the tap density can also be ensured through the thin and short structure to simultaneously increase the specific surface area and tap density of the particles in the medium particle stage.
  • the flow rate of the metal solution into the reaction kettle is 20-40L/h; the flow rate of the alkali solution into the reaction kettle is 8-18L/h.
  • the pH can be maintained in a stable range by controlling the flow rate of the metal solution and the flow rate of the alkali solution, which can assist the formation of short and thin "toothpick spherical" primary particles to ensure the formation of medium-sized particles. Specific surface area and tap density to fully improve the electrochemical performance of the battery.
  • step S1 the reaction bottom liquid is obtained by adding ammonia water while stirring in the heated clear water, and the heating temperature range of the clear water is 55-75°C.
  • the stirring speed is maintained at 450-550rpm.
  • clean water needs to be submerged up to the pH probe to ensure the accuracy of the pH test.
  • the temperature and stirring speed of the clean water need to be maintained during the entire primary particle formation process, and the nucleation reaction time to form primary particles is 3-7 hours.
  • the shape and size of the primary particles can be ensured, so that the tap density and specific surface area of the prepared precursor can be fully guaranteed by forming "toothpick spherical" primary particles.
  • the target particle size of the secondary particles is 10.1 ⁇ D50 ⁇ 10.5 ⁇ m. Controlling the target particle size of the secondary particles within this range will, on the one hand, facilitate the formation of a porous spherical structure, and on the other hand, avoid the problem of performance degradation caused by excessively large secondary particle sizes.
  • the pH during the growth of secondary particles is related to the particle size of the particles. Specifically, during the formation of secondary particles, the pH in the reaction kettle is gradually reduced to 11-11.5, and the stirring is gradually reduced simultaneously.
  • the speed steps include: when the D50 of the secondary particles ⁇ 3.5 ⁇ m, the pH is adjusted to 11.5-12.5, and the stirring speed is adjusted to 450-550 rpm; when the secondary particles are 3.5 ⁇ D50 ⁇ 7.5 ⁇ m, the pH is adjusted to 11.5-11.8, the stirring speed is adjusted to 300-450rpm; when the secondary particles are 7.5 ⁇ D50 ⁇ 10.1 ⁇ m, the pH is adjusted to 11-11.5, and the stirring speed is adjusted to 250-300rpm.
  • the smaller the particle size of the secondary particles the higher the corresponding pH, so that the secondary particles can grow to ensure the formation of secondary particles with the target particle size; on the other hand, as the particle size of the secondary particles increases, As the pH increases, the pH gradually decreases, and the stirring speed is lowered accordingly, which can inhibit the formation of small particles in the growing process of secondary particles, allowing the particles to agglomerate and grow to form a more regular porous spherical structure that reaches the target particle size.
  • the tap density and specific surface area of the precursor ensure The electrochemical performance of the battery.
  • Embodiments of the present invention also provide a ternary cathode material, which is prepared by the above-mentioned porous spherical ternary precursor. Therefore, the ternary cathode material can also improve the electrochemical performance of the battery, ensure the cycle performance of the battery, and save the manufacturing cost of the battery.
  • the ternary cathode material is obtained by mixing the above-mentioned porous spherical ternary precursor and a lithium source and then sintering.
  • the proportion of lithium source is less than 5%, and the lithium source can be selected from raw materials that can provide lithium ions, such as lithium carbonate or lithium hydroxide.
  • An embodiment of the present invention also provides a positive electrode sheet, which is prepared from the above-mentioned positive electrode material.
  • the positive electrode sheet may include a current collector and a positive active material layer disposed on at least one side of the current collector.
  • the cathode active material layer is obtained by coating the cathode slurry on the current collector, drying and cold pressing.
  • the positive electrode slurry includes positive electrode materials, conductive agents, binders and solvents.
  • the current collector can be aluminum foil, and the conductive agent and binder each account for less than 5%.
  • the conductive agent can be carbon black, carbon nanotubes, graphene, etc., and the binder can be polyvinylidene fluoride. (PVDF), the solvent can be N-methylpyrrolidone (NMP).
  • the positive electrode plate can also improve the electrochemical performance of the battery, ensure the cycle performance of the battery, and save the manufacturing cost of the battery.
  • An embodiment of the present invention also provides a battery, including the positive electrode sheet of the aforementioned embodiment.
  • the battery specifically includes a casing, a positive electrode piece, a separator, a negative electrode piece, and an electrolyte.
  • the positive electrode sheet, the separator and the negative electrode sheet are stacked, and a bare battery core is formed by lamination or winding. After the bare battery core is installed in the case and the electrolyte is injected, the battery can be obtained.
  • the negative electrode sheet may include a current collector and a negative active material layer.
  • the current collector may be copper foil.
  • the negative active material layer is obtained by coating the current collector with negative active slurry, drying and cold pressing.
  • the negative electrode active slurry includes negative electrode materials, conductive agents, binders and solvents.
  • the amount of conductive agent and binder is less than 5%, and the negative electrode material can be selected from soft carbon, hard carbon or composite carbon, etc.
  • the conductive agent can be selected from conductive carbon black, conductive graphite, vapor-phase grown carbon fiber, carbon nanotubes, etc.
  • the binder can be styrene-butadiene rubber, and the solvent can be N-methylpyrrolidone (NMP).
  • the battery is prepared from a porous spherical ternary precursor. Therefore, the battery also has the advantages of high electrochemical performance, good cycle performance, and low manufacturing cost.
  • This embodiment provides a battery, which is prepared by the following method:
  • step S1 Preparation of positive electrode plate, step S1 specifically includes:
  • Step S11 specifically includes Sa: input clean water into the reaction kettle, and ensure that the clean water can submerge the pH probe, and the reaction kettle rises Warm to 60°C, start stirring and maintain 500rpm, add ammonia water with a concentration of 2.3g/L, adjust the pH to 12, and obtain the reaction bottom liquid;
  • the ultra-high nickel ternary precursor and lithium hydroxide are mixed in a ratio of 93:2 and sintered to obtain a ternary cathode material.
  • the composite positive electrode piece, separator and negative electrode piece are arranged in sequence, and the sheets are stacked to prepare a bare cell, the bare cell is installed into the case and the electrolyte is injected; the battery after the liquid injection is allowed to stand, precharged, After exhaust gas is extracted, sealed, and divided into volumes, a lithium-ion battery is prepared.
