Method for producing particulate (oxy)hydroxide or oxide, particulate (oxy)hydroxide or oxide and use thereof

Abstract

A process for producing particulate (oxy)hydroxides or oxides of TM, wherein TM represents a metal, said process being carried out in a cascade of at least three stirred-tank reactors.

Description

[Technical Field]

[0001] The present invention relates to a method for producing particulate (oxy)hydroxides or oxides of TM, wherein TM represents a metal, TM comprises nickel and at least one metal selected from cobalt and manganese, and the nickel content of TM is at least 80 mol %, said method being carried out in a cascade of at least three stirred tank reactors and comprising the following steps: (a) providing an aqueous solution (α1) containing a water-soluble salt of Ni and optionally at least one transition metal other than Ni, an aqueous solution (β1) containing an alkali metal hydroxide, and an aqueous solution (γ1) containing a complexing agent selected from ammonia, glycine, tartrate, citrate, and oxalate; (b) combining Solution (α1), Solution (β1), and, if applicable, Solution (γ1) in a first stirred tank reactor at a pH value in the range of 11.0 to 13.5, thereby producing slurried solid particles of hydroxide of TM; (c) transferring the particles from step (b) as a slurry to a second stirred tank reactor; (d) providing an aqueous solution (α2) containing a water-soluble salt of Ni, at least one metal selected from Co and Mn, and optionally at least one transition metal other than nickel, an aqueous solution (β2) containing an alkali metal hydroxide, and an aqueous solution (γ2) containing a complexing agent selected from ammonia, glycine, tartrate, citrate, and oxalate; (e) combining in a second stirred tank reactor solution (α2), solution (β2) and, where applicable, solution (γ2) at a pH value in the range of 10.5 to 12.0 and with an average specific energy input in the range of 2 to 8 W / l, which is 0.20 to 0.75 times lower than in step (b), thereby growing solid particles of hydroxide of TM; (f) transferring the particles from step (e) as a slurry to a third reactor, which is a stirred tank reactor; (g) combining solution (α2), solution (β2) and, if applicable, solution (γ2) in said third stirred tank reactor at a pH value in the range of 10.5 to 12.0; Including, The average specific energy input in step (g) is in the range of 0.5 to 2 W / l, which is 0.20 to 0.75 times lower than in step (e), and the pH value is determined at 23°C. [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, preferably as a hydroxide. The oxide is either pre-calcined to convert it to an oxide or oxyhydroxide, or mixed with a lithium source, such as, but not limited to, LiOH, Li2O, or especially Li2CO3, and calcined at high temperatures. The lithium source can be used as a hydrate(s) or in a 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 solid-state reaction occurs to form the electrode active material. The heat treatment is carried out in the heated zone of an oven or kiln.

[0004] A typical class of cathode active materials that achieves high energy density contains a large amount of Ni (Ni-rich), e.g., at least 80 mol % based on the non-lithium metal content, but energy density still needs improvement.

[0005] 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.

[0006] It has been found desirable to produce precursors with narrow particle size distributions, see for example EP 2 720 305 A.

[0007] CN 112591807 A discloses a multi-step co-precipitation method that results in a highly dense precursor. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] EP 2 720 305 A [Patent Document 2] CN 112591807 A Summary of the Invention [Problem to be solved by the invention]

[0009] The object of the present invention was to provide a method by which a cathode active material precursor can be produced that has high porosity, narrow particle size distribution, low tendency to form agglomerates, and high reactor efficiency. It was also an object to provide a cathode active material precursor that has narrow particle size distribution and low tendency to form agglomerates.

[0010] It has been found that precursor starting materials for cathode active materials with high volumetric energy densities can be obtained by avoiding particle agglomeration at the beginning of the seed batch growth stage. Without wishing to be bound by any theory, we hypothesize that a high solids content helps to efficiently avoid unwanted agglomeration. Conventional two-stage processes cannot start with a sufficiently high solids content, as this would result in an undesirably high solids content in the final batch. [Means for solving the problem]

[0011] Thus, a method as defined at the outset has been found, hereinafter also referred to as the method of the present invention. The method of the present invention is a method for producing a particulate oxyhydroxide or oxide of TM, which may also be referred to as a precursor, since the particulate oxyhydroxide or oxide subsequently serves as a precursor for the electrode active material. The method of the present invention comprises the following steps (a), (b), (c), (d), (e), (f) and (g), hereinafter also referred to as steps (a), (b), (c), (d), (e), (f) and (g), respectively, or more simply as (a), (b), (c), (d), (e), (f) and (g). The method of the present invention may comprise further (optional) steps. Steps (a) and (b) are described in more detail below. [Brief explanation of the drawings]

[0012] [Figure 1] Figure 1 shows a cascade with three stirred tank reactors, each equipped with an overflow system, clarifier, baffles, and two buffer tanks. [Figure 2] Figure 2 shows a cascade with three stirred-tank reactors, each equipped with an overflow system, baffles, and two buffer tanks, where the second and third stirred-tank reactors are equipped with clarifiers, but the first stirred-tank reactor is not. [Figure 3] FIG. 3 shows a cross-sectional SEM micrograph of P-CAM.1, showing a porous core and shell, and a concentric layer between the core and shell that is denser than the core and shell. DETAILED DESCRIPTION OF THE INVENTION

[0013] The resulting TM (oxy)hydroxides or oxides are particulate. The particle size distribution can be determined by light scattering, laser diffraction, or electroacoustic spectroscopy, with laser diffraction being preferred. The particle size distribution can be characterized by the scan of (D90-D10) divided by D50, where D50 is the median. Preferably, the resulting (oxy)hydroxides have a span of less than 0.3, more preferably 0.10-0.28, and even more preferably 0.15-0.25.

