Method for producing (oxy)hydroxide, and (oxy)hydroxide

Abstract

1. A method for producing a particulate (oxy)hydroxide of TM, wherein TM represents a combination of nickel and at least one metal selected from Co and Mn, said method comprising the steps of: (a) providing one or more aqueous solutions (α) containing a water-soluble salt of Ni, 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, an aqueous solution (β) containing an alkali metal hydroxide, and optionally an aqueous solution (γ) containing a complexing agent; (b) combining solution(s) (α), solution (β), and, if applicable, solution (γ) in one or more substeps in a continuous stirred tank reactor at a pH value in the range of 10.5 to 12.5 as determined at 23°C to produce solid particles of hydroxide, wherein the solid particles are slurried; Including, The stirred tank reactor used in step (b) or at least one sub-step (b) is equipped with a solid-liquid separator through which a mother liquor containing slurried particles of hydroxide in the range of 2 mg / l to 20 g / l is removed.

Description

[Technical Field]

[0001] The present invention relates to a method for producing particulate (oxy)hydroxide of TM, wherein TM represents a combination of nickel and at least one metal selected from Co and Mn, said method comprising the following steps: (a) providing one or more aqueous solutions (α) containing a water-soluble salt of Ni, 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, an aqueous solution (β) containing an alkali metal hydroxide, and optionally an aqueous solution (γ) containing a complexing agent; (b) combining solution(s) (α), solution (β), and, if applicable, solution (γ) in one or more substeps in a stirred tank reactor at a pH value in the range of 10.5 to 12.5 determined at 23°C to produce solid particles of hydroxide, wherein the solid particles are slurried; Including, The stirred tank reactor used in step (b) or at least one sub-step (b) is equipped with a solid-liquid separator through which a mother liquor containing slurried particles of hydroxide in the range of 2 mg / l to 20 g / l is removed. [Background technology]

[0002] Lithiated transition metal oxides are currently used as electrode active materials in lithium-ion batteries. Extensive research and development has been conducted over the past several years to improve properties such as charge density and specific energy, as well as other properties such as cycle life degradation and capacity loss that adversely affect the life or applicability of lithium-ion batteries. Further efforts are being made to improve manufacturing methods.

[0003] In a typical process for preparing cathode materials for lithium-ion batteries, a so-called precursor is first formed by co-precipitating a transition metal, which may or may not be basic, as a carbonate, oxide, or preferably as a hydroxide. This precursor is then mixed with a lithium source, such as, but not limited to, LiOH, Li2O, or especially Li2CO3, and calcined at high temperature. The lithium salt(s) can be used as hydrate(s) or in dehydrated form. Calcination or calcination, also commonly referred to as thermal treatment or heat treatment of the precursor, is typically carried out at temperatures ranging from 600 to 1000°C. During the heat treatment, a reaction occurs to form the electrode active material. The heat treatment is carried out in the heated zone of an oven or kiln.

[0004] The properties of the precursor are reflected to some extent in the properties of each electrode active material, such as particle size distribution, the content of each transition metal, etc. Therefore, by controlling the properties of the precursor, it is possible to affect the properties of the electrode active material.

[0005] Cathode active materials with narrow particle size distributions, and therefore precursors thereof, have been the subject of research. EP 2 720 305 A discloses a two-stage process in which the pH value is lowered in the second stage, the so-called particle growth stage, relative to the first stage. EP 2 818 452 A discloses a two-stage process in which a mother liquor is removed during the particle growth step. Care is taken to avoid removing solids with the mother liquor. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] EP 2 720 305 A [Patent Document 2] EP 2 818 452 A Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a method for producing a precursor having a narrow particle size distribution and high sphericity. A further object of the present invention was to provide a precursor for an electrode active material having a narrow particle size distribution and excellent sphericity. [Means for solving the problem]

[0008] Thus, a method as defined at the beginning has been found, also referred to as "the method of the invention" or "the method according to the (present) invention". The method of the invention comprises at least two steps, also referred to below as step (a) and step (b), or more simply as (a) and (b). The method of the invention may comprise further (optional) steps. Steps (a) and (b) are explained in more detail below. The method of the invention allows for the production of precursors with a narrow particle size distribution and high sphericity. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 shows the setup for carrying out the method of the present invention and the comparative method, and shows the reactor design for carrying out the synthesis of P-CAM.1. [Figure 2] Figure 2 is a SEM cross-sectional micrograph of P-CAM.1. [Figure 3] Figure 3 is an SEM micrograph of particles in the mother liquor that emerged from the clarifier approximately 10 minutes before the synthesis of P-CAM.1 was complete. DETAILED DESCRIPTION OF THE INVENTION

[0010] In step (b), if a certain amount of particles is similarly removed through a clarifier, the span of particulate (oxy)hydroxides in the resulting TM has been found to be in the range of 0.20-0.33.

[0011] The method of the present invention is a method for producing particulate (oxy)hydroxide of TM, which therefore functions as a precursor of the electrode active material and is therefore also called a precursor.

[0012] In one embodiment of the invention, the precursor obtained is composed of secondary particles which are agglomerates of primary particles, said primary particles having the shape of platelets.

[0013] In one embodiment of the present invention, the specific surface area (BET) of the obtained precursor is 2 to 70 m 2 / g, determined for example by nitrogen adsorption according to DIN-ISO 9277:2003-05. The outgassing temperature is 120°C.

[0014] The precursor is an (oxy)hydroxide of TM, where TM comprises Ni, Co and at least one metal selected from Mn and Al, and optionally at least one further metal selected from Ti, Zr, Mo, W, Mg and Nb.

[0015] In one embodiment of the present invention, TM is a metal combination according to general formula (I): (Ni a Co b Mn c ) 1-d M d (I) (wherein a is in the range of 0.6 to 0.95, preferably 0.8 to 0.94, b is in the range of 0.025 to 0.2, preferably 0.025 to 0.15; c is in the range of 0 to 0.2, preferably 0 to 0.15; d is in the range of 0 to 0.1, M is selected from Mg, Al, Ti, Zr, Mo, W, Nb and Ta; a+b+c=1 and b+c>0 Or, M comprises Al and d>0).

[0016] In another embodiment of the present invention, TM corresponds to general formula (Ia): (Ni a Co b Mn c ) 1-d M d (I a) (wherein a is in the range of 0.25 to 0.4, b is in the range of 0 to 0.2, c is in the range of 0.6 to 0.75, d is in the range of 0 to 0.1, M is selected from Mg, Al, Ti, Zr, Mo, W, Nb and Ta; a+b+c=1).

[0017] In either case, the TM may contain trace amounts of additional metal ions as impurities, such as trace amounts of ubiquitous metals such as sodium, iron, calcium, or zinc, but such trace amounts are not considered within the context of this invention. Trace amounts in this context mean amounts of 0.05 mol % or less, relative to the total metal content of the TM.

[0018] The precursor is a particulate material. In one embodiment of the present invention, the precursor has an average particle size D50 in the range of 3 to 20 μm, preferably 4 to 16 μm. The average particle size can be determined, for example, by light scattering, laser diffraction, or electroacoustic spectroscopy. The particle size refers to the particle size of secondary particles.