  • step S11 specifically includes:
  • Sb Mix nickel sulfate hexahydrate, cobalt sulfate heptahydrate, and manganese sulfate monohydrate in a ratio of 97:2:1 to a total concentration of 2mol/L
  • To prepare a metal solution add 610g of zirconium sulfate to every 800L of metal solution, and add 150g of zirconium sulfate to the sodium hydroxide solution to form an alkali solution. Mix the metal solution, ammonia with a concentration of 6-12mol/L and ammonia with a concentration of 6-12mol/L.
  • the sodium hydroxide solution is passed into the reaction kettle through a metering pump at a flow rate of 25L/h of metal solution, 9L/h of sodium hydroxide solution, and 1.5L/h of ammonia water. After the liquid is introduced, the pH of the original reaction bottom liquid is maintained at 12, resulting in The nuclear reaction lasts for 3-7 hours, the particles grow up, and the prepared polycrystalline particles overflow into the aging tank;
  • step S11 specifically includes:
  • Sb Mix nickel sulfate hexahydrate, cobalt sulfate heptahydrate, and manganese sulfate monohydrate in a ratio of 97:2:1 to form a metal solution with a total concentration of 2mol/L.
  • ammonia water with a concentration of 8mol/L and sodium hydroxide solution with a concentration of 10mol/L are passed into the reaction kettle through a metering pump according to the flow rate of metal solution 25L/h, sodium hydroxide solution 9L/h, and ammonia water 1.5L/h. After entering the liquid, maintain the pH of the original reaction bottom liquid at 12, nucleate for 3-7 hours, the particles will grow up, and the prepared polycrystalline particles will overflow into the aging tank;
  • step S11 specifically includes:
  • Sb Mix nickel sulfate hexahydrate, cobalt sulfate heptahydrate, and manganese sulfate monohydrate in a ratio of 97:2:1 to form a metal solution with a total concentration of 2mol/L.
  • ammonia water with a concentration of 10mol/L and sodium hydroxide solution with a concentration of 12mol/L are passed into the reaction kettle through a metering pump according to the flow rate of metal solution 25L/h, sodium hydroxide solution 9L/h, and ammonia water 1.5L/h. After entering the liquid, maintain the pH of the original reaction bottom liquid at 12, nucleate for 3-7 hours, the particles will grow up, and the prepared polycrystalline particles will overflow into the aging tank;
  • step S11 specifically includes:
  • Sa Input clean water into the reaction kettle, and ensure that the clean water can submerge the pH probe. Heat the reaction kettle to 60°C, start stirring and maintain 500rpm, add ammonia water with a concentration of 3g/L, adjust the pH to 12.5, and obtain the reaction bottom liquid;
  • Comparative Example 1 provides a battery, and the difference between its preparation method and that of Example 1 is that step S11 specifically includes:
  • Sa Input clean water into the reaction kettle, and ensure that the clean water can flood the pH probe. Heat the reaction kettle to 60°C, start stirring and maintain 550rpm, add ammonia water with a concentration of 3g/L, adjust the pH to 12.5, and obtain the reaction bottom liquid;
  • Comparative Example 2 provides a battery, and the difference between its preparation method and that of Example 1 is that step S11 specifically includes:
  • the ultra-high nickel ternary precursor prepared in step S11 of Examples 1-5 and Comparative Examples 1-2 was subjected to performance testing.
  • the testing included nitrogen adsorption (BET) test, tap density test, sulfur content and particle size test. .
  • BET nitrogen adsorption
  • the tap density test uses a tap density meter to test
  • the particle size test uses a particle size meter to test D50 data.
  • Table 1 The test results are shown in Table 1.
  • the porous spherical ternary precursor prepared by the preparation method provided by the embodiments of the present invention has the advantages of large specific surface area and high compaction.
  • the preparation method provided by the embodiment of the present invention can also reduce the sulfur content in the precursor by rapidly increasing the pH after the precursor reaches the target particle size, thereby fully reducing the manufacturing cost.
  • the precursor can also obtain better specific surface area and tap density; and compared with Comparative Example 1-2, the specific surface area and tap density can be simultaneously improved; at the same time, according to Examples 1-4 and Embodiment 5 It can be seen from the comparison that under the same preparation environment, doping M-containing compounds in the precursor will significantly increase the particle size of the precursor particles and reduce the specific surface area and tap density to a certain extent. However, due to the thin and short structure of the primary particles, the secondary particles The secondary particles are porous and spherical, so that the specific surface area and tap density of the precursor will not decrease too much. Compared with Comparative Examples 1-2, the specific surface area and tap density can still be simultaneously increased.
  • the batteries prepared in step S3 of Examples 1-5 and Comparative Examples 1-2 were subjected to performance tests.
  • the test items included charging capacity (0.1C) test and cycle retention rate test.
  • the cycle test was specifically tested at 25°C. Capacity retention rate under the conditions of charging from 2C to 4.5V and then charging from 1.5C to 4.5V with a cut-off current of 0.05C.
  • the test results are shown in Table 2.
  • the battery prepared by using the porous spherical ternary precursor provided by the embodiments of the present invention has better cycle performance and better charging capacity.
  • the battery provided by the embodiment of the present invention has more excellent electrochemical performance.
  • the embodiments of the present invention can improve the charging capacity and cycle performance to a certain extent by doping metal elements in the porous spherical ternary precursor.
  • embodiments of the present invention provide a porous spherical ternary precursor and a preparation method thereof, which can achieve the organic unity of large specific surface area and high vibration while ensuring the cycle performance of the battery, so as to fully improve the battery life.
  • the electrochemical performance of the battery is provided.
  • Embodiments of the present invention also provide a ternary positive electrode material, a positive electrode sheet and a battery, all of which are prepared by the above-mentioned porous spherical ternary precursor. Therefore, it also has the advantage of improving the electrochemical performance of the battery.