[0014] In one embodiment of the present invention, the particle shape of the secondary particles of the obtained precursor is spherical, i.e., particles having a spherical shape. Spherical does not simply mean perfectly spherical, but also includes particles in which the maximum and minimum diameters of at least 90% (number average) of a representative sample differ by 10% or less.

[0015] In one embodiment of the present invention, the resulting precursor is composed of secondary particles that are aggregates of primary particles.

[0016] In one embodiment of the present invention, the specific surface area (BET) of the resulting precursor is 2 to 120 m 2 / g, determined for example by nitrogen adsorption according to DIN-ISO 9277:2003-05.

[0017] The precursor is an (oxy)hydroxide of TM, which comprises Ni and optionally 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, Sb and Ta. Preferably, the precursor comprises nickel and at least one metal selected from Co and Mn, more preferably the precursor comprises nickel, cobalt and manganese.

[0018] The oxides of TM may contain residual hydroxyl or carbonate groups in the range of 100 to 1,000 ppm (by mass), determined, for example, by differential scanning calorimetry ("DSC") as mass loss at temperatures ranging from 180 to 450°C.

[0019] 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 0.80 to 0.97, preferably 0.83 to 0.95, b is 0 or 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 or 0.01 to 0.15; d is in the range of 0 to 0.1, preferably 0 to 0.05; M is selected from Ti, Zr, Mo, W, Al, Mg, Nb, Sb, and Ta; a+b+c=1). Preferably, d=zero.

[0020] 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 the present invention. Trace amounts in this context mean amounts of 0.05 mol % or less, relative to the total metal content of the TM.

[0021] Step (a) comprises providing an aqueous solution (α1) containing a water-soluble salt of Ni and optionally 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, Sb and Ta, an aqueous solution (β1) containing an alkali metal hydroxide, and optionally an aqueous solution (γ1) containing a complexing agent selected from ammonia, glycine, tartrate, citrate, and oxalate.

[0022] The term water-soluble salts 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, cobalt and manganese are preferably Ni 2+ and Co 2+ and Mn 2+ Examples of water-soluble salts of nickel, cobalt, and manganese include sulfates, nitrates, acetates, and halides, particularly chlorides. Nitrates and sulfates are preferred, and sulfates are more preferred.

[0023] Said aqueous solution (α1) preferably contains Ni and further metal(s) in the relative concentrations intended as the TM of the precursor or in a fraction of the precursor. Preferably, solution (α1) contains salts of nickel, cobalt and manganese.

[0024] Said aqueous solution (α1) preferably comprises Ni and optionally further metal(s) in a total concentration of 0.5 to 2.2 mol / l.

[0025] Solution (α1) can have a pH value in the range of 2 to 5. In embodiments where a higher pH value is desired, ammonia can be added to solution (α1). In other embodiments, ammonia is not added to solution (α1).

[0026] In step (a), an aqueous solution of an alkali metal hydroxide, hereinafter also referred to as solution (β1), is further provided. Examples of alkali metal hydroxides are cesium hydroxide, preferably potassium hydroxide, and a combination of sodium hydroxide and potassium hydroxide, and even more preferably sodium hydroxide.

[0027] In embodiments in which solution (β1) comprises an alkali metal hydroxide, said solution (β1) may further comprise a certain amount of carbonate, for example, intentionally added by aging the solution or the respective alkali metal hydroxide, or 0.1 to 2% by weight relative to the amount of the respective alkali metal hydroxide.

[0028] The solution (β1) can have a concentration of alkali metal hydroxide in the range of 0.1 to 12 mol / l, preferably 6 to 10 mol / l.

[0029] The pH value of the solution (β1) is preferably greater than or equal to 13, for example 14.5. In the context of the present invention, pH values ​​are determined at 23° C., unless otherwise stated.

[0030] In the method of the present invention, it is preferred to use ammonia. The solution (γ1) contains, where applicable, a complexing agent selected from ammonia, glycine, tartrate, citrate, and oxalate. In the context of the present invention, the term glycine includes the compound glycine and its alkali metal salts, such as the potassium salt or preferably the sodium salt. The terms tartrate and oxalate include the respective free acids and mono- and di-alkali metal salts, such as mono- or di-potassium salt, mono- or disodium salt, or a mixture of sodium and potassium salts. The term "citrate" includes citric acid and its alkali metal salts, such as mono-, di-, or trisodium salt, mono-, di-, and tripotassium salt.