[0019] The span of the particle size distribution of the precursor is in the range of 0.20 to 0.33, preferably 0.21 to 0.29, and is defined as [(D90)-(D10)] / (D50), where the values ​​of (D90), (D50), and (D10) are determined by dynamic light scattering.

[0020] Although the particulate matter may have an irregular shape, in a preferred embodiment the particulate matter has a regular shape, for example an ellipsoid or even a sphere. The aspect ratio may range from 1 to 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 more specifically, the ratio of the particle size in the longest dimension to the particle size in the shortest dimension. A perfectly spherical particle has an aspect ratio of 1.

[0021] Step (a) comprises providing at least one aqueous solution (α) containing a water-soluble salt of Ni, at least one metal selected from Co and Mn, and optionally at least one further metal selected from Ti, Zr, Mo, W, Al, Mg, Nb and Ta, an aqueous solution (β) containing an alkali metal hydroxide, and optionally an aqueous solution (γ) containing a complexing agent, for example ammonia.

[0022] The term water-soluble salts of cobalt and nickel or manganese, or of metals other than nickel and cobalt and manganese, refers to salts that have a solubility in distilled water at 25°C of 25 g / l or more, the amount of salt being determined omitting water of crystallization and water resulting from aquo complexes. The water-soluble salts of nickel and cobalt and manganese are preferably Ni 2+ and Co 2+ and Mn 2+ Examples of water-soluble salts of nickel and cobalt include sulfates, nitrates, acetates, and halides, especially chlorides. Nitrates and sulfates are preferred, with sulfates being more preferred.

[0023] Thus, the term "water-soluble compounds of aluminum" refers to compounds such as Al2(SO4)3, Al(NO3)3, KAl(SO4)2, NaAlO2, and NaAl(OH)4. Depending on the choice of water-soluble compounds of aluminum, the pH value of the aqueous solution (α) may range from 1 to 3 or may exceed 13.

[0024] Examples of suitable Mg compounds are MgSO4, Mg(NO3)2, magnesium acetate and MgCl2, with MgSO4 being preferred.

[0025] Examples of suitable compounds of Ti are Ti(SO4)2, TiOSO4, TiO(NO3)2, Ti(NO3)4, with Ti(SO4)2 being preferred. Examples of suitable Zr compounds are zirconium acetate, Zr(SO4)2, ZrOSO4, ZrO(NO3)2, Zr(NO3)4, with Zr(SO4)2 being preferred.

[0026] Examples of suitable Nb compounds are (NH4)Nb(C2O4)3 and (NH4)NbO(C2O4)2. Examples of suitable Mo compounds are MoO3, Na2MoO4 and (NH4)2MoO4.

[0027] Examples of suitable W compounds are WO3, WO3·H2O, Na2WO4, ammonium tungstate, and tungstic acid.

[0028] Solution (α) may have a pH value in the range of 2 to 5. In embodiments where a higher pH value is desired, ammonia may be added to solution (α). However, it is preferred not to add ammonia to solution (α). When it is intended to provide a solution containing NaAlO2 and NaAl(OH)4, it is preferred to provide at least two aqueous solutions, where one solution contains nickel, 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 contains NaAlO2 or NaAl(OH)4.

[0029] The concentrations of nickel and other components of the TM can optionally be selected within wide ranges, with the total metal concentration of each preferably being selected to be within the range of 1 to 1.8 moles of metal per kg of solution, more preferably 1.3 to 1.7 moles of metal per kg of solution.

[0030] Furthermore, in step (a), an aqueous solution of an alkali metal hydroxide, hereinafter also referred to as solution (β), is provided. Examples of alkali metal hydroxides are potassium hydroxide and a combination of sodium hydroxide and potassium hydroxide, more preferably sodium hydroxide.

[0031] In one embodiment of the present invention, solution (β) mainly contains alkali metal hydroxides and a certain amount of carbonates, for example, 0.1 to 2 mass % relative to the amount of each alkali metal hydroxide, which carbonates are intentionally added or are produced by aging solution (β) or the respective alkali metal hydroxides.

[0032] The solution (β) has a hydroxide concentration in the range of 0.1 to 12 mol / l, preferably 6 to 10 mol / l.

[0033] The pH value of the solution (β) is preferably 13 or higher, for example 14.5.

[0034] Solution (γ) contains a complexing agent, examples of which are ammonia and organic acids or their alkali or ammonium salts, where the organic acids have at least two functional groups per molecule, at least one of which is a carboxylate group.

[0035] Examples of organic acids with two identical functional groups are adipic acid, oxalic acid, succinic acid, and glutaric acid. An example of an organic acid with three identical functional groups is citric acid.

[0036] In one embodiment of the invention, the organic acid is selected from malic acid, tartaric acid, citric acid, and glycine.

[0037] In one embodiment of the present invention, the concentration of the complexing agent(s) in solution (γ) is in the range of 1 to 30% by mass. In an embodiment in which the complexing agent is selected from ammonia, the concentration is preferably in the range of 10 to 30% by mass. In an embodiment in which the complexing agent(s) is selected from organic acids or their alkali or ammonium salts, the organic acids having at least two functional groups per molecule, at least one of the functional groups being a carboxylate group, the concentration of the complexing agent in solution (γ) may be in the range of 0.2 to 10% by mass.

[0038] A more preferred complexing agent is ammonia.

[0039] Step (b) comprises combining solution(s) (α), solution (β), and, where applicable, solution (γ) in one or more substeps in a stirred-tank reactor at a pH value in the range of 10.5 to 12.5, determined at 23°C, to produce solid hydroxide particles, the solid particles being slurried. Preferably, step (b) is carried out as a discontinuous process.

[0040] In embodiments where step (b) is carried out in a single sub-step (also called a "single step" or "single operation"), step (b) is preferably carried out at a constant pH value.

[0041] In embodiments where step (b) is carried out in at least two substeps, hereinafter also referred to as substep (b1), substep (b2), and, if applicable, substep (b3), etc., the at least two substeps, e.g., substeps (b1) and (b2), are carried out at different pH values, e.g., pH values ​​differing by 0.2 to 1.5 units, and each pH value is determined at 23°C.

[0042] In one embodiment of the present invention, such sub-step (b1) comprises combining solution (α), solution (β) and, where applicable, solution (γ) in a continuously operated stirred tank reactor at a pH value in the range of 12.0 to 12.5 determined at 23°C, thereby producing solid particles of hydroxide, said solid particles being slurried; and Substep (b2) comprises transferring the slurry from step (b) to a stirred tank reactor where solution (α), solution (β), and, if applicable, solution (γ) are combined with the slurry at a pH value in the range of 11.0 to 12.0 determined at 23°C; Here, the stirred tank reactor used in sub-step (b2) is equipped with a solid-liquid separator through which a mother liquor containing slurried particles of hydroxide in the range of 2 mg / l to 20 g / l is removed.

