WO2025168564A1 - Procédé de fabrication d'un (oxy)hydroxyde particulaire à distribution étroite du diamètre des particules - Google Patents

Procédé de fabrication d'un (oxy)hydroxyde particulaire à distribution étroite du diamètre des particules

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Publication number
WO2025168564A1
WO2025168564A1 PCT/EP2025/052824 EP2025052824W WO2025168564A1 WO 2025168564 A1 WO2025168564 A1 WO 2025168564A1 EP 2025052824 W EP2025052824 W EP 2025052824W WO 2025168564 A1 WO2025168564 A1 WO 2025168564A1
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WIPO (PCT)
Prior art keywords
range
solution
stirred tank
tank reactor
hydroxide
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Pending
Application number
PCT/EP2025/052824
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English (en)
Inventor
Sven Laufer
Patric Mueller
Ralf Dirk LOEFFLER
Tobias Ferdinand Otto SCHIKARSKI
Fatih CETINEL
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BASF SE
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BASF SE
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Publication of WO2025168564A1 publication Critical patent/WO2025168564A1/fr
Pending legal-status Critical Current
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Classifications

    • 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
    • C01G53/05—Hydroxides; Oxyhydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1868—Stationary reactors having moving elements inside resulting in a loop-type movement
    • B01J19/1881—Stationary reactors having moving elements inside resulting in a loop-type movement externally, i.e. the mixture leaving the vessel and subsequently re-entering it
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00765—Baffles attached to the reactor wall
    • B01J2219/00768—Baffles attached to the reactor wall vertical
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • 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

Definitions

  • aqueous solution(s) (a) Providing one or more aqueous solution(s) (a) containing water-soluble salts of Ni and of at least one transition metal selected from Co and Mn, and, optionally, at least one further metal selected from Ti, Zr, Mo, W, Al, Mg, Nb, and Ta, and an aqueous solution (P) containing an alkali metal hydroxide and, optionally, an aqueous solution (y) containing a complexing agent,
  • step (c) transferring slurry from step (b) into a stirred tank reactor (A) where a solution (a) and a solution (P) and, if applicable, a solution (y) are combined with the slurry at a pH value in the range of from 10.0 to 12.5, determined at 23°C,
  • the present invention is directed towards cathode active materials and their precursors, and to a set-up useful for the inventive process.
  • Lithiated transition metal oxides are currently used as electrode active materials for lithium-ion batteries. Extensive research and developmental work have been performed in the past years to improve properties like charge density, specific energy, but also other properties like the reduced cycle life and capacity loss that may adversely affect the lifetime or applicability of a lithium-ion battery. Additional effort has been made to improve manufacturing methods.
  • inventive process comprises at least four steps, hereinafter also referred to as step (a), step (b), step (c) and step (d), or - even more briefly - (a), (b), (c) and (d), respectively.
  • inventive process may include further - optional - steps. Steps (a), (b), (c) and (d) are described in more detail below.
  • the inventive process is a process for making a particulate (oxy) hydroxi de of TM.
  • Said particulate (oxy) hydroxi de then serves as a precursor for electrode active materials, and it may therefore also be referred to as precursor.
  • the resultant precursor is comprised of secondary particles that are agglomerates of primary particles. Said primary particles have the shape of platelets.
  • the precursor is an (oxy)hydroxide of TM wherein TM comprises Ni and at least one metal selected from Co and Mn and Al, and, optionally, at least one further metal selected from Ti, Zr, Mo, W, Mg, and Nb.
  • TM is a combination of metals according to general formula (I)
  • TM may contain traces of further metal ions, for example traces of ubiquitous metals such as sodium, iron, calcium or zinc, as impurities but such traces will not be taken into account in the description of the present invention. Traces in this context will mean amounts of 0.05 mol-% or less, referring to the total metal content of TM.
  • precursors are particulate materials.
  • precursors have an average particle diameter (d50) in the range of from 3 to 20 pm, preferably from 4 to 16 pm.
  • the average particle diameter may be determined, e. g., by light scattering or LASER diffraction or electroacoustic spectroscopy.
  • the above particle diameter refers to the secondary particle diameter.