[0031] In one embodiment of the present invention, the solution (γ1) has an ammonia concentration in the range of 1 to 30% by mass.

[0032] In one embodiment of the present invention, the solution (γ1) contains a complexing agent selected from glycine, tartrate, citrate, and oxalate, or their respective alkali metal salts, in the range of 0.05 to 1.0 mol % relative to TM.

[0033] Step (b) involves combining solution (α1), solution (β1), and, if applicable, solution (γ1), at a pH value ranging from 11.0 to 13.5, preferably from 11.2 to 12.5, thereby producing TM hydroxide particles. The particles are slurried in an aqueous medium. Again, pH values ​​are determined at 23°C unless otherwise specified.

[0034] 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 40 to 65°C.

[0035] In one embodiment of the present invention, step (b) is carried out at a pressure ranging from 500 mbar to 10 bar, preferably at atmospheric pressure.

[0036] In one embodiment of the present invention, an average specific energy of 8 to 20 W / l, preferably 9 to 17 W / l, is introduced into the slurry using, for example, a pitched blade turbine, preferably a Rushton turbine, or a combination of a pitched blade turbine and a Rushton turbine. The agitator can be of single, two or multi-stage type, for example three or four stages, with two and three stages being preferred.

[0037] The energy input can be kept constant or can be varied during step (b).

[0038] In one embodiment of the present invention, step (b) is carried out in a continuous stirred tank reactor ("CSTR"). A CSTR is typically equipped with an overflow. In step (b), a slurry having particles with an average diameter (D50) in the range of 3-5 μm is preferably removed and fed to a second stirred tank reactor. Step (b) is preferably carried out in a batch reactor.

[0039] In one embodiment of the present invention, the solids content of the slurry removed from step (b) is in the range of 100-800 g / L. The solids content is determined by dissolving the precipitate in sulfuric acid and measuring the metal content by IC (inductively coupled plasma).

[0040] In one embodiment of the present invention, step (b) is carried out in a continuous stirred tank reactor operated at an average residence time ranging from 5 to 15 hours, preferably from 7 to 12 hours. In embodiments in which step (b) is carried out in a batch reactor, an average residence time of 15 to 60 hours is preferred. In embodiments in which step (b) is carried out in a batch reactor, an average residence time of 15 to 60 hours is preferred. In embodiments in which step (b) has varying flow rates, e.g., due to varying feed rates of solution (α2), solution (β2), and, if applicable, solution (γ2), the transient residence time can be calculated. Typically, in embodiments in which the flow rates of at least one of solution (α2), solution (β2), and, if applicable, solution (γ2), are strongly varied, the average residence time does not correspond to a maximum or minimum residence time.

[0041] In step (c), the particles from step (b) are transferred as a slurry to a second stirred tank reactor, which is preferably operated as a batch reactor. To accommodate the continuous feed of slurry from step (b), it is preferable to have two or more tank reactors for step (e) that can be operated in parallel.

[0042] Step (d) comprises providing an aqueous solution (α2) comprising 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, Sb, and Ta, an aqueous solution (β2) comprising an alkali metal hydroxide, and optionally an aqueous solution (γ2) comprising ammonia.

[0043] In the context of the present invention, the term "solution containing a metal" is intended to mean that such solution contains a salt of said metal.

[0044] Said aqueous solution (α2) preferably contains Ni and further metal(s) in the relative concentrations intended as TM of the precursor or in one fraction of the precursor.

[0045] The solution (α2) may have the same composition as the solution (α1), or may have a different composition.

[0046] Said aqueous solution (α2) preferably comprises Ni and optionally further metal(s) in a total concentration of 0.1 to 12 mol / l, preferably 6 to 10 mol / l.

[0047] The aqueous solution (α2) 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 the solution (α2).

[0048] Said aqueous solution (α2) preferably comprises Ni and optionally further metal(s) in a total concentration of 0.5 to 2.2 mol / l.

[0049] Step (a) also provides an aqueous solution of alkali metal hydroxide, hereinafter also referred to as solution (β2). Solution (β2) can have a concentration of alkali metal hydroxide ranging from 0.1 to 12 mol / l, preferably from 6 to 10 mol / l.

[0050] The pH value of the solution (β2) is preferably above 13, for example 14.5.

[0051] In the process of the present invention, ammonia is used, which can be supplied separately as a solution (γ2) or a solution (β2) or a solution (α2).

[0052] The solution (β2) may have the same composition as the solution (β1) or a different composition, but preferably has the same composition.

[0053] The solution (γ2) may have the same composition as the solution (γ1) or a different composition, but preferably has the same composition.

[0054] In one embodiment of the present invention, the solution (γ2) has an ammonia concentration in the range of 1 to 30% by mass.

[0055] In one embodiment of the present invention, the solution (γ2) contains a complexing agent selected from glycine, tartrate, citrate, and oxalate, or their respective alkali metal salts, in the range of 0.05 to 1.0 mol % relative to TM.