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Abstract

本发明公开了一种多孔球形三元前驱体及其制备方法、三元正极材料、正极极片和电池，涉及电池技术领域；该方法包括：将金属溶液、氨水和碱液一起通入反应釜，开启搅拌并将pH维持在11.5-12.5进行造粒形成一次颗粒；继续造粒使一次颗粒团聚形成二次颗粒，在二次颗粒长大至目标粒径的过程中，将反应釜内的pH逐渐降低至11-11.5，并同步逐渐降低搅拌速度，以使二次颗粒逐渐长大呈多孔球形，且待二次颗粒长大至目标粒径后，将反应釜内的pH迅速升高至11.5-12.5并保持预设时间后得到中间前驱体；将中间前驱体处理得到多孔球形三元前驱体。该方法能在保证电池的循环性能的前提下，实现前驱体大比表面积和高振实的有机统一。

Description

一种多孔球形三元前驱体及其制备方法、三元正极材料、正极极片和电池 技术领域
本发明涉及电池技术领域，具体而言，涉及一种多孔球形三元前驱体及其制备方法、三元正极材料、正极极片和电池。
背景技术
世界经济飞速发展的同时，不可再生化石能源日益消耗，亟待寻找新兴、可替代的新能源，为可持续发展开辟新道路。近几年，以新能源为主的汽车行业迅速崛起。由于锂离子电池能量密度大、绿色清洁、携带方便、可重复使用等优点，深受人们喜爱和关注。其中镍钴锰三元材料应用于锂离子电池正极材料最为广泛，截止去年年底，已占据锂离子电池正极材料最大装车量份额。
三元材料成为研究的热点，其中三元前驱体功不可没。正极材料几乎完全继承前驱体的各项理化指标。前驱体的各项参数如比表面积、振实密度、粒度分布等直接影响电池的电化学性能，较大的比表面积能够极大增加材料与电解液的接触面积，较高的振实密度能够保持电池的循环稳定性以及提升体积能量密度。
但是，比表面积和振实作为三元前驱体两个重要参数，二者常保持对立，即高振实前驱体的一次颗粒之间比较紧，难以获得较高的比表面积，高比表面积的一次颗粒较为疏松，难以具备较高的振实。
鉴于此，特提出本发明。
发明内容
本发明的目的在于提供一种多孔球形三元前驱体及其制备方法，在保证电池的循环性能的前提下，实现大比表面积和高振实的有机统一，显著提高了电池的电化学性能。
本发明的目的还在于提供一种三元正极材料、正极极片和电池，三者均通过上述的多孔球形三元前驱体制备得到。
本发明的方案记载如下：
第一方面，本发明提供一种多孔球形三元前驱体的制备方法，包括：
将镍盐、钴盐和锰盐混合得到的金属溶液、氨水和碱液一起通入具有pH为11.5-12.5的反应底液的反应釜中，开启搅拌并将反应釜中的pH维持在11.5-12.5进行造粒形成一次颗粒；
继续造粒使一次颗粒团聚形成二次颗粒，在二次颗粒长大至目标粒径的过程中，将反应釜内的pH逐渐降低至11-11.5，并同步逐渐降低搅拌速度，以使二次颗粒逐渐长大呈多孔球形，且待二次颗粒长大至目标粒径后，将反应釜内的pH迅速升高至11.5-12.5并保持预设时间后得到中间前驱体；
将中间前驱体进行后处理得到多孔球形三元前驱体。
在可选的实施方式中，二次颗粒的目标粒径为10.1<D50≤10.5μm；
优选地，在二次颗粒形成过程中，将反应釜内的pH逐渐降低至11-11.5，并同步逐渐降低搅拌速度的步骤包括：
当二次颗粒的D50≤3.5μm时，pH对应调节为11.5-12.5，搅拌速度对应调节为450-550rpm；当二次颗粒的3.5＜D50≤7.5μm时，pH对应调节为11.5-11.8，搅拌速度对应调节为300-450rpm；当二次颗粒的7.5<D50≤10.1μm时，pH对应调节为11-11.5，搅拌速度对应调节为250-300rpm。
在可选的实施方式中，在金属溶液与碱液混合之前，还包括将含M的化合物加入金属溶液中；
优选地，含M的化合物为三氧化钼、三氧化钨、硫酸锆中的一种；
优选地，每800-900L的金属溶液需加入610-700g的含M的化合物。
在可选的实施方式中，多孔球形三元前驱体的化学通式为NixCoyMnzMw(OH)2，其中，0.92≤x≤0.97；0.02≤y≤0.06；0.01≤z≤0.02；0.001≤w≤0.02；x+y+z+w＝1；
优选地，多孔球形三元前驱体的比表面积为13-15m2/g；
优选地，多孔球形三元前驱体的振实密度为2.05-2.30g/cm3；
优选地，多孔球形三元前驱体的含硫量为1500-1800ppm；
优选地，镍盐为六水硫酸镍、氯化镍中的任一种；
优选地，钴盐为七水硫酸钴、氯化钴中的任一种；
优选地，锰盐为一水硫酸锰。
在可选的实施方式中，金属溶液通入反应釜的流量为20-40L/h；碱液通入反应釜的流量为8-18L/h。
在可选的实施方式中，金属溶液的浓度为1.6-2.2mol/L。
在可选的实施方式中，氨水浓度为1.8-3.2g/L。
在可选的实施方式中，所述碱液为氢氧化钠溶液；优选地，所述氢氧化钠溶液的浓度为6-12mol/L。
在可选的实施方式中，形成一次颗粒的搅拌速度维持在450-550rpm。
在可选的实施方式中，形成一次颗粒的造核反应时间为3-7h。
在可选的实施方式中，预设时间为10-40min。
在可选的实施方式中，反应底液通过在升温后的清水中边搅拌边加入氨水后得到；
优选地，清水的升温温度范围为55-75℃；
优选地，搅拌速度维持在450-550rpm。
第二方面，本发明提供一种多孔球形三元前驱体，多孔球形三元前驱体通过前述实施方式中任一项的多孔球形三元前驱体的制备方法制备得到。
第三方面，本发明提供一种三元正极材料，包括前述实施方式中任一项的多孔球形三元前驱体的制备方法制备得到的多孔球形三元前驱体；或者，包括前述实施方式的多孔球形三元前驱体。