[0043] In one embodiment of the present invention, the particles obtained from step (b1) have an average diameter (D50) in the range of 1 to 6 μm.

[0044] In one embodiment of the present invention, the residence time of the slurry in step (b1) is in the range of 10 minutes to 6 hours, preferably in the range of 30 minutes to 9 hours, more preferably in the range of 4 to 8 hours. Step (b1) can be carried out in a continuous mode or a discontinuous mode, with the discontinuous mode being preferred.

[0045] In one embodiment of the present invention, step (b) is carried out at a temperature in the range of 10 to 85°C, preferably at a temperature in the range of 20 to 70°C.

[0046] In one embodiment of the invention, step (b) is carried out at constant pressure, for example at atmospheric pressure. In another embodiment, step (b) is carried out at elevated pressure, for example up to 50 bar.

[0047] In one embodiment, to carry out substep (b2), the slurry from substep (b1) is transferred to a stirred tank reactor where solution (α), solution (β), and, where applicable, solution (γ) are combined with the slurry at a pH value in the range of 11.0 to 12.0 determined at 23° C. Preferably, the pH value in substep (b2) is lower than in step (b1), e.g., at least 0.2 units, more preferably at least 0.3 units lower.

[0048] The transfer can be carried out immediately after forming the slurry or after an ageing period (see below) in a storage vessel.

[0049] In one embodiment of the present invention, the solids content of the slurry transferred to substep (b2) or the storage vessel (see below) is in the range of 200 to 1200 g / l. Prior to the start of substep (b2), the slurry from step (b1) is preferably diluted to 2 to 100 g / l, for example with deionized water or mother liquor, in the reactor where substep (b2) is carried out. The solids content can be determined by density measurement or ICP (inductively coupled plasma) or Coriolis meter and refers to the slurried particles. Dissolved compounds, such as (but not limited to) Na2SO4, are ignored in this context.

[0050] In one embodiment of the present invention, step (b) is carried out under an inert atmosphere, for example, under a noble gas such as nitrogen or argon. Oxygen-deficient air, for example, air with 2% or less O by weight, can also be used, especially if the TM does not contain manganese. CO is not a suitable atmosphere because solution (β) is strongly alkaline.

[0051] In one embodiment, in substep (b2), the slurry from substep (b1) is transferred to a stirred tank reactor operated batchwise, where solution (α), solution (β), and, if applicable, solution (γ) are combined with the slurry at a pH value in the range of 11.0 to 12.0, the pH value being determined at 23°C.

[0052] Solution (α), solution (β), and, if applicable, solution (γ) in substep (b2) are defined as above. They may have the same composition throughout step (b) or may be different, but within the framework of the above definition, for example, one of them contains a water-soluble salt of nickel and at least one of cobalt and manganese. In such a case, they are also referred to as solution (α'), solution (β'), and, if applicable, solution (γ'), respectively. However, preferably, the composition of solution (α) in step (b) is kept constant.

[0053] Even more preferably, the composition of solution (α) and the composition of solution (β) are kept constant during step (b).

[0054] The stirred tank reactor used in step (b) or in particular sub-step (b2) is equipped with a solid-liquid separator through which a mother liquor containing slurried particles of hydroxide in the range of 0.002 to 20 g / l is removed, i.e. the slurried particles are removed from the stirred tank reactor together with the mother liquor without being returned.

[0055] This can be achieved by intentionally exceeding the capacity of commercial clarifiers. In embodiments where membranes are used for solid-liquid separation, the mesh is selected to be larger than the average particle size of the hydroxide being slurried.

[0056] The particles removed during step (b), particularly in sub-step (b2), may have a wide particle size distribution, for example, from 0.2 to 20 μm, with a span of 0.3 to 1.0.

[0057] In one embodiment, the composition of solution (α) (or (α'), if applicable), e.g., the concentrations of nickel and cobalt or manganese, is varied during the course of substep (b2). In another embodiment of the invention, the composition of solution (α) (or (α'), if applicable) remains constant.

[0058] In one embodiment of the present invention, the duration of sub-step (b2) is in the range of 30 minutes to 80 hours, preferably in the range of 10 to 70 hours, more preferably in the range of 15 to 60 hours.

[0059] In one embodiment of the present invention, sub-step (b2) is carried out at a temperature in the range of 10 to 85°C, preferably at a temperature in the range of 20 to 70°C.

[0060] In one embodiment of the invention, sub-step (b2) is carried out at constant pressure, for example at atmospheric pressure. In another embodiment, step (b) is carried out at elevated pressure, for example up to 50 bar.

[0061] In one embodiment of the invention, the process of the invention is carried out in a cascade of at least two stirred tank reactors, the first of which is equipped with an overflow system through which slurry is removed from the first stirred tank reactor and transferred directly or indirectly to a second stirred tank reactor.

[0062] In a preferred embodiment, the slurry is removed from the continuous stirred tank reactor in which step (b) is carried out and transferred to a stirred storage vessel, where it is stored under stirring for a period of 15 minutes to 24 hours, preferably 30 minutes to 10 hours, before being transferred to a second stirred tank reactor. This operation is also called the storage step. During the storage step, neither solution (α), solution (β), nor solution (γ) is added. The storage is preferably carried out under inert gas (see above).

[0063] In one embodiment of the present invention, the temperature during the storage step is in the range of 20 to 70°C, preferably 30 to 70°C.

[0064] In one embodiment of the present invention, the pH value of the slurry in the storage vessel is in the range of 10.0 to 13.0, preferably 11.0 to 12.0, determined at 23°C.

[0065] In one embodiment of the present invention, simultaneously, 5-30% by volume, preferably 10-20% by volume, of the slurry is in the storage vessel and 70-95% by volume, preferably 80-90% by volume, of the slurry is in the tank reactor(s) in which step (b) is carried out. In this context, the amount of slurry placed in the piping or related parts is ignored.

[0066] In one embodiment of the present invention, the slurry in the storage vessel is stirred from time to time, for example with an average energy input of 0.2 to 1 W / l, which is useful for avoiding settling of the solids in the slurry.

[0067] Substep (b2) can be followed by further steps, such as a work-up step I. An example of a work-up step I is the removal of (oxy)hydroxide particles by solid-liquid separation methods, such as filtration.

[0068] In such a step I, the particles from substep (b2) are separated from the liquid phase by a solid-liquid separation method, preferably filtration or centrifugation. The liquid phase is sometimes called the mother liquor. Filtration can be carried out, for example, in a belt filter or a filter press.

[0069] To remove the mother liquor, the filter cake is preferably washed, for example with water or an alkali metal hydroxide or alkali metal carbonate solution. Filtration is suction or pressure supported.

[0070] Step I may be carried out at any temperature as long as the water is in a liquid state, for example, 5 to 95°C, preferably 20 to 60°C.

[0071] Step I results in a solid material that is a particulate (oxy)hydroxide or oxide of TM. The material typically has a high moisture content, e.g., 1-30% by weight, and can be dried, for example, in air at a temperature in the range of 80-150°C or under reduced pressure ("vacuum") to a moisture content in the range of 100-5,000 ppm (ppm is ppm by weight). The moisture content can be determined by drying in a vacuum at 100°C until no mass changes. The moisture content may also be determined by Karl Fischer titration.