[0056] Step (e) comprises combining solution (α2), solution (β2) and, if applicable, solution (γ2) at a pH value in the range of 10.5 to 12.0, preferably at a lower pH than in step (b), e.g., at least 0.5 units lower, preferably 11 to 12.5, thereby growing particles of hydroxide of TM, which are slurried in an aqueous medium.

[0057] In one embodiment of the present invention, step (e) is carried out at a temperature in the range of 10 to 85° C., preferably 40 to 65° C. Steps (b) and (e) may be carried out at different temperatures or, preferably, at the same temperature.

[0058] In one embodiment of the present invention, step (e) is carried out at a pressure ranging from 500 mbar to 10 bar, preferably at atmospheric pressure.

[0059] In step (e), an average specific energy input of 2 to 8 W / L, preferably 2 to 7 W / L, is introduced into the slurry in step (e), the energy input being 0.20 to 0.75 times less than in step (b), for example using a stirrer as used in step (b). The average specific energy input may be constant or may vary over the time period of step (e). If the average specific energy input is not constant, the above value refers to an average value.

[0060] In one embodiment of the present invention, the average particle size of the (oxy)hydroxide produced in step (e) is in the range of 6.5 to 9.5 μm, which is in any case larger than at the end of step (b) and step (c).

[0061] In one embodiment of the present invention, the solids content at the start of step (e) is in the range of 20-60 g / l. If the slurries obtained in steps (b) and (c) have a higher concentration and therefore a higher solids content, step (e) begins with diluting the slurry with an aqueous medium such as water, for example, by charging an aqueous medium such as water, diluted ammonia, etc. into each tank reactor.

[0062] In one embodiment of the present invention, the solids content at the end of step (e) is in the range of 200 to 800 g / l.

[0063] In one embodiment of the present invention, step (e) has a duration ranging from 7 to 45 hours, preferably from 15 to 40 hours, but in any case shorter than step (b).

[0064] The feed rate of one or more of solutions (α2), (β2), and (γ2) in step (e) may be constant or variable, for example, increased, decreased, or oscillated. When the feed rate is constant, the average residence time is the same as the residence time.

[0065] For example, in embodiments of step (e) in which the flow rates vary due to changes in the feed rates of solution (α2), solution (β2), and, if applicable, solution (γ2), the transient residence time can be calculated. Typically, in embodiments in which the flow rates of at least one of solution (α2), solution (β2), and, if applicable, solution (γ2), vary strongly, the average residence time does not correspond to a maximum or minimum residence time.

[0066] Step (f) comprises transferring the particles from step (e) as a slurry to a third reactor which is a stirred tank reactor, preferably a batch reactor, such as a draft tube reactor, which are known per se and are described, for example, in T. Kumaresan et al., Hydrometallurgy 2014, 150, 107.

[0067] Step (g) comprises combining solution (α2), solution (β2), and, if applicable, solution (γ2) in the third stirred-tank reactor at a pH value in the range of 10.5 to 12.0, wherein the average specific energy input in step (g) is lower than in step (e). Solutions (α2), (β2), and (γ2) in step (g) may have the same or different compositions as in step (e), preferably they have the same composition.

[0068] At the start of step (g), the solids content in the third stirred tank reactor is relatively low, for example, 60-180 g / L. If the slurry resulting from step (e) has a higher concentration and therefore a higher solids content, step (g) begins with diluting the slurry with an aqueous medium such as water, for example, by charging each tank reactor with an aqueous medium such as water, diluted ammonia, etc.

[0069] At the end of step (g), the solids content is high, for example 200-800 g / l.

[0070] In one embodiment of the present invention, in step (g), an average specific energy input of 0.2 to 2 W / L, preferably 0.2 to 1.9 W / L, is introduced into the slurry, which is 0.20 to 0.75 times less energy than in step (e), for example, using a pitched blade turbine, propeller agitator, or hydrofoil. The specific energy input may be constant or variable over the time period of step (g). If the specific energy input is not constant, the above value refers to an average value.

[0071] In one embodiment of the present invention, step (g) is carried out at a temperature in the range of 10 to 85° C., preferably 40 to 65° C. Steps (g) and (e) may be carried out at different temperatures or, preferably, at the same temperature.

[0072] In one embodiment of the present invention, step (g) is carried out at a pressure ranging from 500 mbar to 10 bar, preferably at atmospheric pressure.

[0073] In one embodiment of the invention, step (g) has a duration ranging from 2 to 7 hours, but in any case shorter than step (e).

[0074] The feed rate of one or more of solutions (α2), (β2), and (γ2) in step (g) may be constant or variable, for example, increased, decreased, or oscillated. When the feed rate is constant, the average residence time is the same as the residence time.

[0075] In one embodiment of the present invention, the tank reactors of steps (b), (e) and (g) have different volumes. In another embodiment, the tank reactors of steps (b), (e) and (g) are the same size and volume.

[0076] In one embodiment of the present invention, step (g) is carried out in a draft tube reactor. The draft tube is equivalent to a tube located within the vessel body of the tank reactor, with its upper edge or at least one opening located below the gauge of the slurry in the tank reactor. Thus, the slurry is circulated through such a draft tube. An agitator element is disposed within the draft tube.