第四方面，本发明提供一种正极极片，包括前述实施方式的正极材料。
第五方面，本发明提供一种电池，包括前述实施方式的正极极片。
本发明至少具备以下优点或有益效果：
本发明提供了一种多孔球形三元前驱体的制备方法，在二次颗粒长大至目标粒径的过程中，将反应釜内的pH逐渐降低至11-11.5，并同步逐渐降低搅拌速度，以使二次颗粒逐渐长大呈多孔球形，且待二次颗粒长大至目标粒径后，将反应釜内的pH迅速升高至11.5-12.5并保持预设时间后得到中间前驱体；将中间前驱体进行后处理得到多孔球形三元前驱体。
该方法的有益效果包括以下几点：
(1)该方法能保证一次颗粒粗细均匀，形态大致呈现细短状的“牙签球形”，不仅利于在二次颗粒形成过程中保证多孔结构的形成，以保证整个前驱体的比表面积，还利于保证振实密度，以提高电池的电化学性能；
(2)该方法能保证粒子团聚并长大至目标粒径，且能抑制小颗粒粒子生成，使目标粒径的粒子的形态和结构呈稳定的多孔球形，以在能保证电池的循环性能的同时，实现大比表面积和高振实的有机统一；
(3)该方法既能保证二次颗粒形态和结构的稳定性，减少二次颗粒的破碎和开裂，以保证电池的电化学性能；又能增大整个二次颗粒的粒度分布，使得各尺寸粒径分布更均匀，以保证多孔球形结构的二次颗粒结构和形态的均匀性和稳定性，以进一步地在保证电池的循环性能的同时，实现大比表面积和高振实的有机统一；
(4)该方法能降低前驱体中的硫含量，使得除硫作业更简单便捷，以能降低除硫成本。
综上，本发明的实施例提供的多孔球形三元前驱体的制备方法能在保证电池的循环性 能的前提下，实现大比表面积和高振实的有机统一，以充分提高电池的电化学性能。
本发明的实施例还提供了一种三元正极材料、正极极片和电池，三者均通过上述的多孔球形三元前驱体制备得到。因此，也具有能提高电池的电化学性能的优点。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本发明的实施例提供的多孔球形三元前驱体的SEM形貌图；
图2为本发明的实施例提供的多孔球形三元前驱体的切片形貌图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
以下结合实施例对本发明的特征和性能作进一步的详细描述。
图1为本发明的实施例提供的多孔球形三元前驱体的SEM形貌图；图2为本发明的实施例提供的多孔球形三元前驱体的切片形貌图。请参阅图1与图2，本发明的实施例提供了一种多孔球形三元前驱体，其通过以下方法制备得到：
S1：将镍盐、钴盐和锰盐混合得到的金属溶液、氨水和碱液一起通入具有pH为11.5-12.5的反应底液的反应釜中，开启搅拌并将反应釜中的pH维持在11.5-12.5进行造粒形成一次颗粒；
S2：继续造粒使一次颗粒团聚形成二次颗粒，在二次颗粒长大至目标粒径的过程中，将反应釜内的pH逐渐降低至11-11.5，并同步逐渐降低搅拌速度，以使二次颗粒逐渐长大呈多孔球形，且待二次颗粒长大至目标粒径后，将反应釜内的pH迅速升高至11.5-12.5并保持预设时间后得到中间前驱体；
S3：将中间前驱体进行后处理得到多孔球形三元前驱体。
详细地，在步骤S1中，在造粒形成一次颗粒的过程中，通过将pH控制在11.5-12.5之间，使得造粒形成的一次颗粒的粗细和形态相对均匀，大致呈现细短状的“牙签球形”，也类似于细短的椭球状，以能在二次颗粒团聚过程中通过类球形结构保证多孔形态的形成，以保证比表面积，也能通过细短结构保证振实密度，以同时提高中颗粒阶段的颗粒的比表面积和振实密度。并且，在此过程中，若pH低于11.5，则一次小颗粒会出现团聚，不利于 保证“牙签球形”的形态稳定性，若pH高于12.5，则一次颗粒粒度过小，使得颗粒的粗细和形态无法满足造粒需求。
在步骤S2中，通过控制逐步降低二次颗粒形成过程中的pH，使得pH从11.5-12.5能逐步降低至11-11.5，能保证颗粒能团聚并长大至目标粒径，且能抑制小颗粒粒子生成，使目标粒径的粒子的形态和结构呈稳定的多孔球形，以在能保证电池的循环性能的同时，实现大比表面积和高振实的有机统一；同时，通过控制逐步降低二次颗粒形成过程中的搅拌速率，能进一步地保证二次颗粒形态和结构的稳定性，减少二次颗粒的破碎和开裂，以保证电池的电化学性能。
另外，在二次颗粒长大至目标粒径后通过快速增高pH，既能控制二次颗粒的粒度，以将二次颗粒的粒径维持在目标粒径下，又能通过pH的增高形成小颗粒结构，以增大整个二次颗粒的粒度分布，使得各尺寸粒径分布更均匀，以保证多孔球形结构的二次颗粒结构和形态的均匀性和稳定性，以进一步地在保证电池的循环性能的同时，实现大比表面积和高振实的有机统一。并且，在二次颗粒长达过程中，通过控制形成较为规则球形结构，使得电池充放电过程中，电解液对前驱体制备得到的极片的各个位置的浸润更规则和均匀，减少充放电过程中副反应的产生，以保证电池的循环性能，延长电池的使用寿命。除此之外，通过迅速升高pH，也能相应降低前驱体中的硫含量，使得除硫作业更简单便捷，以能降低除硫成本。
在步骤S3中，后处理包括依次进行的离心、干燥、混批、过筛以及除磁作业，以保证多孔球形三元前驱体能用于制备正极材料、正极极片以及电池。
综上，本发明的实施例提供的多孔球形三元前驱体的制备方法能在保证电池的循环性能的前提下，实现大比表面积和高振实的有机统一，以充分提高电池的电化学性能。并且，多孔球形三元前驱体的比表面积可提高至13-15m2/g，多孔球形三元前驱体的振实密度可提高至2.05-2.30g/cm3；多孔球形三元前驱体的含硫量可下降至1500-1800ppm。