  • the span of the particle diameter distribution of inventive precursors may be in the range of from 0.10 to 0.19, preferably 0.15 to 0.19.
  • the span is defined as [(d90) - (d10)]/(d50), with the values of (d90), (d50) and (d10) being the respective percentiles and determined by dynamic light scattering.
  • (d50) is the median value but sometimes also referred to as average particle diameter.
  • the (d1) value is at least 80% of the average value (D50).
  • the value of (d1) is the respective percentile and determined by dynamic light scattering. For example, for a precursor with an average particle diameter of 13.9 pm, the (d1) value is at least 11.1 pm.
  • the various percentiles are preferably volume based.
  • Said particulate material may have an irregular shape but in a preferred embodiment, said particulate material has a regular shape, for example spheroidal or even spherical.
  • the aspect ratio may be in the range of from 1 and 10, preferably from 1 to 3 and even more preferably from 1 to 1.5.
  • the aspect ratio is defined as the ratio of width to length or specifically the particle diameter in the longest dimension versus the particle diameter in the shortest dimension. Perfectly spherical particles have an aspect ratio of 1.
  • Step (a) includes providing at least one aqueous solution (a) containing water-soluble salts of Ni and of at least one transition metal selected from Co and Mn, and, optionally, at least one further metal selected from Ti, Zr, Mo, W, Al, Mg, Nb, and Ta, and an aqueous solution (P) containing an alkali metal hydroxide and, optionally, an aqueous solution (y) containing a complexing agent, for example ammonia.
  • aqueous solution a) containing water-soluble salts of Ni and of at least one transition metal selected from Co and Mn, and, optionally, at least one further metal selected from Ti, Zr, Mo, W, Al, Mg, Nb, and Ta
  • P aqueous solution
  • y containing a complexing agent, for example ammonia.
  • water-soluble salts of cobalt and nickel or manganese or of metals other than nickel and cobalt and manganese refers to salts that exhibit a solubility in distilled water at 25°C of 25 g/l or more, the amount of salt being determined under omission of crystal water and of water stemming from aquo complexes.
  • Water-soluble salts of nickel and cobalt and manganese may preferably be the respective water-soluble salts of Ni 2+ and Co 2+ and Mn 2+ .
  • Examples of water- soluble salts of nickel and cobalt are the sulfates, the nitrates, the acetates and the halides, especially chlorides. Preferred are nitrates and sulfates, of which the sulfates are more preferred.
  • water-soluble compounds of aluminum then refers to compounds like Ah(SO 4 )3, AI(NO 3 ) 3 , KAI(SO 4 ) 2 , NaAICh and NaAI(OH) 4 .
  • the pH value of aqueous solution (a) may be in the range of from 1 to 3 or above 13.
  • MgSO 4 examples of suitable compounds of Mg are MgSO 4 , Mg(NOs)2, magnesium acetate and MgCh, with MgSO 4 being preferred.
  • Ti(SO 4 )2 examples include Ti(SO 4 )2, TiOSO 4 , TiO(NOs)2, Ti(NOs) 4 , with Ti(SO 4 )2 being preferred.
  • Zr(SO 4 )2 examples include zirconium acetate, Zr(SO 4 )2, ZrOSO 4 , ZrO(NOs)2, Zr(NOs) 4 , with Zr(SO 4 )2 being preferred.
  • Examples of suitable compounds of Nb are (NH 4 )Nb(C2O 4 )3 and (NH 4 )NbO(C2O 4 )2.
  • Examples of suitable compounds of Mo are MoOs, Na2MoO 4 , and (NH 4 )2MoO 4 .
  • Suitable compounds of W are WO3, WO3 ⁇ H2O, Na2WO 4 , ammonium tungstate and tungstic acid.
  • Solution (a) may have a pH value in the range of from 2 to 5. In embodiments wherein higher pH values are desired, ammonia may be added to solution (a). However, it is preferred to not add ammonia to solution (a). In case it is intended to provide a solution containing NaAICh and NaAI(OH) 4 it is preferred to provide at least two aqueous solutions, one containing nickel and at least one of cobalt and manganese and, optionally, at least one of Ti, Zr, Mo, W, Mg, Nb, and Ta, and another aqueous solution containing NaAICh or NaAI(OH)4.