[0077] In one embodiment of the present invention, in steps (b), (e), and (g), the mother liquor is removed from the reactor using, for example, a clarifier, such as a lamellar clarifier, a candle filter, or a thickener. The mother liquor may contain, for example, 2 mg / L to 20 g / L of solid particles of the precursor, or may be free of solid particles visible to the naked eye.

[0078] In one embodiment of the present invention, the slurry from steps (b) and (e) is transferred to a buffer vessel before being subjected to the subsequent co-precipitation step. In one embodiment of the present invention, the average particle size of the (oxy)hydroxide produced in step (g) is in the range of 9.5 to 18 μm, but in any case is larger than at the end of step (e).

[0079] In one embodiment of the present invention, the process of the present invention additionally comprises a step (h) of separating the particulate (oxy)hydroxide by solid-liquid separation and then drying it.

[0080] By carrying out the method of the present invention, an aqueous slurry is formed. From the aqueous slurry, particulate mixed hydroxides can be obtained by one or more solid-liquid separation steps, such as filtration or centrifugation. Additional processing steps, such as washing with water, ammonia, or aqueous NaOH, dehydration, and drying under inert gas or air, can be employed. Drying under air causes partial oxidation to yield the TM mixed oxyhydroxide. Drying can be carried out at temperatures ranging from 100 to 150°C.

[0081] In one embodiment of the present invention, the method of the present invention comprises step (i) of heating at a temperature in the range of 400-550°C in the absence of a lithium compound, whereby the precursor is converted to an oxide of TM. Step (i) can be carried out in a rotary kiln, a fluidized bed, or a roller hearth kiln.

[0082] In one embodiment of the present invention, step (i) is carried out under an atmosphere of air, oxygen-enriched air, or pure oxygen.

[0083] In one embodiment of the present invention, step (i) has a duration ranging from 1 to 12 hours.

[0084] The precursors obtained according to the method of the present invention are excellent starting materials for cathode active materials suitable for the fabrication of batteries having high volumetric energy densities, which depend on the pressed density and discharge capacity of a given cathode active material.

[0085] A further aspect of the present invention relates to a precursor, hereinafter also referred to as the precursor of the present invention. In one embodiment of the present invention, the precursor of the present invention is a particulate (oxy)hydroxide of TM having a particle size distribution (D90-D10) / D50 span of less than 0.30, the TM comprising nickel and at least one metal selected from cobalt and manganese, and the secondary particles of the precursor of the present invention are composed of primary particles. The secondary particles have a core, a shell, and porous concentric layers having a density higher than that of the core and shell. The concentric layers can be seen in scanning electron microscope ("SEM") photographs. The average pore volume of the precursor of the present invention, which is an (oxy)hydroxide, is in the range of 0.033 to 0.1 ml / g, as measured by nitrogen adsorption. Preferably, the thickness of the intermediate layer may be in the range of 0.5 to 6.0 μm, and the core diameter is in the range of 2.0 to 6.0 μm.

[0086] Another embodiment of the precursor of the present invention is a particulate oxide of TM, having a particle size distribution span (D90-D10) / D50 of less than 0.30, e.g., 0.20-0.29, the TM comprising nickel and at least one metal selected from cobalt and manganese, the particles being composed of primary particles, and having an average pore volume in the range of 0.1-0.5 ml / g, preferably 0.12-0.3 ml / g, as measured by nitrogen adsorption.

[0087] In both cases, the span refers to secondary particles, which are essentially agglomerates of radially oriented primary particles.

[0088] The span of the precursor of the present invention is less than 0.30, for example, in the range of 0.10 to 0.28, preferably 0.18 to 0.26. The D10, D90 and median percentiles are preferably determined by light scattering or laser diffraction or electroacoustic spectroscopy, more preferably by laser diffraction.

[0089] TM is defined as above.

[0090] The particulate (oxy)hydroxides of the TM of the present invention have a total pore / interstitial volume in the range of 0.033-0.1 ml / g, preferably 0.035-0.07 ml / g, in the pore diameter range of 20-600 Å, determined by N adsorption according to DIN 66134 (1998), and sample preparation for N adsorption measurements is performed by degassing at 120°C for 60 minutes.

[0091] In a preferred embodiment, the particulate transition metal (oxy)hydroxide of the present invention has an average pore diameter, determined by N2 adsorption, in the range of 50 to 250 Å.

[0092] In one embodiment of the present invention, the particulate transition metal (oxy)hydroxide of the present invention has an average secondary particle size D50 in the range of 2 to 20 μm, preferably 2 to 16 μm, and even more preferably 10 to 16 μm.

[0093] 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 0.80 to 0.97, preferably 0.83 to 0.95, b is 0 or 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 or 0.01 to 0.15; d is in the range of 0 to 0.1, preferably 0 to 0.05; M is selected from Ti, Zr, Mo, W, Al, Mg, Nb, Sb, and Ta; a+b+c=1).