[0072] Following step I or drying, the particulate (oxy)hydroxide or oxide of the TM may be subjected to step (d), which involves heat treatment of the solids from step I in a rotary kiln or flash calciner.

[0073] In one embodiment of step (d), the moist solid material is introduced into the rotary kiln by a chute or vibrating chute, a spiral conveyor or a screw conveyor, preferably a screw conveyor having a single screw or multiple screws.

[0074] A further aspect of the invention relates to particulate (oxy)hydroxides of TM, hereinafter also referred to as (oxy)hydroxides of the invention or precursors of the invention, which are advantageously prepared according to the method of the invention.

[0075] In the (oxy)hydroxide of the present invention, TM means a combination of nickel and at least one metal selected from cobalt and manganese, and said (oxy)hydroxide of the present invention has an average particle size (d50) in the range of 3 to 20 μm, preferably 4 to 16 μm, and has a core-shell structure, wherein both the core and the shell exhibit an essentially radial arrangement of platelet-like primary particles, and the core and the shell are separated by a porous layer containing randomly arranged primary particles.

[0076] The porous layer can be detected by scanning electron microscopy ("SEM") or transmission electron microscopy ("TEM"). Usually, only a small amount of voids are detected in the porous layer. Preferably, the porous layer between the core and the shell has an average thickness in the range of 0.1 to 1.0 μm.

[0077] The fraction of radially arranged primary particles can be determined, for example, by SEM (scanning electron microscopy) of cross sections of at least five secondary particles.

[0078] "Essentially radially arranged" does not require a perfect radial orientation, but includes deviations of up to 5 degrees from a perfect radial orientation upon SEM analysis.

[0079] Furthermore, at least 70% by volume of the secondary particles are filled with radially arranged primary particles, preferably only a small inner portion of the particle volume, e.g., up to 30% by volume, preferably up to 20% by volume, is filled with, e.g., randomly oriented, non-radially arranged primary particles.

[0080] In the porous layer, the void ratio is preferably more than 10% when calculated from five representative particles selected by SEM.

[0081] The (oxy)hydroxides of the present invention have a particle size distribution with a span [(d90)-(d10)] / (d50) in the range of 0.2 to 0.33, preferably 0.21 to 0.29. The diameters (D10), (D50) and (D90) can be determined by dynamic light scattering and are related to their respective percentiles.

[0082] In one embodiment of the present invention, TM in the (oxy)hydroxide of the present invention is a combination of metals according to general formula (I), (Ni a Co b Mn c ) 1-d M d (I) (wherein a is in the range of 0.6 to 0.95, preferably 0.8 to 0.94, b is in the range of 0.025 to 0.2, c is in the range of 0 to 0.2, d is in the range of 0 to 0.1, M is selected from Mg, Al, Ti, Zr, Mo, W, Al, Mg, Nb, and Ta; a+b+c=1).

[0083] In another embodiment of the present invention, TM in the (oxy)hydroxide of the present invention is a combination of metals according to general formula (Ia), (Ni a Co b Mn c ) 1-d M d (I a) (wherein a is in the range of 0.25 to 0.4, b is in the range of 0 to 0.2, c is in the range of 0.6 to 0.75, d is in the range of 0 to 0.1, M is selected from Mg, Al, Ti, Zr, Mo, W, Al, Mg, Nb, and Ta; a+b+c=1).

[0084] The (oxy)hydroxides of the present invention are preferably obtained according to the process of the present invention.

[0085] The (oxy)hydroxides of the present invention are excellent precursors for cathode active materials suitable for the fabrication of batteries with high volumetric energy density and excellent cycling stability. Such cathode active materials are prepared by mixing them with a lithium source, such as LiOH, Li2O2, or Li2CO3, followed by calcination at a temperature ranging from 600 to 1000°C. In particular, in embodiments in which the TM of the (oxy)hydroxides of the present invention corresponds to formula (I), the calcination is preferably carried out in an atmosphere of oxygen or oxygen-enriched air, e.g., having at least 60% oxygen by volume, preferably 80% oxygen by volume, and more preferably at least 90% oxygen by volume. In embodiments in which the TM of the (oxy)hydroxides of the present invention corresponds to formula (Ia), the calcination can be carried out in an air atmosphere.

[0086] Examples of equipment suitable for the calcination include a rotary kiln, a roller hearth kiln, and a pusher kiln.

[0087] In one embodiment of the present invention, the temperature is increased before reaching a desired temperature of 700° C. to 1000° C., preferably 750° C. to 900° C. For example, a mixture of a precursor, a lithium source, and an Al oxide or hydroxide is first heated to 350° C. to 550° C., then kept constant for 10 minutes to 4 hours, and then the temperature is increased to 650° C. to 1000° C., preferably 650° C. to 850° C.

[0088] In embodiments in which at least one solvent was used in the mixing step, such solvent(s) are removed as part of the process, for example, by filtration, evaporation, or distillation of such solvent(s). Evaporation and distillation are preferred.

[0089] In one embodiment of the present invention, the calcination is carried out in a roller hearth kiln, a pusher kiln, or a rotary kiln, or a combination of at least two of them. A rotary kiln has the advantage that the material produced therein is very homogenized. In roller hearth kilns and pusher kilns, different reaction conditions for different processes can be set very easily. In laboratory-scale experiments, box furnaces, tube furnaces, and split-tube furnaces can also be used.

[0090] By carrying out the calcination process of the present invention, a cathode active material having excellent properties and a narrow particle size distribution can be obtained in a simple process. Preferably, the electrode active material thus obtained has a particle size of 0.1 to 0.8 μm as determined in accordance with DIN-ISO 9277:2003-05. 2 / g.

[0091] A further aspect of the present invention relates to a cathode active material, hereinafter also referred to as the cathode active material of the present invention. The cathode active material of the present invention has the chemical formula Li 1+x TM 1-x O2, where TM is defined as above, x ranges from 0 to 0.05, preferably from 0.01 to 0.03, and they have a span ranging from 0.20 to 0.33, preferably from 0.21 to 0.29.

[0092] By carrying out the calcination in the above manner, the essentially radial arrangement of the primary particles (for example, at least 80%, preferably at least 90%) is retained, resulting in a cathode active material with excellent capacity retention.

[0093] A further aspect of the present invention relates to an electrode, in particular a cathode (hereinafter also referred to as the cathode of the present invention). The cathode of the present invention comprises: (A) at least one cathode active material of the present invention; (B) Carbon in a conductive state, (C) at least one binder Includes:

[0094] In a preferred embodiment of the present invention, the cathode of the present invention comprises, based on the sum of (A), (B), and (C): (A) 80 to 99% by weight of the cathode active material of the present invention; (B) 0.5 to 19.5 mass% carbon; (C) 0.5 to 9.5 mass % of a binder polymer Contains:

[0095] The cathode according to the present invention contains a conductively modified carbon, also referred to simply as carbon (B). Carbon (B) can be selected from soot, activated carbon, carbon nanotubes, graphene, and graphite. Carbon (B) can be added directly during the preparation of the electrode material according to the present invention.