  • the concentration of nickel and other constituents of TM can be selected within wide ranges.
  • the respective total metal concentration is selected to be within a range of 1 to 1.8 mol of the metal/kg of solution, more preferably 1.3 to 1.7 mol of the metal/kg of solution.
  • step (a) an aqueous solution of alkali metal hydroxide is provided, hereinafter also referred to as solution (P).
  • alkali metal hydroxides are potassium hydroxide and a combination of sodium and potassium hydroxide, and even more preferred is sodium hydroxide.
  • solution (P) mainly contains alkali metal hydroxide and some amount of carbonate, e.g., 0.1 to 2 % by weight, referring to the respective amount of alkali metal hydroxide, added deliberately or by aging of the solution (P) or the respective alkali metal hydroxide.
  • the pH value of solution (P) is preferably 13 or higher, for example 14.5.
  • Solution (y) contains a complexing agent.
  • complexing agents are ammonia and organic acids or their alkali or ammonium salts wherein said organic acid bears at least two functional groups per molecule and at least one of the functional groups is a carboxylate group.
  • organic acids that bear two identical functional groups are adipic acid, oxalic acid, succinic acid and glutaric acid.
  • organic acids that bears three identical functional groups is citric acid.
  • said organic acid is selected from malic acid, tartaric acid, citric acid, and glycine.
  • the concentration of complexing agent(s) in solution (Y) is in the range of froml to 30 % by weight.
  • the complexing agent is selected from ammonia its concentration is preferably in the range of from 10 to 30 % by weight.
  • the complexing agent(s) is or are selected from organic acids or their alkali or ammonium salts wherein said organic acid bears at least two functional groups per molecule and at least one of the functional groups is a carboxylate group
  • the concentration of said complexing agent in solution (y) may be in the range of from 0.2 to 10% by weight.
  • More preferred complexing agent is ammonia.
  • Step (b) includes combining solution(s) (a) and solution (P) and, if applicable, solution (y) in one or more sub-steps, in a stirred tank reactor, at a pH value in the range of from 11.2 to 14.0, preferably 12.0 to 13.0, determined at 23°C, thereby creating solid particles of hydroxide. Said solid particles are slurried.
  • Step (b) may be performed in a continuously operated stirred tank reactor but is preferably performed as a discontinuous process.
  • Step (b) may be performed in one or more sub-steps or in a single sub-step.
  • step (b) is preferably performed at a constant pH value.
  • step (b) is performed in at least two sub-steps, hereinafter also referred to as sub-step (b1), sub-step (b2), and, if applicable, sub-step (b3) etc.
  • at least two substeps for example sub-steps (b1) and (b2), are performed at different pH values, for example at a pH values that differs by 0.2 to 1.5 units, each determined at 23°C.
  • step (b) is performed at a temperature in the range from 10 to 85°C, preferably at temperatures in the range from 20 to 70°C.
  • step (b) is performed at constant pressure, for example at ambient pressure. In other embodiments, step (b) is performed at elevated pressure, for example up to 50 bar.
  • step (b) is performed under an inert atmosphere, for example nitrogen or a rare gas such as argon.
  • an inert atmosphere for example nitrogen or a rare gas such as argon.
  • Oxygen-depleted air for example with up to 2% by weight of O2, is feasible as well, especially when TM does not contain manganese. Due to the strong alkalinity of solution (P), CO2 is not a suitable atmosphere.
  • slurry is removed from the continuous stirred tank reactor in which step (b) is carried out and transferred to a stirred storage vessel where the slurry is stored under stirring for a time period of from 15 minutes to 24 hours, preferably from 30 minutes to 10 hours, before being transferred to the second stirred tank reactor.
  • Said operation is also referred to as storage step.
  • neither solution (a) nor solution (P) nor solution (Y) is added.
  • Said storage is preferably under inert gas, vide supra.
  • the temperature during the storage step is in the range of from 20 to 70°C, preferably 30 to 70°C.
  • the pH value of the slurry in the storage vessel is in the range of from 10.0 to 13.0 determined at 23°C, preferably from 11.0 to 12.0.
  • Step (c) includes transferring slurry from step (b) into a stirred tank reactor (A) where a solution
  • Step (c) is preferably carried out in a batch mode. Solutions (a) and (P) in step (c) may have a composition different from the composition of solutions a) and (P) in step (b) or preferably the same.