[0094] 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 the present invention. Trace amounts in this context mean amounts of 0.05 mol % or less, relative to the total metal content of the TM.

[0095] The precursors of the present invention may contain carbonates. The carbonates may be inadvertently introduced, for example, from carbonate salts of alkali metal hydroxides or by absorption of CO2 upon exposure to air. The precursors of the present invention may also contain counterions from, for example, the water-soluble salt that provided the nickel source during the preparation of the precursor. Such counterions are preferably sulfates. The amount of impurities such as carbonates or counterions from the nickel source and additional metals preferably does not exceed 1% by weight of the precursors of the present invention.

[0096] In one embodiment of the present invention, the precursor of the present invention has a molecular weight of 2 to 120 m. 2 / g, preferably 4 to 50m 2 / g, which can be determined by nitrogen adsorption after outgassing the sample at 200°C for at least 30 minutes according to DIN ISO 9277:2010.

[0097] As outlined above, secondary particles are essentially agglomerates of radially oriented primary particles.

[0098] Furthermore, at least 60% of the volume of the secondary particles is filled with radially oriented primary particles, and preferably only a small inner portion of the volume of the particles, e.g., at most 40%, preferably at most 20%, is filled with non-radially oriented primary particles, e.g., randomly oriented.

[0099] The oxide precursors of the present invention have a pore size range of 0.1-0.5 ml / g, preferably 0.12-0.3 ml / cm, in the pore size range of 20-600 Å, determined by N adsorption according to DIN 66134 (1998), when sample preparation for N adsorption measurement is performed by degassing at 120°C for 60 minutes. 3 The total pore / intrusion volume ranges from

[0100] In a preferred embodiment, the average pore diameter of the oxide precursor of the present invention is in the range of 30 to 500 Å, preferably 50 to 200 Å, as determined by N 2 adsorption.

[0101] In one embodiment of the present invention, the inventive precursor has an average secondary particle size D50 in the range of 2 to 20 μm, preferably 2 to 16 μm, even more preferably 10 to 16 μm.

[0102] In one embodiment of the present invention, the (oxy)hydroxide of the TM of the present invention - at least 60% by volume of the secondary particles consist of primary particles that are radially oriented or exhibit a maximum deviation to a perfect radial orientation of 11 degrees; and wherein said particulate precursor has a total pore / interstitial volume in the range of 0.033-0.1 ml / g, as determined by N2 adsorption.

[0103] In one embodiment of the present invention, in the oxide of the present invention, - at least 60% by volume of the secondary particles consist of primary particles that are radially oriented or exhibit a maximum deviation to the full radial orientation of 11 degrees, and - wherein said TM particulate oxide has a total pore / interstitial volume in the range of 0.1-0.5 ml / g as determined by N2 adsorption.

[0104] The precursors of the present invention have excellent spherical shape. They are almost perfectly spherical and have an average shape factor of 0.98 or more. The (average) shape factor is determined as follows:

[0105] The shape factor of an individual particle is calculated from the perimeter and area determined from a top-view SEM image: Shape factor = (4π·area) / (perimeter) 2 .

[0106] A perfect sphere has a shape factor of 1.0, while deviations from a perfect sphere have a shape factor <1.0.

[0107] To determine the average shape factor, first determine the shape factors of at least 50 particles in a representative sample and average them, which is why it is sometimes called the average shape factor.

[0108] In one embodiment of the present invention, the precursor of the present invention has a viscosity of 2 to 120 mPa, determined according to DIN, after heating to 120°C. 2 / g.

[0109] The precursor obtained according to the method of the present invention is an excellent starting material 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 the precursor with a lithium source, e.g., LiO, LiOH, or LiCO, respectively, either free of water or as a hydrate, and calcining the mixture at a temperature ranging from 600 to 1000°C. Accordingly, a further aspect of the present invention is the use of the precursor of the present invention for the fabrication of a cathode active material for a lithium-ion battery. Another aspect of the present invention is a method for the fabrication of a cathode active material for a lithium-ion battery, hereinafter also referred to as the "light calcination" of the present invention, comprising the steps of mixing the precursor of the present invention with a lithium source and heat-treating the mixture at a temperature ranging from 600 to 1000°C. Preferably, the ratio of the precursor of the present invention to the lithium source in such a method is selected so that the molar ratio of Li to TM is in the range of 0.95:1 to 1.2:1.

[0110] The precursors yield cathode active materials with exceptional volumetric energy densities. Without wishing to be bound by any theory, it is hypothesized that the orientation and high sphericity of the primary crystallites result in such advantageous properties.

[0111] Examples of calcination according to the present invention include heat treatment at temperatures ranging from 600 to 900° C., preferably from 650 to 850° C. The terms “heat treatment” and “heat treatment” are used interchangeably in the context of the present invention.