[0096] The cathode according to the present invention may contain further components, such as a current collector (D), for example, but not limited to, aluminum foil. They may further contain a binder polymer (C), hereinafter also referred to as binder (C). The current collector (D) will not be further described here.

[0097] Suitable binders (C) are preferably selected from organic (co)polymers. Suitable (co)polymers, i.e., homopolymers or copolymers, can be selected, for example, from (co)polymers obtainable by anionic (co)polymerization, catalytic (co)polymerization, or free-radical (co)polymerization, in particular from polyethylene, polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers selected from ethylene, propylene, styrene, (meth)acrylonitrile, and 1,3-butadiene. Polypropylene is also suitable. Polyisoprene and polyacrylates are furthermore suitable. Polyacrylonitrile is particularly preferred.

[0098] In the context of the present invention, polyacrylonitrile is understood to mean not only polyacrylonitrile homopolymers but also copolymers of acrylonitrile with 1,3-butadiene or styrene, with polyacrylonitrile homopolymers being preferred.

[0099] In the context of the present invention, polyethylene refers not only to homopolyethylenes but also to copolymerized ethylene at least 50 mol % and up to 50 mol % of at least one further comonomer, such as α-olefins, for example propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, and also isobutene, vinyl aromatics, for example styrene, and also (meth)acrylic acid, vinyl acetate, vinyl propionate, C1-C2 copolymers of (meth)acrylic acid. 10 -Alkyl esters, in particular methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and also copolymers of ethylene with maleic acid, maleic anhydride and itaconic anhydride. Polyethylene can be HDPE or LDPE.

[0100] In the context of the present invention, polypropylene is understood to mean not only homopolypropylene but also copolymers of propylene with at least 50 mol % copolymerized propylene and up to 50 mol % of at least one further comonomer, such as ethylene, and α-olefins, such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene. The polypropylene is preferably isotactic or essentially isotactic polypropylene.

[0101] In the context of the present invention, polystyrene is not only a homopolymer of styrene, but also a C1-C6 copolymer of acrylonitrile, 1,3-butadiene, (meth)acrylic acid,10 -alkyl esters, divinylbenzene, in particular 1,3-divinylbenzene, copolymers with 1,2-diphenylethylene and α-methylstyrene are also understood to mean.

[0102] Another preferred binder (C) is polybutadiene.

[0103] Other suitable binders (C) are selected from polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyimides and polyvinyl alcohol.

[0104] In one embodiment of the present invention, the binder (C) has an average molecular weight M ranging from 50,000 g / mol to 1,000,000 g / mol, preferably up to 500,000 g / mol. W The (co)polymers are selected from the group consisting of:

[0105] The binder (C) may be a crosslinked or non-crosslinked (co)polymer.

[0106] In a particularly preferred embodiment of the present invention, the binder (C) is selected from halogenated (co)polymers, in particular fluorinated (co)polymers.Halogenated or fluorinated (co)polymers are understood to mean (co)polymers that contain at least one (co)polymerized (co)monomer having at least one halogen atom or at least one fluorine atom per molecule, more preferably at least two halogen atoms or at least two fluorine atoms per molecule.Examples include polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymer, perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and ethylene-chlorofluoroethylene copolymer.

[0107] Suitable binders (C) are especially polyvinyl alcohol and halogenated (co)polymers such as polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.

[0108] A further aspect of the present invention is (1) A cathode comprising the cathode active material (A) of the present invention, carbon (B), and a binder (C); (2) an anode, and (3) at least one electrolyte An electrochemical cell comprising:

[0109] The embodiment of the cathode (1) has already been described in detail above.

[0110] The anode (2) may contain at least one anode active material, such as carbon (graphite), TiO2, lithium titanium oxide, silicon, or tin. The anode (2) may further contain a current collector, such as a metal foil, such as copper foil.

[0111] The electrolyte (3) may include at least one non-aqueous solvent, at least one electrolyte salt, and optionally an additive.

[0112] The non-aqueous solvent for the electrolyte (3) can be liquid or solid at room temperature and is preferably selected from polymers, cyclic or acyclic ethers, cyclic and acyclic acetals, and cyclic or acyclic organic carbonates.

[0113] Examples of suitable polymers are, in particular, polyalkylene glycols, preferably poly-C1-C4-alkylene glycols, and especially polyethylene glycols, where the polyethylene glycols may contain up to 20 mol % of one or more C1-C4-alkylene glycols. The polyalkylene glycols are preferably polyalkylene glycols with two methyl or ethyl end caps.

[0114] The molecular weight M of suitable polyalkylene glycols, especially suitable polyethylene glycols, W may be at least 400 g / mol.

[0115] The molecular weight M of suitable polyalkylene glycols, especially suitable polyethylene glycols, W can be up to 5,000,000 g / mol, preferably up to 2,000,000 g / mol.

[0116] Examples of suitable acyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, with 1,2-dimethoxyethane being preferred.

[0117] Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.

[0118] Examples of suitable acyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.

[0119] An example of a suitable cyclic acetal is 1,3-dioxane, and especially 1,3-dioxolane.

[0120] Examples of suitable acyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.

[0121] Examples of suitable cyclic organic carbonates are compounds of general formulae (II) and (III): [ka] (In the formula, R 1 , R 2 and R 3 can be the same or different and are selected from hydrogen and C1-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably R 2 and R 3 (Both cannot be tert-butyl).

[0122] In a particularly preferred embodiment, R 1 is methyl and R 2 and R 3 are each hydrogen or R 1 , R 2 and R 3 are hydrogen atoms.

[0123] Another preferred cyclic organic carbonate is vinylene carbonate of formula (IV).

[0124] [ka]

[0125] Preferably, the solvent or solvents are used in an anhydrous state, ie with a water content in the range of 1 ppm to 0.1% by weight, which can be determined, for example, by Karl Fischer titration.

[0126] The electrolyte (3) further comprises at least one electrolyte salt. Suitable electrolyte salts are, in particular, lithium salts. Examples of suitable lithium salts are LiPF, LiBF, LiClO, LiAsF, LiCF, SO, LiC(C n F 2n+1 SO2)3, lithium imide, e.g., LiN(C n F 2n+1 SO2)2 (wherein n is an integer ranging from 1 to 20), LiN(SO2F)2, Li2SiF6, LiSbF6, LiAlCl4, and compounds of the general formula (C n F 2n+1 SO2) t YLi salt wherein t=1 when Y is selected from oxygen and sulfur; when Y is selected from nitrogen and phosphorus, t=2; When Y is selected from carbon and silicon, t=3).

[0127] Preferred electrolyte salts are selected from LiC(CF3SO2)3, LiN(CF3SO2)2, LiPF6, LiBF4, LiClO4, with LiPF6 and LiN(CF3SO2)2 being particularly preferred.