  • the residence time in step (c) is in the range of from 30 minutes to 36 hours.
  • step (c) is preferably lower than in step (b), for example by 0.2 to 2.0 units, determined at 23°C.
  • step (b) the pH value in step (c) is 12.5
  • step (b) is performed at a pH value of least 12.7, for example 12.7 to 14.0 or 12.8 to 13.5. In another example, when the pH value in step (b) is 12.0, step (b) is performed at a pH value of at most 11.9, for example 10.0 to 11.8 or 10.5 to 11.5.
  • step (c) is performed at a temperature in the range from 10 to 85°C, preferably at temperatures in the range from 20 to 70°C.
  • step (c) is performed at constant pressure, for example at ambient pressure. In other embodiments, step (c) is performed at elevated pressure, for example up to 50 bar.
  • step (c) is performed under an inert atmosphere, for example nitrogen or a rare gas such as argon.
  • Oxygen-depleted air for example with up to 2% by weight of O2, is feasible as well, especially when TM does not contain manganese. Due to the strong alkalinity of solution (P), CO2 is not a suitable atmosphere.
  • the stirred tank reactor (A) comprises at least piping through which slurry formed in step (c) is transferred into a side vessel (B) in which step (d) is performed. While step (b) and step (c) are performed subsequently, step (d) is performed at least partially at the same time as step (c).
  • step (d) slurry from step (c) is transferred to a side vessel (B) that contains one to 150 candle filters, preferably 10 to 100 candle filters, through which liquid is withdrawn from the reaction, and slurry is returned into stirred tank reactor from step (c). Said returned slurry has a higher particle content than the slurry transferred to the side vessel (B), and step (d) thus results in a thickening of the slurry.
  • candle filters are arranged as registers.
  • the amounts of slurry are selected in a way that there is no turbulence around the candle filter(s), and a laminar flow is accomplished instead.
  • a laminar flow is accomplished by inlet baffle(s) or a distributor installed at the upper part of side vessel (B).
  • stirred tank reactor (A) may be performed by flushing, for example with inert gas such as nitrogen, or by water or filtrate from step (d). It should be noted that volumes of water or filtrate needed to be applied in the flushing that are smaller than the volumes of liquid that are withdrawn.
  • candle filter(s) are made from sintered metal or from polymers such as polypropylene or polyethylene. They need to stand a pressure of at least 5 bar, preferably at least 8 bar. A maximum pressure is, e.g., 10 bar.
  • candle filter(s) have a diameter of from 60 to 150 mm and a length of from 800 to 2500 mm.
  • Candle filters may be designed as symmetrical or asymmetrical.
  • Symmetrical candle filters have a porous structure with a pore size distribution characterized by an average pore size that is essentially the same over the entire candle.
  • the average pore size varies across the candle, with the size generally increasing from one surface to the other.
  • candle filter(s) have a pore diameters of 5 pm or less, for example 0.3 to 5 pm, preferably 0.5 to 3 pm.
  • the pores may be uniform in diameter or have a pore diameter distribution.
  • candle filters have a filter cloth from porous materials such as polypropylene, polyethylene such as HDPE, PVDF (polyvinylidendifluoride), poly- eetheretherketone, fleece, polytetrafluoroethylene, polyethersulfone (“PES”) or paper, polysulfone or the like, with an average pore diameter of up to 10 pm.
  • Pores from filter cloth may have a diameter of from 0.1 to 5 pm, preferably 0.3 to 3 pm.
  • Polypropylene may be employed as monofilament or multifilament. While monofilament based fabrics have the advantages of a high filtration speed and that the filter cake is removed more easily, and less solids are retained in the filter cloth, multifilament based fabrics have the advantages of higher mechanical stability, resulting in less wear.
  • the volume ratio of side vessel (B) to stirred tank reactor (A) is in the range of from 1 :20 to 1 :4. Side vessel (B) is then smaller than stirred tank reactor (A).
  • Step (d) is performed multiple times. In one embodiment of the present invention, about 10% to up to the 10-fold of the volume of stirred tank reactor are transferred into side vessel (B) per hour and returned back into stirred tank reactor (A).