[0112] In one embodiment of the present invention, the mixture obtained for the firing of the present invention is heated to 600-900°C at a heating rate of 0.1-10°C / min. In one embodiment of the present invention, the temperature is increased before reaching a desired temperature of 600 to 900° C., preferably 650 to 800° C. For example, the mixture obtained from step (d) is first heated to 350 to 550° C., then kept constant for 10 minutes to 4 hours, then heated to 650 to 800° C., and then kept at 650 to 800° C. for 10 minutes to 10 hours.

[0113] In one embodiment of the present invention, the firing of the present invention is carried out in a roller hearth kiln, a pusher kiln, or a rotary kiln, or a combination of at least two of the above. Rotary kilns have 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. For laboratory-scale tests, box furnaces, tube furnaces, and split-tube furnaces are also possible.

[0114] In one embodiment of the present invention, the calcination of the present invention is carried out in an oxygen-containing atmosphere, such as a nitrogen-air mixture, a noble gas-oxygen mixture, air, oxygen, or oxygen-enriched air. In a preferred embodiment, the atmosphere in step (d) is selected from air, oxygen, and oxygen-enriched air. The oxygen-enriched air may be, for example, a 50:50 volume ratio mixture of air and oxygen. Other options include a 1:2 volume ratio mixture of air and oxygen, a 1:3 volume ratio mixture of air and oxygen, a 2:1 volume ratio mixture of air and oxygen, and a 3:1 volume ratio mixture of air and oxygen.

[0115] In one embodiment of the present invention, the calcination of the present invention is carried out under a gas flow, such as pure oxygen and oxygen-enriched air, such as oxygen:air in a volume ratio of 3:1 to 10:1, determined at ambient temperature and pressure. Such a gas flow can be called a forced gas flow. Such a gas flow can be in the range of 0.5 to 15 m 3 / h·kg general formula Li 1+x TM 1-x The volume is determined under normal conditions: 298 Kelvin and 1 atmosphere. The gas flow is useful for removing gaseous cleavage products such as water and carbon dioxide.

[0116] In one embodiment of the present invention, the firing of the present invention has a duration ranging from 1 to 30 hours, preferably 10 to 24 hours. Time at temperatures above 600°C counts as heating and holding, while cooling time is ignored in this context.

[0117] 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), which is best prepared from the precursor of the present invention.

[0118] The cathode active material of the present invention has the general formula Li 1+x TM 1-xO2, x is in the range of -0.01 to +0.05, preferably +0.01 to 0.04, the span of the particle size distribution (D90-D10) / D50 is less than 0.30, TM comprises nickel and at least one metal selected from cobalt and manganese, and the cathode active material has a total pore / interstitial volume in the range of 0.0035 to 0.01 ml / g, as determined by N2 adsorption.

[0119] In one embodiment of the present invention, the cathode material of the present invention has a second outer shell comprising at least one oxide compound of W or B, such as, for example, B2O3, LiBO2, Li2WO4, WO3, etc. The second outer shell may have a continuous structure or an island structure.

[0120] The above spans refer to secondary particles, which are aggregates of essentially radially oriented primary particles. In this context, essentially radially oriented means that up to 10% of the primary particles in a representative sample exhibit a deviation of 11° or less from ideal radial alignment, including particles with a perfect radial orientation of the primary particles. This determination can be made by analysis of SEM micrographs.

[0121] The span of the cathode active material of the present invention is less than 0.30, for example, in the range of 0.10 to 0.28, preferably 0.18 to 0.26. The D10, D90 and median percentiles are preferably determined by light scattering or laser diffraction or electroacoustic spectroscopy, more preferably laser diffraction.

[0122] The cathode active material of the present invention has a total pore / interstitial volume in the range of 0.033-0.1 ml / g, preferably 0.035-0.09 ml / g, in the pore diameter range of 20-600 Å, as determined by N adsorption according to DIN 66134 (1998), and the sample preparation for N adsorption measurement is performed by degassing at 120°C for 60 minutes.

[0123] In a preferred embodiment, the average pore size of the cathode active material of the present invention is in the range of 50 to 250 Å, as determined by N 2 adsorption.

[0124] In one embodiment of the present invention, the cathode active material of the present invention has an average secondary particle size D50 in the range of 2 to 20 μm, preferably 2 to 16 μm, and even more preferably 10 to 16 μm.

[0125] 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 0.80 to 0.97, preferably 0.83 to 0.95, b is 0 or 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 or 0.01 to 0.15; d is in the range of 0 to 0.1, preferably 0 to 0.05; M is selected from Ti, Zr, Mo, W, Al, Mg, Nb, Sb, and Ta; a+b+c=1).

[0126] The cathode active materials of the present invention are suitable for fabricating lithium ion batteries, particularly cathodes for lithium ion batteries.

[0127] 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:

[0128] 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 mass 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:

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] Another preferred binder (C) is polybutadiene.

[0137] Other suitable binders (C) are selected from polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyimides and polyvinyl alcohol.

[0138] 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:

[0139] The binder (C) may be a crosslinked or non-crosslinked (co)polymer.

[0140] 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.

[0141] 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.

[0142] 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:

[0143] The embodiment of the cathode (1) has already been described in detail above.

[0144] 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.