作为可选的方案，在本发明的实施例中，在步骤S1中，碱液为氢氧化钠溶液，在金属溶液与碱液混合之前，还包括将含M的化合物与金属溶液混合。含M的化合物为三氧化钼、三氧化钨、硫酸锆中的一种。通过在金属溶液中混合含M的化合物，能在前驱体的合成阶段实现金属元素(钼、钨、锆)的掺杂。示例性地，每800-900L的金属溶液通常需要适配610-700g的含M的化合物。在此步骤掺杂特定比例的金属元素，既不会影响多孔球形结构的形成和稳定性，还能在烧结成正极材料的时候，进一步地提高正极材料的容量，以进一步地提高电池的电化学性能。基于掺杂有含M的化合物，本发明的实施例提供的多孔球形三元前驱体的化学通式为NixCoyMnzMw(OH)2，其中，0.92≤x≤0.97；0.02≤y≤0.06；0.01≤z≤0.02； 0.001≤w≤0.02；x+y+z+w＝1。且镍盐可选择为六水硫酸镍、氯化镍中的任一种；钴盐可选择为七水硫酸钴、氯化钴中的任一种；锰盐可选择为一水硫酸锰。镍盐、钴盐以及锰盐的使用比例大致为(94-98):(1-3):(1-3)，示例性地，可选择为97:2:1。
进一步可选地，在本发明的实施例中，在步骤S1中，金属溶液的浓度为1.6-2.2mol/L；氨水浓度为1.8-3.2g/L；氢氧化钠溶液的浓度为6-12mol/L。通过对混合液各成分的浓度进行控制，能匹配对应的pH值，以制备得到呈现细短状的“牙签球形”，也类似于细短的椭球状的一次颗粒，以能在二次颗粒团聚过程中通过类球形结构保证多孔形态的形成，以保证比表面积，也能通过细短结构保证振实密度，以同时提高中颗粒阶段的颗粒的比表面积和振实密度。
同时，在本发明的实施例中，金属溶液通入反应釜的流量为20-40L/h；碱液通入反应釜的流量为8-18L/h。在一次颗粒造粒过程中，通过金属溶液流量和碱液流量的控制能将pH维持在一个稳定区间，以能辅助细短状的“牙签球形”的一次颗粒的形成，以保证中颗粒阶段的比表面积和振实密度，以充分改善电池的电化学性能。
更进一步地，在步骤S1中，反应底液通过在升温后的清水中边搅拌边加入氨水后得到，清水的升温温度范围为55-75℃。搅拌速度维持在450-550rpm。在加入氨水之前，清水需要淹没至pH探头，以保证pH测试的精确性。同时，清水的温度和搅拌速度在整个一次颗粒形成过程中均需要维持，且形成一次颗粒的造核反应时间为3-7h。通过对造核时间的控制，能保证一次颗粒形态和尺寸，以能通过形成“牙签球形”状的一次颗粒充分保证制备得到的前驱体的振实密度和比表面积。
同理，在本发明的实施例中，在步骤S2中，二次颗粒的目标粒径为10.1<D50≤10.5μm。将二次颗粒的目标粒径控制在此范围内，一方面利于形成多孔球形结构，另一方面，可避免二次颗粒粒径过大所造成的性能降低的问题。同时，二次颗粒长大过程中的pH与颗粒的粒径是相关联的，具体地，在二次颗粒形成过程中，将反应釜内的pH逐渐降低至11-11.5，并同步逐渐降低搅拌速度的步骤包括：当二次颗粒的D50≤3.5μm时，pH对应调节为11.5-12.5，搅拌速度对应调节为450-550rpm；当二次颗粒的3.5＜D50≤7.5μm时，pH对应调节为11.5-11.8，搅拌速度对应调节为300-450rpm；当二次颗粒的7.5<D50≤10.1μm时，pH对应调节为11-11.5，搅拌速度对应调节为250-300rpm。
一方面，二次颗粒的粒径越小对应的pH越高，使得二次颗粒可长大，以能保证形成目标粒径的二次颗粒；另一方面，随着二次颗粒的粒径的增大，pH逐渐降低，搅拌速度随之下调，能抑制二次颗粒在逐渐长大中的小颗粒粒子的生成，使得颗粒能团聚并长大形成达到目标粒径且较为规则的多孔球形结构，以充分保证前驱体的振实密度和比表面积，保证 电池的电化学性能。
本发明的实施例还提供了一种三元正极材料，其通过上述的多孔球形三元前驱体制备得到。因此，该三元正极材料也能提高电池的电化学性能，保证电池的循环性能，节约电池的制造成本。
详细地，三元正极材料具体通过上述的多孔球形三元前驱体与锂源混合后烧结得到。锂源的占比小于5％，且锂源可选择为碳酸锂或氢氧化锂等能提供锂离子的原料。
本发明的实施例还提供了一种正极极片，其通过上述的正极材料制备得到。其中，正极极片可包括集流体和设置于集流体至少一侧的正极活性材料层。正极活性材料层通过正极浆料涂覆在集流体后烘干且冷压后得到。正极浆料包括正极材料、导电剂、粘结剂以及溶剂。其中，集流体可选择为铝箔，导电剂和粘结剂各自所占比例均小于5％，导电剂可选择为炭黑、碳纳米管、石墨烯等，粘结剂可选择为聚偏氟乙烯(PVDF)，溶剂可选择为N-甲基吡咯烷酮(NMP)。
由于上述的正极极片通过多孔球形三元前驱体制备得到。因此，该正极极片也能提高电池的电化学性能，保证电池的循环性能，节约电池的制造成本。
本发明的实施例还提供了一种电池，包括前述实施方式的正极极片。并且，该电池具体包括壳体、正极极片、隔膜、负极极片以及电解液。其中，正极极片、隔膜以及负极极片层叠设置，通过叠片或卷绕的方式形成裸电芯，裸电芯装入壳体并注入电解液后即可得到电池。其中，负极极片可包括集流体和负极活性材料层，集流体可选择为铜箔，负极活性材料层通过负极活性浆料涂覆于集流体后干燥并冷压得到。其中，负极活性浆料包括负极材料、导电剂、粘结剂以及溶剂。导电剂、粘结剂的用量均少于5％，且负极材料可选择为软碳、硬碳或者复合碳等，导电剂可选择导电炭黑、导电石墨、气相生长碳纤维、碳纳米管等，粘结剂可选择为苯乙烯-丁二烯橡胶，溶剂可选择为N-甲基吡咯烷酮(NMP)。
由于上述的电池通过多孔球形三元前驱体制备得到。因此，该电池也具有电化学性能高，循环性能好，制造成本低的优点。