  • the residence time of a certain portion of solids in side vessel (B) is in the range of some seconds, for example 10 seconds, to up to 5 minutes.
  • the residence time in side vessel (B) decreases with increasing solids content of the slurry transferred from stirred tank reactor (A) into side vessel (B). Such decrease may be performed stepwise or continuously.
  • a major filter cake build-up in said side vessel is prevented by flushing back the filter cake into stirred tank reactor (A) together with the slurry.
  • the filter cake build-up in side vessel (B) is kept in the range of from 5 seconds to 10 minutes, and the filter cake is discharged into the stirred tank reactor (A).
  • Liquid withdrawn in step (d) is an aqueous medium containing alkali metal salt with anions from the nickel salt and the transition metal salt(s) that are dissolved to form aqueous solution (a), traces non-precipitated transition metal salts, and furthermore complexing agent from solution (Y), if applicable.
  • Liquid withdrawn in step (d) is preferably a clear and translucent liquid, but it may contain small particles of hydroxide.
  • the solid particles content in liquor withdrawn in step (d) through the candle filter(s) is below 1 mg/l.
  • slurry from step (b) is transferred to a side vessel (B) as well, and a step (d) is performed likewise.
  • Said side vessel may be the same as for slurry from step (c) or in a separate.
  • a coaxial mixer is used for addition of at solution (a) and (P) or solution (a) and (y), see, e.g., WO 2020/207901.
  • aqueous solution (a) is introduced through the inner pipe of a coaxial mixer and aqueous solution (y) is introduced through the outer pipe, this will lead to a minor degree of incrustations.
  • step (d) to achieve a suited flow distribution device into the inflow section of side vessel (B) may be improved by insertion of an inlet baffle or a distributor.
  • Such inlet baffle or distributor may improve the homogeneity of distribution of residence time in the side vessel and minimize the hold-up of side vessel (B).
  • the inventive process is performed in parallel in several stirred tank reactors (A) that are connected to a side vessel (B), and liquid from the reaction is withdrawn through candle filter(s).
  • A stirred tank reactor
  • side vessel (B) liquid from the reaction is withdrawn through candle filter(s).
  • Such embodiments are useful when large quantities of (oxy) hydroxi de are desired with the same composition.
  • a hydroxide of TM is obtained.
  • partial oxidation and dewatering may take place, and an oxyhydroxide is formed.
  • a further aspect of the present invention refers to particulate (oxy) hydroxi de of TM, hereinafter also referred to as inventive (oxy) hydroxi des or inventive precursors.
  • inventive precursors are advantageously made according to the inventive process.
  • TM refers to a combination of nickel with of at least one metal selected from cobalt and manganese, wherein said inventive (oxy)hydroxide has an average parti- cle diameter (d50) in the range of from 3 to 20 pm, preferably 4 to 16 pm.
  • inventive (oxy)hydroxide preferably has a monomodal particle diameter distribution.
  • TM refers to a combination of nickel with of at least one metal selected from cobalt and manganese, wherein said inventive (oxy)hydroxide has an average particle diameter (d50) in the range of from 3 to 20 pm, preferably 4 to 16 pm, and a core-shell structure wherein both core and shell show an essentially radial alignment of platelet-shaped primary particles, and wherein core and shell are separated by a porous layer that contains randomly arranged primary particles.
  • the porous layer may be detected by scanning electron microscopy (“SEM”) or transmission electron microscopy (“TEM”). In said porous layer, usually only few voids may be detected.
  • said porous layer between core and shell has an average thickness in the range of from 0.1 to 1.0 pm.
  • the portion of radially aligned primary particles may be determined, e.g., by SEM (Scanning Electron Microscopy) of a cross-section of at least 5 secondary particles.
  • Essentially radially alignment does not require a perfect radial orientation but includes that in an SEM analysis, a deviation to a perfectly radial orientation is at most 5 degrees.
  • At least 70% of the secondary particle volume is filled with radially oriented primary particles.
  • a minor inner part for example at most 30%, preferably at most 20%, of the volume of those particles is filled with non-radially oriented primary particles, for example, in random orientation.
  • the share of voids is more than 10% if determined by choosing 5 representative particles in SEM and calculating the voids.