[0128] In a preferred embodiment of the present invention, the electrolyte (3) contains at least one flame retardant. Useful flame retardants may be selected from trialkyl phosphates (wherein the alkyls are different or the same), triaryl phosphates, alkyl dialkyl phosphonates, and halogenated trialkyl phosphates. Preferred are tri-C1-C4-alkyl phosphates (wherein the C1-C4-alkyls are different or the same), tribenzyl phosphate, triphenyl phosphate, C1-C4-alkyl di-C1-C4-alkyl phosphonates, and fluorinated tri-C1-C4-alkyl phosphates.

[0129] In a preferred embodiment, the electrolyte (3) comprises at least one flame retardant selected from trimethyl phosphate, CH3-P(O)(OCH3)2, triphenyl phosphate, and tris-(2,2,2-trifluoroethyl) phosphate.

[0130] The electrolyte (3) may contain 1 to 10 mass % of a flame retardant based on the total mass of the electrolyte.

[0131] In one embodiment of the present invention, the battery according to the present invention includes one or more separators (4) by which the electrodes are mechanically separated. Preferred separators (4) are polymer films, particularly porous polymer films, that are unreactive with metallic lithium. Particularly preferred materials for separators (4) are polyolefins, particularly film-forming porous polyethylene and film-forming porous polypropylene.

[0132] The separator (4) made of polyolefin, particularly polyethylene or polypropylene, can have a porosity in the range of 35 to 50%. The preferred pore size is, for example, in the range of 30 to 500 nm.

[0133] In another embodiment of the present invention, the separator (4) can be selected from PET nonwoven fabrics filled with inorganic particles. Such separators can have a porosity in the range of 40 to 55%. Suitable pore sizes are, for example, in the range of 80 to 750 nm.

[0134] The battery according to the invention may further comprise a housing which may have any shape, for example a cube or a cylindrical disk. In one variant, a metal foil configured as a pouch is used as the housing.

[0135] The battery according to the invention offers very good discharge and cycling behaviour, especially with regard to capacity loss, especially at high temperatures (above 45°C, eg up to 60°C).

[0136] The battery according to the present invention may comprise two or more electrochemical cells which are combined with one another, for example, connected in series or in parallel. A series connection is preferred. In the battery according to the present invention, at least one electrochemical cell contains at least one electrode according to the present invention. Preferably, in the electrochemical cell according to the present invention, the majority of the electrochemical cells contain the electrode according to the present invention. Even more preferably, in the battery according to the present invention, all electrochemical cells contain the electrode according to the present invention.

[0137] The present invention further provides a method for using the battery according to the present invention in a device, in particular a mobile device. Examples of mobile devices are vehicles, such as automobiles, bicycles, aircraft, or water vehicles, such as boats or ships. Other examples of mobile devices are manually operated devices, such as computers, in particular laptops, telephones, or powered hand tools, for example in the construction sector, in particular drills, battery-powered screwdrivers, or battery-powered staplers.

[0138] The invention is further illustrated by the examples and the drawing (see Figure 1). [Example]

[0139] Typically: A Mastersizer 3000 from Malvern Panalytical GmbH was used. The sample was filled into the instrument until a light blocking ratio between 4.0 and 14.0% was obtained. The volume-based particle size distribution (PSD) of each was determined by laser diffraction based on Mie scattering theory. The refractive index of H2O was selected as the dispersion medium, with a refractive index of 1.33, and that of the solid phase was selected as 2.19.

[0140] I. Preparation of Inventive and Comparative Precursors I.1 General, step (a) Percentages are by weight unless otherwise specified. All pH measurements were performed at 23°C unless otherwise specified. rpm: revolutions per minute.

[0141] The following aqueous solutions were provided: Solution (α.1): NiSO4, CoSO4 and MnSO4 dissolved in deionized water (molar ratio 91:4.5:4.5, total transition metal concentration 1.45 mol / kg); Solution (α.2): NiSO4, CoSO4 and MnSO4 dissolved in deionized water (molar ratio 83:12:5, total transition metal concentration 1.45 mol / kg); Solution (β.1): 25% by weight NaOH dissolved in deionized water, Solution (γ.1): 25% by weight ammonia in deionized water.

[0142] I.2 Preparation of the precursor P-CAM.1 of the invention I.2.1 Preparation of the Seed Slurry, Step (b1.1): A 50 L stirred vessel equipped with a baffle and a 0.21 m diameter, three-stage pitched blade agitator (blade angle 45°) was filled with 40 L of deionized water. The agitator element was activated to achieve an average energy dissipation of 0.8 W / L, and the water was heated to 55 °C. Solution (γ.1) was then added to obtain an NH3 concentration of 0.23 wt. %. The pH of the solution was then adjusted to 12.2 by adding solution (β.1).

[0143] The agitator speed was then increased and operated continuously at 420 rpm (average energy input: 12.6 W / L). The simultaneous feed of solutions (α.1), (β.1), and (γ.1) was then initiated. The total feed flow rate was adjusted to provide an average residence time of 7.5 hours. The ammonia to metal molar ratio was adjusted to 0.17. The pH value in the vessel was maintained at a constant value of 12.35 by adjusting the flow rate of NaOH in the pH control circuit. The apparatus was operated continuously while maintaining a constant liquid level in the reactor. The resulting seed suspension from step (b1.2) was recovered by free overflow from the vessel. The resulting slurry contained approximately 110 g / L of mixed hydroxides of Ni, Co, and Mn, with an average particle size (D50) of 3.9 μm and a span of 1.28.

[0144] I.2.2 Precipitation, process (b2.1) The setup according to Figure 1 was filled with 680 L of deionized water, submerging both agitator stages. The agitator speed was adjusted to 130 rpm (0.36 W / L), and the water was heated to 55 °C through a double jacket. The temperature was maintained constant at 55 °C throughout the batch. Next, 20.9 kg of solution (β.1) was added. In the next step, 43 kg of the seed slurry obtained in step (b1.1) was added to the mixture to achieve an initial solids content of approximately 5 g / L. The pH value after all feed additions was 11.65. The agitator speed was then adjusted to 396 rpm (corresponding to 7.9 W / L), and the feeds of solutions (α.1), (β.1), and (γ.1) were started simultaneously. The agitator speed was gradually reduced during the batch synthesis, with the final agitator speed reaching 220 rpm (1.65 W / L). The pH was kept constant at 11.5 by adjusting the addition of solutions (β.1) and (γ.1) so that the NH concentration in the mother liquor was 0.7% by mass. The ratio of the reactor volume (800 l) to the volumetric flow rates of all feeds (corresponding to the residence time) was initially set so as to give an average residence time of 40 h. However, the feeds were increased during the synthesis, resulting in a final residence time corresponding to 5 h.

[0145] Initially, the clarifier was empty. After 1 hour of reaction time, the transfer of the suspension to the clarifier was started at a volumetric flow rate of 360 L / h. After 10 minutes, the transfer of the suspension from the clarifier to the reactor was started at a volumetric flow rate of 340 L / h. The volumetric flow rates of the transfer of the suspension to the clarifier and the transfer of the suspension to the reactor were adjusted during the above feed ramps to keep the reactor volume constant at 800 L during the entire synthesis.