下面结合具体的实施例和对比例对上述多孔球形三元前驱体的制备过程和性能进行详细地说明：
实施例1
本实施例提供了一种电池，其通过以下方法制备得到：
S1：正极极片的制备，步骤S1具体包括：
S11：多孔球形三元前驱体的制备：
步骤S11具体包括Sa：将清水输入反应釜内，且确保清水能淹没pH探头，反应釜升 温至60℃，开启搅拌维持500rpm，加入浓度为2.3g/L的氨水，调节pH为12，得到反应底液；
Sb：将六水硫酸镍、七水硫酸钴、一水硫酸锰按照比例97:2:1混合成总浓度为2mol/L的金属溶液，每850L的金属溶液加入650g的硫酸锆，将金属溶液、浓度为6-12mol/L的氨水与浓度为6-12mol/L的氢氧化钠溶液通过计量泵按照金属溶液25L/h、氢氧化钠溶液9L/h，氨水1.5L/h流量一起通入反应釜内，进液后维持原有反应底液的pH为12，造核反应3-7小时，颗粒长大，制备的多晶颗粒溢流进入陈化槽中；
Sc：随着二次颗粒的长大缓慢降低pH、搅拌，其中当D50≤3.5，pH为12，搅拌：500rpm，当3.5＜D50≤7.5，pH:11.8，搅拌：400rpm，当7.5<D50≤10.5，pH:11.5，搅拌：280rpm；颗粒目标尺寸：10.1-10.5μm，达到目标粒度D50长大至10.3μm，升高pH至12.5，并保持30min，然后调节至原来pH，反复操作，离心、干燥、混批、过筛、除磁，得到超高镍三元前驱体Ni0.9685Co0.02Mn0.01M0.0015(OH)2。
S12：正极材料的制备：
将超高镍三元前驱体与氢氧化锂按照93:2的配比混合并烧结后得到三元正极材料。
S13：极片的制备：
将三元正极材料、乙炔黑、聚偏氟乙烯(PVDF)按照93:3:2混合均匀，加入NMP搅拌得到正极浆料。将正极浆料涂覆于铝箔的两个侧表面，并烘干和冷压后得到正极极片。
S2：负极片的制备：
将硬碳、乙炔黑、苯乙烯-丁二烯橡胶按照93:3:2的比例混合均匀，加入NMP搅拌，制成负极浆料；将负极浆料涂布在铜箔集流体上，经烘干和冷压后得到负极极片。
S3：电池的制备：
将复合正极极片、隔膜以及负极极片依次设置，并叠片制备成裸电芯后，将裸电芯装入壳体后注入电解液；将注液后的电池进行静置、预充、抽废气、封口、分容后，制备成锂离子电池。
实施例2
本实施例提供了一种电池，其制备方法与实施例1的制备方法的区别在于，步骤S11具体包括：
Sa：将清水输入反应釜内，且确保清水能淹没pH探头，反应釜升温至60℃，开启搅拌维持480rpm，加入浓度为3g/L的氨水，调节pH为12.5，得到反应底液；
Sb：将六水硫酸镍、七水硫酸钴、一水硫酸锰按照比例97:2:1混合成总浓度为2mol/L 的金属溶液，每800L的金属溶液加入610g的硫酸锆，氢氧化钠溶液加150g硫酸锆配置成碱液，将金属溶液、浓度为6-12mol/L的氨水与浓度为6-12mol/L的氢氧化钠溶液通过计量泵按照金属溶液25L/h、氢氧化钠溶液9L/h，氨水1.5L/h流量一起通入反应釜内，进液后维持原有反应底液的pH为12，造核反应3-7小时，颗粒长大，制备的多晶颗粒溢流进入陈化槽中；
Sc：随着二次颗粒的长大缓慢降低pH、搅拌，其中当D50≤3.5，pH为12.0，搅拌：480rpm，当3.5＜D50≤7.5，pH:11.7，搅拌：450rpm，当7.5<D50≤10.5，pH:11.4，搅拌：260rpm；颗粒目标尺寸：10.1-10.5μm，达到目标粒度D50长大至10.3μm，升高pH至12.5，并保持30min，然后调节至原来pH，反复操作，离心、干燥、混批、过筛、除磁，得到超高镍三元前驱体Ni0.9685Co0.02Mn0.01M0.0015(OH)2。
实施例3
本实施例提供了一种电池，其制备方法与实施例1的制备方法的区别在于，步骤S11具体包括：
Sa：将清水输入反应釜内，且确保清水能淹没pH探头，反应釜升温至60℃，开启搅拌维持460rpm，加入浓度为1.8g/L的氨水，调节pH为11.5，得到反应底液；
Sb：将六水硫酸镍、七水硫酸钴、一水硫酸锰按照比例97:2:1混合成总浓度为2mol/L的金属溶液，每880L的金属溶液加入640g的硫酸锆，将金属溶液、浓度为8mol/L的氨水与浓度为10mol/L的氢氧化钠溶液通过计量泵按照金属溶液25L/h、氢氧化钠溶液9L/h，氨水1.5L/h流量一起通入反应釜内，进液后维持原有反应底液的pH为12，造核反应3-7小时，颗粒长大，制备的多晶颗粒溢流进入陈化槽中；
Sc：随着二次颗粒的长大缓慢降低pH、搅拌，其中当D50≤3.5，pH为11.7，搅拌：460rpm，当3.5＜D50≤7.5，pH:11.5，搅拌：350rpm，当7.5<D50≤10.5，pH:11.2，搅拌：270rpm；颗粒目标尺寸：10.1-10.5μm，达到目标粒度D50长大至10.3μm，升高pH至12.5，并保持30min，然后调节至原来pH，反复操作，离心、干燥、混批、过筛、除磁，得到超高镍三元前驱体Ni0.9685Co0.02Mn0.01M0.0015(OH)2。
实施例4
本实施例提供了一种电池，其制备方法与实施例1的制备方法的区别在于，步骤S11具体包括：
Sa：将清水输入反应釜内，且确保清水能淹没pH探头，反应釜升温至60℃，开启搅 拌维持550rpm，加入浓度为4g/L的氨水，调节pH为13，得到反应底液；
Sb：将六水硫酸镍、七水硫酸钴、一水硫酸锰按照比例97:2:1混合成总浓度为2mol/L的金属溶液，每900L的金属溶液加入700g的硫酸锆，将金属溶液、浓度为10mol/L的氨水与浓度为12mol/L的氢氧化钠溶液通过计量泵按照金属溶液25L/h、氢氧化钠溶液9L/h，氨水1.5L/h流量一起通入反应釜内，进液后维持原有反应底液的pH为12，造核反应3-7小时，颗粒长大，制备的多晶颗粒溢流进入陈化槽中；