  • inventive (oxy)hydroxides have a particle size (d1) of at least 80% of the average particle diameter (D50).
  • inventive (oxy) hydroxi des have a particle size distribution with a span [(d90) - (d10)]/(d50) in the range of from 0.10 to 0.19, preferably from 0.11 to 0.18.
  • the diameters (d10), (d50) and (d90) may be determined by dynamic light scattering and refer to the respective percentiles.
  • TM in inventive (oxy)hydroxides is a combination of metals according to general formula (I)
  • variables in formula (I) are defined as follows: a is in the range of from 0.25 to 0.4, b is in the range of from zero to 0.2, c is in the range of from 0.6 to 0.75, and d is in the range of from zero to 0.1,
  • inventive precursors have a porous layer between core and shell with an average thickness in the range of from 0.1 to 1.0 pm.
  • Inventive (oxy)hydroxides are excellent precursors for cathode active materials which are suitable for producing batteries with a high volumetric energy density and excellent cycling stability. Another aspect of the present invention is thus the use of inventive precursors for the manufacture of cathode active materials for lithium-ion batteries.
  • Such cathode active materials are made by mixing inventive precursor with a source of lithium, e.g., LiOH or U2O2 or U2CO3, followed by calcination, for example at a temperature in the range of from 750 to 900°C.
  • TM of inventive (oxy)hydroxides corresponds to formula (I)
  • said calcination is preferably performed in an atmosphere of oxygen or oxygen-enriched air, for example with at least 60 vol-% of oxygen, preferably 80 vol-% of oxygen and more preferably at least 90 vol-% oxygen.
  • the variable a in formula (I) is in the range of from 0.25 to 0.4, said calcination may be performed in air atmosphere.
  • Suitable set-ups for said calcination are rotary kilns, roller hearth kilns, and pusher kilns.
  • the temperature is ramped up before reaching the desired temperature of from 750 to 900°C.
  • a mixture of precursor and source of lithium and oxide or hydroxide of Al is heated to a temperature to 350 to 550°C and then held constant for a time of 10 min to 4 hours, and then it is raised to 650°C up to 1000°C, preferably 650 to 850°C.
  • solvent(s) are removed, for example by filtration, evaporation or distilling of such solvents).
  • Preferred are evaporation and distillation.
  • said calcination is performed in a roller hearth kiln, a pusher kiln or a rotary kiln or a combination of at least two of the foregoing.
  • Rotary kilns have the advantage of a very good homogenization of the material made therein.
  • roller hearth kilns and in pusher kilns different reaction conditions with respect to different steps may be set quite easily.
  • box-type and tubular furnaces and split tube furnaces are feasible as well.
  • the electrode active materials so obtained have a specific surface (BET) in the range of from 0.1 to 0.8 m 2 /g, determined according to DIN-ISO 9277:2003-05.
  • BET specific surface
  • such cathode active materials also have a high breaking strength.
  • Another aspect of the present invention is related to a set-up, hereinafter also referred to as inventive set-up, in which an inventive process may be performed.
  • (B) a side vessel connected to stirred tank reactor (A) through at least two pipes, (P1) and (P2), (C) one to 150 candle filters located in side vessel (B) through which liquid may be withdrawn from the reaction and slurry is returned into said stirred tank reactor (A) through pipe (P2).
  • Side vessel (B) together with the candle filter(s) may serve as a thickener.
  • the inventive set-up additionally comprises a means for introducing aqueous medium such as water or mother liquor, or a gas such as nitrogen into side vessel (B) for the purpose of flushing back slurry into stirred tank reactor (A).
  • Such means may be selected from pumps and pressure generators.
  • the present invention is further illustrated by a working example and by a drawing.
  • (A.1) Stirred tank reactor, with baffles, volume: 200 liter, with feed inlets for solutions (a.1), (p.1), (y.1) and double jacket for heating omitted [simplified drawing]
  • side vessel (B.1) one candle filter (not displayed), material: polyethylene, pore diameter: 0.3 to 3 pm, length 1000 mm: diameter: 80 mm. Filter cloth: HDPE, pore diameter up to 0.8 pm, air permeability 0.2 to 0.5 L/(dm 2 min)
  • Another pipe is attached at the bottom of the side vessel (B.1) and leads to stirred tank reactor (A.1).