[0146] Once the clarifier was filled (after about 6 hours), the mother liquor containing particles flowed out of the tank reactor. During the synthesis, the average particle content of the mother liquor withdrawn from the overflow of the lamellar clarifier was 32 mg / L. The average size (D50) of the particles present in the withdrawn mother liquor was 7.6 μm. An SEM micrograph of the particles in the mother liquor withdrawn at the end of the synthesis is shown in Figure 3. The total duration of the synthesis was 23.5 h and the solid content in the reactor was 382 g / L, which was determined by dissolving the suspension with H2SO4 and subsequent ICP analysis of Ni, Co, and Mn.

[0147] After the batch was completed, all feed streams were stopped, the reactor and clarifier were discharged into a stirred suspension buffer vessel, and the slurry was filtered through a filter press. The filter cake was washed with solution (β.1) and deionized water and dried at 120 °C for 14 h to obtain precursor P-CAM.1, with a molar composition of Ni:Co:Mn = 91:4.5:4.5, an average particle size (d50) of 13.9 μm, and a span of 0.31. Cross-sectional SEM images of P-CAM.1 reveal a core-shell structure containing essentially radially arranged primary particles. A small porous layer is visible between the core and shell. I.3 Preparation of comparative precursor CP-CAM.2 The protocol of Example P-CAM.1 was followed to some extent, but different feed flows were applied. The ratio of the reactor volume (800 l) to the volumetric flow rates of all feeds (corresponding to the residence time) started at 40 h and was increased during the synthesis, resulting in a final residence time corresponding to 9 h. The lower feed flow rates resulted in a lower hydraulic load on the clarifier and a different solid-liquid separation behavior. During the synthesis, the mother liquor removed from the overflow of the lamellar clarifier had an average particle content of 1.4 mg / l.

[0148] The duration of the entire synthesis was 43.7 h, and the final solid content in the reactor was 396 g / L, which was determined by dissolving the suspension with H2SO4 and subsequent ICP analysis of Ni, Co, and Mn.

[0149] After the batch was completed, all feed streams were stopped, the reactor and clarifier were discharged into a stirred suspension buffer vessel, and the slurry was filtered through a filter press. The filter cake was washed with solution (β.1) and deionized water and dried at 120 °C for 14 h to obtain precursor CP-CAM.2 with a molar composition of Ni:Co:Mn = 91:4.5:4.5, an average particle size (D50) of 14.0 μm, and a span of 0.37.

[0150] I.4 Preparation of the precursor P-CAM.3 of the invention I.4.1 Production of Slurried Seeds, Process (b1.3) The protocol of step (b1.1) was followed, but solution (α.2) was used instead of solution (α.1). The resulting slurry contained about 110 g / l of mixed hydroxides of Ni, Co, and Mn, the mixed hydroxides having an average particle size (D50) of 4.0 μm and a span of 1.32.

[0151] I.4.2 Production of Slurried Seeds, Step (b2.3) The protocol of step (b2.1) was followed, but solution (α.2) was used instead of solution (α.1).

[0152] During step (b2.3), the mother liquor removed from the clarifier had an average particle content of 42 mg / l. The average diameter (D50) of the particles present in the removed mother liquor was 7.2 μm.

[0153] The total duration of the synthesis was 22.7 h and the solid content in the reactor was 374 g / L, which was determined by dissolving the suspension with H2SO4 and subsequent ICP analysis of Ni, Co, and Mn.

[0154] After the batch was completed, all feed streams were stopped, the reactor and clarifier were discharged into a stirred suspension buffer vessel, and the slurry was filtered through a filter press. The filter cake was washed with solution (β.1) and deionized water and dried at 120 °C for 14 h to obtain precursor P-CAM.2, with a molar composition of Ni:Co:Mn = 83:12:5, an average particle size (D50) of 14.1 μm, and a span of 0.27. A cross-sectional SEM image of P-CAM.3 reveals a core-shell structure containing essentially radially arranged primary particles. A small porous layer is visible between the core and shell.

[0155] I.5 Preparation of comparative precursor CP-CAM.4 The protocol of Example CP-CAM.2 was essentially followed. During the synthesis, the mother liquor removed through the clarifier had an average particle content of 1.2 mg / l.

[0156] The duration of the entire synthesis was 41.6 h and the final solid content in the reactor was 381 g / L, which was determined by dissolving the suspension with H2SO4 followed by ICP analysis of Ni, Co, and Mn.

[0157] After the batch was completed, all feed streams were stopped, the reactor and clarifier were discharged into a stirred suspension buffer vessel, and the slurry was filtered through a filter press. The filter cake was washed with solution (β.1) and deionized water and dried at 120 °C for 14 h to obtain precursor CP-CAM.4 with a molar composition of Ni:Co:Mn = 83:12:5, an average particle size (D50) of 13.8 μm, and a span of 0.36.

[0158] II. Synthesis of Cathode Active Material II.1 Preparation of CAM.1 of the invention P-CAM.1 was mixed with LiOH at a molar ratio of Li / TM of 1.04 and calcined at 765 °C for 8 h in a laboratory phosphorus furnace. After natural cooling to ambient temperature, the resulting CAM.1 was deagglomerated in a laboratory grinder. The resulting CAM.1 had an average particle size of 13.7 μm and a span of 0.30.

[0159] II.2 Production of comparative C-CAM.2 CP-CAM.2 was mixed with LiOH at a molar ratio of Li / TM of 1.04 and calcined in a laboratory phosphorus furnace at 765 °C for 8 h. After natural cooling to ambient temperature, the resulting C-CAM.2 was deagglomerated in a laboratory grinder. The resulting C-CAM.2 had an average particle size of 13.9 μm and a span of 0.36.

[0160] In electrochemical cells / lithium ion batteries, the CAM.1-containing cathodes exhibited superior performance compared to the C-CAM.2-containing cathodes.

[0161] II.3 Preparation of CAM.3 of the invention P-CAM.3 was mixed with LiOH in a molar ratio of Li / TM of 1.04 and calcined in a laboratory phosphorus furnace at 780 °C for 8 h. After natural cooling to ambient temperature, the resulting CAM.1 was deagglomerated in a laboratory grinder. The resulting CAM.3 had an average particle size of 13.9 μm and a span of 0.26.

[0162] II.4 Production of comparative C-CAM.4 CP-CAM.4 was mixed with LiOH in a molar ratio of Li / TM of 1.04 and calcined in a laboratory phosphorus furnace at 780 °C for 8 h. After natural cooling to ambient temperature, the resulting C-CAM.4 was deagglomerated in a laboratory grinder. The resulting C-CAM.2 had an average particle size of 13.6 μm and a span of 0.35.