Sc：随着二次颗粒的长大缓慢降低pH、搅拌，其中当D50≤3.5，pH为12.5，搅拌：550rpm，当3.5＜D50≤7.5，pH:11.8，搅拌：450rpm，当7.5<D50≤10.5，pH:11.5，搅拌：300rpm；颗粒目标尺寸：10.1-10.5μm，达到目标粒度D50长大至10.3μm，升高pH至12.8，并保持30min，然后调节至原来pH，反复操作，离心、干燥、混批、过筛、除磁，得到超高镍三元前驱体Ni0.9685Co0.02Mn0.01M0.0015(OH)2。
实施例5
本实施例提供了一种电池，其制备方法与实施例1的制备方法的区别在于，步骤S11具体包括：
Sa：将清水输入反应釜内，且确保清水能淹没pH探头，反应釜升温至60℃，开启搅拌维持500rpm，加入浓度为3g/L的氨水，调节pH为12.5，得到反应底液；
Sb：将六水硫酸镍、七水硫酸钴、一水硫酸锰按照比例97:2:1混合成总浓度为2mol/L的金属溶液，将金属溶液、浓度为8mol/L的氨水与浓度为10mol/L的氢氧化钠溶液通过计量泵按照金属溶液25L/h、氢氧化钠溶液9L/h，氨水1.5L/h流量一起通入反应釜内，进液后维持原有反应底液的pH为12，造核反应3-7小时，颗粒长大，制备的多晶颗粒溢流进入陈化槽中；
Sc：随着二次颗粒的长大缓慢降低pH、搅拌，其中当D50≤3.5，pH为11.6，搅拌：500rpm，当3.5＜D50≤7.5，pH:11.5，搅拌：350rpm，当7.5<D50≤10.5，pH:11.1，搅拌：250rpm；颗粒目标尺寸：10.1-10.5μm，达到目标粒度D50长大至10.3μm，升高pH至12.5，并保持30min，然后调节至原来pH，反复操作，离心、干燥、混批、过筛、除磁，得到超高镍三元前驱体Ni0.9685Co0.02Mn0.01M0.0015(OH)2。
对比例1
对比例1提供了一种电池，其制备方法与实施例1的制备方法的区别在于，步骤S11具体包括：
Sa：将清水输入反应釜内，且确保清水能淹没pH探头，反应釜升温至60℃，开启搅拌维持550rpm，加入浓度为3g/L的氨水，调节pH为12.5，得到反应底液；
Sb：将六水硫酸镍、七水硫酸钴、一水硫酸锰按照比例97:2:1混合成总浓度为2mol/L的金属溶液，将金属溶液、浓度为9mol/L的氨水与浓度为12mol/L的氢氧化钠溶液通过计量泵按照金属溶液25L/h、氢氧化钠溶液9L/h，氨水1.5L/h流量一起通入反应釜内，进液后维持原有反应底液条件不变，造核反应3-7小时，长大到10.3微米，找到出核点，粒度大于10.5，pH比出核点高0.2，粒度小于10.5则pH保持出核点以下0.2，制备的多晶颗粒溢流进入陈化槽中；
Sc：随着二次颗粒的长大缓慢降低pH、搅拌，达到目标粒度D50长大至10.3μm，反复操作，离心、干燥、混批、过筛、除磁，得到超高镍三元前驱体。
对比例2
对比例2提供了一种电池，其制备方法与实施例1的制备方法的区别在于，步骤S11具体包括：
Sa：将清水输入反应釜内，且确保清水能淹没pH探头，反应釜升温至60℃，开启搅拌维持500rpm，加入浓度为2.3g/L的氨水，调节pH为12，得到反应底液；
Sb：将六水硫酸镍、七水硫酸钴、一水硫酸锰按照比例97:2:1混合成总浓度为2mol/L的金属溶液，每100kg氢氧化钠溶液加150g硫酸锆配置成碱液，将金属溶液、氨水与碱液通过计量泵按照金属溶液25L/h、碱液9L/h，氨水1.5L/h流量一起通入反应釜内，进液后维持原有反应底液条件不变，造核反应3-7小时，颗粒长大，制备的多晶颗粒溢流进入陈化槽中；
Sc：随着二次颗粒的长大，维持相同浓度氨水以及pH，达到目标粒度D50长大至10.3μm，离心、干燥、混批、过筛、除磁，得到超高镍三元前驱体。
实验例1
将实施例1-5以及对比例1-2在步骤S11中制备得到的超高镍三元前驱体进行性能测试，测试包括氮气吸附(BET)测试，振实密度测试，硫含量以及粒径测试。其中，振实密度测试采用振实密度仪进行测试，粒径测试采用粒度仪测试D50数据。测试结果如表1所示。
表1.超高镍三元前驱体性能测试结果
根据表1中实施例1-5与对比例1-2的对比可知，本发明的实施例提供的制备方法制备得到的多孔球形三元前驱体具有大比表面积和高振实的优点。同时，本发明的实施例提供的制备方法通过在前驱体达到目标粒径后快速升高pH，还能降低前驱体中的硫含量，以能充分降低制造成本。
另外，根据实施例1-4的数据对比可知，二次颗粒在长大至目标粒径后，反应釜内的pH越高，最后获得的二次颗粒的粒径越大；但是，由于在一次颗粒成形的过程中，能保证一次颗粒呈细短和均匀状，且二次颗粒在成形过程中采用的逐步降低pH的方案，使得二次颗粒能呈多孔球状结构，因而使得粒径较大的前驱体也能获得更优异的比表面积和振实密度；且相较于对比例1-2而言能实现比表面积和振实密度的同步提高；同时，根据实施例1-4与实施例5的对比可知，在同样制备环境下，在前驱体内掺杂含M的化合物会显著增加前驱体颗粒的粒径，并一定程度降低比表面积和振实密度，但由于一次颗粒呈细短结构，二次颗粒呈多孔球状，使得前驱体的比表面积和振实密度不会下降太多，相较于对比例1-2而言仍然能实现比表面积和振实密度的同步提高。
实验例2