  • Flushing arrangement Flushing is performed in the reverse direction via the filtrate (mother liquor) line
  • a 10 I stirred vessel equipped with baffles and a three-stage pitch-blade stirrer (45° blade angle) with a diameter of 0.21 m was charged with 4 liters of de-ionized water.
  • the stirrer element was activated to reach an average energy dissipation of 0.8 W/l and the water was heated to 55°C.
  • solution (y.1) was added to reach an NH3 concentration of 0.23w%.
  • the pH of the solution was adjusted to 12.2 by adding solution (p.1 ).
  • the stirrer rotation speed was increased and constantly operated at 420 rpm (average energy input -12.6 W/l).
  • feeding of solutions (a.1), (p.1 ) and (y.1) was started simultaneously.
  • the total flow of feeds was adjusted to reach an average residence time of 7.5 hours.
  • the molar ratio between ammonia and metal was adjusted to 0.17.
  • the flow rate of the NaOH was adjusted by a pH value regulation circuit to keep the pH value in the vessel at a constant value of 12.4.
  • the apparatus was operated continuously keeping the liquid level in the reaction vessel constant.
  • the resulting seed suspension for step (b1.2) was collected via free overflow from the vessel.
  • the resulting slurry contained about 110 g/l mixed hydroxide of Ni, Co and Mn with an average particle size (D50) of 3.9 pm and a span of 1 .28.
  • the set-up according to Figure 1 is charged with 150 I de-ionized water so that both stirrer stages are submersed.
  • the stirrer speed is adjusted to 130 rpm (0.36 W/l) while the water is heated via the double jacket to 55°C.
  • the temperature is kept constant at 55°C during the complete batch.
  • 7 kg of solution (p.1 ) are added.
  • 12 kg of slurry of seeds from step (b.1 ) is added to the mixture leading to an initial solid content of approx. 5 g/l.
  • the pH value after addition of all feeds is 11 .65.
  • stirrer speed was adjusted to 396 rpm (corresponds to 7.9 W/l), and the feed of solutions (a.1), (p.1 ), and (y.1) is started simultaneously.
  • the stirrer speed is stepwise decreased during the batch synthesis to a final stirrer speed of 130 rpm (0.36 W/l).
  • the pH value is kept constant at 11 .5 by adjusting the addition of solutions (p.1 ) and (y.1) to obtain an ammonia concentration in mother liquor of 0.7w%.
  • the ratio between reactor volume (200 I) and volume flow of total feeds (residence time equivalent) was started in a way that an average residence time of 40 hours would have resulted.
  • the side vessel (B.1) is empty at the beginning. After a reaction time of two hours, suspension transfer to the side vessel (B.1) is started with a volume flow of 50 l/h. 10 minutes later, suspension transfer from side vessel (B.1) back to the reactor is started with a volume flow of 340 l/h.
  • the volume flows of suspension transfer to side vessel (B.1) and back to the reactor (A.1) are adjusted during above mentioned feed ramp to keep reactor volume constant at 200 I during the complete synthesis. Flushing back to stirred tank reactor (A.1) is achieved through nitrogen pressure of 5 bar.
  • the complete synthesis is 24 hours leading to a solids content in the reactor of 450 g/L, measured via H2SO4 dissolution of suspension and subsequent ICP analysis of Ni, Co, Mn.
  • P-CAM.1 is mixed with LiOH in a molar ratio Li/TM of 1.04 and calcined in a laboratory Linn furnace for 8 hours at 765°C. After natural cooling to ambient temperature, the resultant CAM.1 is deagglomerated in a lab mill. The resulting CAM.1 has an average particle size of 13.7 pm and a span of 0.19.