[0163] In electrochemical cells / lithium ion batteries, the CAM.3-containing cathodes exhibited superior performance compared to the C-CAM.4-containing cathodes. [Explanation of symbols]

[0164] A: 800 liter tank reactor B: Supply ports for solutions (α.1), (β.1), and (γ.1) [simplified diagram] C: Agitator blade of a two-stage pitched blade turbine (angle 45°, diameter 0.4 m) D: Mixer engine E: Baffle F: Transfer of suspension from reactor to clarifier G: Transfer of suspension from clarifier to reactor H: Lamella clarifier I: Particle-containing mother liquor removed from the reactor through the overflow of the lamellar clarifier F: Cobalt sulfate aqueous solution supply port, solution (α2.1)

Claims

1. 1. A method for producing a particulate (oxy)hydroxide of TM, wherein TM represents a combination of nickel and at least one metal selected from Co and Mn, said method comprising the following steps: (a) providing one or more aqueous solutions (α) containing a water-soluble salt of Ni, 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, an aqueous solution (β) containing an alkali metal hydroxide, and optionally an aqueous solution (γ) containing a complexing agent; (b) combining solution(s) (α), solution (β), and, if applicable, solution (γ) in one or more substeps in a stirred tank reactor at a pH value in the range of 10.5 to 12.5 as determined at 23° C. to produce solid particles of hydroxide, wherein the solid particles are slurried; Including, The stirred tank reactor used in step (b) or at least one sub-step (b) is equipped with a solid-liquid separation device through which a mother liquor containing slurried particles of hydroxide in the range of 2 mg / l to 20 g / l is removed.

2. TM is a metal combination according to general formula (I), (Ni a Co b Mr c ) 1-d M d (I) (wherein a is in the range of 0.6 to 0.95; b is in the range of 0.025 to 0.2; c is in the range of 0 to 0.2; d is in the range of 0 to 0.1; M is selected from Mg, Al, Ti, Zr, Mo, W, Al, Mg, Nb, and Ta; 2. The method of claim 1, wherein a+b+c=1.

3. TM is a metal combination according to general formula (Ia), (Ni a Co b Mr c ) 1-d M d (I a) (wherein a is in the range of 0.25 to 0.4, b is in the range of 0 to 0.2; c is in the range of 0.6 to 0.75; d is in the range of 0 to 0.1; M is selected from Mg, Al, Ti, Zr, Mo, W, Nb and Ta; 2. The method of claim 1, wherein a+b+c=1.

4. step (b) is carried out in two or more substeps, (b1) and (b2), sub-step (b1) comprises combining solution(s) (α), solution (β), and, where applicable, solution (γ) in a continuously operated stirred tank reactor at a pH value in the range of 12.0 to 12.5, determined at 23°C, to produce solid particles of hydroxide, said solid particles being slurried; sub-step (b2) comprises transferring the slurry from step (b) to a stirred tank reactor where solution (α), solution (β), and, if applicable, solution (γ) are combined with the slurry at a pH value in the range of 11.0 to 12.0 determined at 23°C; 4. The process according to any one of claims 1 to 3, wherein the stirred tank reactor used in substep (b2) is equipped with a solid-liquid separation device through which a mother liquor containing slurried particles of hydroxide in the range of 2 mg / l to 20 g / l is removed.

5. 5. The method according to claim 1, wherein the precursor removed in step (b) has an average particle size (D50) in the range of 0.5 to 20 μm.

6. 6. The method according to any one of claims 1 to 5, wherein in step (b) a clarifier or at least one candle filter is used to remove the mother liquor.

7. 1. A particulate (oxy)hydroxide of TM, wherein TM represents a combination of nickel and at least one metal selected from cobalt and manganese, said particulate (oxy)hydroxide having an average particle size (d50) in the range of 3 to 20 μm, having a core-shell structure, both the core and the shell exhibiting an essentially radial arrangement of platelet-like primary particles, the core and the shell being separated by a porous layer containing randomly arranged primary particles, said particulate (oxy)hydroxide having a particle size distribution with a span [(d90)-(d10)] / (d50) in the range of 0.2 to 0.

33.

8. TM is a metal combination according to general formula (I), (Ni a Co b Mr c ) 1-d M d (I) (wherein a is in the range of 0.6 to 0.95; b is in the range of 0.025 to 0.2; c is in the range of 0 to 0.2; d is in the range of 0 to 0.1; M is selected from Mg, Al, Ti, Zr, Mo, W, Nb and Ta; The particulate (oxy)hydroxide according to claim 7, wherein a+b+c=1.

9. TM is a metal combination according to general formula (Ia), (Ni a Co b Mr c ) 1-d M d (I a) (wherein a is in the range of 0.25 to 0.4, b is in the range of 0 to 0.2; c is in the range of 0.6 to 0.75; d is in the range of 0 to 0.1; M is selected from Mg, Al, Ti, Zr, Mo, W, Nb and Ta; The particulate (oxy)hydroxide according to claim 7, wherein a+b+c=1.

10. 10. A particulate (oxy)hydroxide according to any one of claims 7 to 9, wherein the porous layer between the core and the shell has an average thickness in the range of 0.1 to 1.0 μm.

11. 12. A particulate (oxy)hydroxide according to any one of claims 7 to 11, wherein the span is in the range of 0.21 to 0.

29.

12. 12. A method for producing a cathode active material, comprising the steps of mixing a particulate (oxy)hydroxide according to any one of claims 7 to 11 with a lithium source and, where applicable, a hydroxide or oxide of at least one of Mg, Al, Ti, Zr, Ta, Nb, Mo, W, followed by calcination at a temperature in the range of from 700°C to 900°C.

13. 12. A method for producing a cathode active material, comprising the steps of heating a particulate (oxy)hydroxide according to any one of claims 7 to 11 to a temperature in the range of 400°C to 600°C in the absence of a lithium source to obtain an oxide of TM, then mixing the obtained oxide of TM with a lithium source and, where applicable, a hydroxide or oxide of at least one of Mg, Al, Ti, Zr, Ta, Nb, Mo, W, and then calcining at a temperature in the range of 700°C to 900°C.

14. General formula Li １＋ｘ TM １－ｘ O ２ wherein TM represents a combination of nickel, at least one metal selected from cobalt and manganese, and optionally at least one metal selected from at least one of Mg, Al, Ti, Zr, Ta, Nb, Mo, and W; x is in the range of 0 to 0.03; and the particulate cathode active material has an average particle size (D50) of 3 to 20 μm and a particle size distribution having a span [(D90)−(D10)] / (D50) in the range of 0.20 to 0.

33.

15. 15. The particulate cathode active material of claim 14, wherein the span is in the range of 0.21 to 0.

29.

16. TM is a metal combination according to general formula (I), (Ni a Co b Mr c ) 1-d M d (I) (wherein a is in the range of 0.6 to 0.95; b is in the range of 0.025 to 0.2; c is in the range of 0 to 0.2; d is in the range of 0 to 0.1; M is selected from Mg, Al, Ti, Zr, Mo, W, Nb and Ta; 16. The particulate cathode active material of claim 14 or 15, wherein a+b+c=1.

17. (A) at least one particulate cathode active material according to any one of claims 14 to 16; (B) carbon in a conductive state; (C) at least one binder a cathode.

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