将实施例1-5以及对比例1-2在步骤S3中制备得到的电池进行性能测试，测试项目包括充电容量(0.1C)测试以及循环保持率测试，其中，循环测试具体是测试在25℃的条件下进行2C充到4.5V转1.5C充到4.5V，截止电流为0.05C的循环下的容量保持率。测试结果如表2所示。
表2.电池性能测试结果
根据表2中实施例1-5与对比例1-2的对比可知，本发明的实施例提供的利用多孔球形三元前驱体制备得到的电池具有更优异的循环性能和更好的充电容量，使得本发明的实施例提供的电池具有更优异的电化学性能。同时，根据表2中实施例1-4与实施例5的对比可知，本发明的实施例通过在多孔球形三元前驱体内掺杂金属元素能一定程度改善充电容量和循环性能。
综上所述，本发明的实施例提供了一种多孔球形三元前驱体及其制备方法，其能在保证电池的循环性能的前提下，实现大比表面积和高振实的有机统一，以充分提高电池的电化学性能。本发明的实施例还提供了一种三元正极材料、正极极片和电池，三者均通过上述的多孔球形三元前驱体制备得到。因此，也具有能提高电池的电化学性能的优点。
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种多孔球形三元前驱体的制备方法，其特征在于，包括：
    将镍盐、钴盐和锰盐混合得到的金属溶液、氨水和碱液一起通入具有pH为11.5-12.5的反应底液的反应釜中，开启搅拌并将所述反应釜中的pH维持在11.5-12.5进行造粒形成一次颗粒；
    继续造粒使所述一次颗粒团聚形成二次颗粒，在二次颗粒长大至目标粒径的过程中，将所述反应釜内的pH逐渐降低至11-11.5，并同步逐渐降低搅拌速度，以使所述二次颗粒逐渐长大呈多孔球形，且待所述二次颗粒长大至目标粒径后，将所述反应釜内的pH迅速升高至11.5-12.5并保持预设时间后得到中间前驱体；
    将所述中间前驱体进行后处理得到多孔球形三元前驱体。
  2. 根据权利要求1所述的多孔球形三元前驱体的制备方法，其特征在于：
    所述二次颗粒的目标粒径为10.1<D50≤10.5μm；
    优选地，在所述二次颗粒形成过程中，将所述反应釜内的pH逐渐降低至11-11.5，并同步逐渐降低搅拌速度的步骤包括：
    当所述二次颗粒的D50≤3.5μm时，pH对应调节为11.5-12.5，搅拌速度对应调节为450-550rpm；当所述二次颗粒的3.5＜D50≤7.5μm时，pH对应调节为11.5-11.8，搅拌速度对应调节为300-450rpm；当所述二次颗粒的7.5<D50≤10.1μm时，pH对应调节为11-11.5，搅拌速度对应调节为250-300rpm。
  3. 根据权利要求1所述的多孔球形三元前驱体的制备方法，其特征在于：
    在所述金属溶液与所述碱液混合之前，还包括将含M的化合物加入所述金属溶液中；
    优选地，所述含M的化合物为三氧化钼、三氧化钨、硫酸锆中的一种；
    优选地，每800-900L的所述金属溶液需加入610-700g的所述含M的化合物。
  4. 根据权利要求3所述的多孔球形三元前驱体的制备方法，其特征在于：
    所述多孔球形三元前驱体的化学通式为NixCoyMnzMw(OH)2，其中，0.92≤x≤0.97；0.02≤y≤0.06；0.01≤z≤0.02；0.001≤w≤0.02；x+y+z+w＝1；
    优选地，所述多孔球形三元前驱体的比表面积为13-15m2/g；
    优选地，所述多孔球形三元前驱体的振实密度为2.05-2.30g/cm3；
    优选地，所述多孔球形三元前驱体的含硫量为1500-1800ppm；
    优选地，所述镍盐为六水硫酸镍、氯化镍中的任一种；
    优选地，所述钴盐为七水硫酸钴、氯化钴中的任一种；
    优选地，所述锰盐为一水硫酸锰。
  5. 根据权利要求1所述的多孔球形三元前驱体的制备方法，其特征在于：
    所述金属溶液通入所述反应釜的流量为20-40L/h；所述碱液通入所述反应釜的流量为8-18L/h；
    和/或，
    所述金属溶液的浓度为1.6-2.2mol/L；
    和/或，
    所述氨水浓度为1.8-3.2g/L；
    和/或，
    所述碱液为氢氧化钠溶液；优选地，所述氢氧化钠溶液的浓度为6-12mol/L；
    和/或，
    形成所述一次颗粒的搅拌速度维持在450-550rpm；
    和/或，
    形成所述一次颗粒的造核反应时间为3-7h；
    和/或，
    所述预设时间为10-40min。
  6. 根据权利要求1所述的多孔球形三元前驱体的制备方法，其特征在于：
    所述反应底液通过在升温后的清水中边搅拌边加入氨水后得到；
    优选地，所述清水的升温温度范围为55-75℃；
    优选地，搅拌速度维持在450-550rpm。
  7. 一种多孔球形三元前驱体，其特征在于，所述多孔球形三元前驱体通过权利要求1至6中任一项所述的多孔球形三元前驱体的制备方法制备得到。
  8. 一种三元正极材料，其特征在于，包括权利要求1至6中任一项所述的多孔球形三元前驱体的制备方法制备得到的多孔球形三元前驱体；或者，包括权利要求7所述的多孔球形三元前驱体。
  9. 一种正极极片，其特征在于，包括权利要求8所述的正极材料。
  10. 一种电池，其特征在于，包括权利要求9所述的正极极片。
PCT/CN2023/079086 2022-08-25 2023-03-01 一种多孔球形三元前驱体及其制备方法、三元正极材料、正极极片和电池 Ceased WO2024040908A1 (zh)

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