  • cathodes containing CAM.1 have excellent properties. In addition, their pressed density and compressability is high.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un (oxy)hydroxyde particulaire de TM où TM se réfère à une combinaison de nickel et d'au moins un métal choisi parmi Co et Mn et ledit procédé comprenant les étapes consistant à : (a) fournir une ou plusieurs solution(s) aqueuse(s) (α) contenant des sels hydrosolubles de Ni et d'au moins un métal de transition choisi parmi Co et Mn, et, facultativement, au moins un autre métal choisi parmi Ti, Zr, Mo, W, Al, Mg, Nb et Ta, et une solution aqueuse (β) contenant un hydroxyde de métal alcalin et, facultativement, une solution aqueuse (γ) contenant un agent complexant, (b) combiner la ou les solution(s) (α) et la solution (β) et, le cas échéant, la solution (γ) à une valeur de pH se situant dans la plage de 11,2 et 14,0, déterminée à 23°C dans un réacteur à cuve agitée, créant ainsi des particules solides d'hydroxyde, lesdites particules solides étant mises en bouillie, (c) transférer la bouillie provenant de l'étape (b) dans un réacteur à cuve agitée (A) où une solution (α) et une solution (β) et, le cas échéant, une solution (γ) sont combinées avec la bouillie à une valeur de pH se situant dans la plage de 10,0 à 12,5, déterminée à 23°C, (d) procédé dans lequel la bouillie provenant du réacteur à cuve agitée (A) est transférée dans une cuve latérale (B) qui contient un à 150 filtres à bougie (C) à travers lesquels le liquide est retiré de la réaction, et la bouillie est renvoyée dans le réacteur à cuve agitée à partir de l'étape (c).
PCT/EP2025/052824 2024-02-09 2025-02-04 Procédé de fabrication d'un (oxy)hydroxyde particulaire à distribution étroite du diamètre des particules Pending WO2025168564A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2720305A1 (fr) 2011-06-07 2014-04-16 Sumitomo Metal Mining Co., Ltd. Hydroxyde composite contenant du nickel et procédé de fabrication dudit hydroxyde, matériau actif positif pour batterie secondaire à électrolyte non aqueux et procédé de fabrication dudit matériau actif, et batterie secondaire à électrolyte non aqueux
EP2818452A1 (fr) 2012-02-23 2014-12-31 Sumitomo Metal Mining Co., Ltd. Hydroxyde de nickel composite et procédé de production associé, matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux et procédé de production associé, et batterie secondaire à électrolyte non aqueux
WO2020207901A1 (fr) 2019-04-10 2020-10-15 Basf Se Procédé pour la précipitation d'un hydroxyde mixte, et matériaux actifs de cathode fabriqués à partir d'un tel hydroxyde
CN113603159A (zh) * 2021-08-25 2021-11-05 湖南杉杉能源科技有限公司 一种多层铝掺杂的镍钴锰前驱体及其制备方法
CN116002776A (zh) * 2023-01-06 2023-04-25 湖南中伟新能源科技有限公司 三元前驱体及其制备方法、正极材料
WO2023135055A1 (fr) * 2022-01-17 2023-07-20 Basf Se Procédé de fabrication d'(oxy) hydroxydes particulaires et d'(oxy) hydroxydes particulaires (oxy)

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2720305A1 (fr) 2011-06-07 2014-04-16 Sumitomo Metal Mining Co., Ltd. Hydroxyde composite contenant du nickel et procédé de fabrication dudit hydroxyde, matériau actif positif pour batterie secondaire à électrolyte non aqueux et procédé de fabrication dudit matériau actif, et batterie secondaire à électrolyte non aqueux
EP2818452A1 (fr) 2012-02-23 2014-12-31 Sumitomo Metal Mining Co., Ltd. Hydroxyde de nickel composite et procédé de production associé, matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux et procédé de production associé, et batterie secondaire à électrolyte non aqueux
WO2020207901A1 (fr) 2019-04-10 2020-10-15 Basf Se Procédé pour la précipitation d'un hydroxyde mixte, et matériaux actifs de cathode fabriqués à partir d'un tel hydroxyde
CN113603159A (zh) * 2021-08-25 2021-11-05 湖南杉杉能源科技有限公司 一种多层铝掺杂的镍钴锰前驱体及其制备方法
WO2023135055A1 (fr) * 2022-01-17 2023-07-20 Basf Se Procédé de fabrication d'(oxy) hydroxydes particulaires et d'(oxy) hydroxydes particulaires (oxy)
CN116002776A (zh) * 2023-01-06 2023-04-25 湖南中伟新能源科技有限公司 三元前驱体及其制备方法、正极材料

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