[0145] The electrolyte (3) may include at least one non-aqueous solvent, at least one electrolyte salt, and optionally an additive.

[0146] 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.

[0147] 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.

[0148] The molecular weight M of suitable polyalkylene glycols, especially suitable polyethylene glycols, W may be at least 400 g / mol.

[0149] 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.

[0150] 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.

[0151] Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.

[0152] Examples of suitable acyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.

[0153] An example of a suitable cyclic acetal is 1,3-dioxane, and especially 1,3-dioxolane.

[0154] Examples of suitable acyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.

[0155] 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).

[0156] In a particularly preferred embodiment, R 1is methyl and R 2 and R 3 are each hydrogen or R 1 , R 2 and R 3 are hydrogen atoms.

[0157] Another preferred cyclic organic carbonate is vinylene carbonate of formula (IV).

[0158] [ka]

[0159] 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.

[0160] 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).

[0161] Preferred electrolyte salts are selected from LiC(CF3SO2)3, LiN(CF3SO2)2, LiPF6, LiBF4, LiClO4, with LiPF6 and LiN(CF3SO2)2 being particularly preferred.

[0162] 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.

[0163] 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.

[0164] The electrolyte (3) may contain 1 to 10 mass % of a flame retardant based on the total mass of the electrolyte.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] 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).

[0170] 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.

[0171] 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.

[0172] The invention is further illustrated by examples and figures. [Example]

[0173] Typically: For the experimental example, three cascades of 3.2 L glass stirred-tank reactors equipped with baffles and two-stage, four-blade pitch-blade turbines (45° angle, 0.06 m diameter) were used. Each stirred-tank reactor was further equipped with a settling device and an overflow through which the mother liquor was withdrawn from the reactor.

[0174] All pH values ​​were measured at 23°C.

[0175] rpm: revolutions per minute Total solids were determined by dissolving an aliquot of each suspension with H2SO4 followed by ICP analysis for Ni, Co, and Mn.

[0176] Figure 1: Cascade with three stirred tank reactors, each equipped with an overflow system, clarifier, baffles, and two buffer tanks.

[0177] Figure 2: Cascade with three stirred-tank reactors, each equipped with an overflow system, baffles, and two buffer tanks. The second and third stirred-tank reactors are equipped with clarifiers, but the first stirred-tank reactor is not.

[0178] I. Precursor Preparation I.1 Preparation of the (oxy)hydroxide P-CAM.1 and dehydrated oxy-P-CAM.1 of the present invention Process (a.1) The following aqueous solutions were provided: Solution (α1.1): NiSO4, CoSO4 and MnSO4 dissolved in deionized water (molar ratio 91:4.5:4.5, total transition metal concentration 1.45 mol / kg); Solution (β1.1): 25% by weight NaOH dissolved in deionized water; Solution (γ1.1): 25% by weight ammonia in deionized water, Percentages are by weight unless otherwise specified.

[0179] Before step (b.1) The first stirred tank reactor of the cascade was charged with 2.7 liters of deionized water and heated to 55°C under stirring at 500 rpm (average specific energy input: 0.63 W / l). Then 165 g of solution (γ.1) were added and the pH value was adjusted to 12.45 by adding solution (β.1).

[0180] Process (b.1) The agitator speed was then adjusted to 750 rpm (16 W / L) and the simultaneous feeding of solutions (α1.1), (β1.1), and (γ1.1) was initiated. The agitator speed was kept constant during step (b.1). The total flow rate was adjusted so that the ratio of the total flow rate to the reactor volume (3.2 L) was 10 h (equivalent to the residence time). The temperature was kept constant at 45 °C. The molar feed ratio of ammonia to TM was set to 0.25 and kept constant during step (b.1). The pH was adjusted to 11.5. The mother liquor was continuously removed from the reaction system to increase the solid content. Step (b.1) lasted for 47 h, resulting in a slurry with a solid content of 427 g / L in the stirred-tank reactor (excluding the clarifier).

[0181] All feed streams were stopped and the suspension from the reactor and clarifier was discharged into a stirred suspension buffer vessel. The suspension contained slurried particles with an average particle size (d50) of 4.3 μm and a span of 0.7.

[0182] Process (c.1) The second reactor of the cascade was charged with 2.6 l of deionized water and heated to 55 ° C under stirring (500 rpm, specific energy input: 0.65 W / l). 83 g of solution (γ2.1) were added. 530 g of the suspension from step (b.1) were then added to the reactor. The solids content at the start of step (e.1) was 52 g / l.

[0183] Process (d.1) The following aqueous solutions were provided: Solution (α2.1): NiSO4, CoSO4 and MnSO4 dissolved in deionized water (molar ratio 91:4.5:4.5, total transition metal concentration 1.45 mol / kg); Solution (β2.1): 25% by weight NaOH dissolved in deionized water; Solution (γ2.1): 25% by weight ammonia in deionized water, Each of the solutions (α2.1), (β2.1) and (γ2.1) in step (g.1) had the same composition.

[0184] Process (e.1) After that, simultaneous feeding of solutions (α2.1), (β2.1), and (γ2.1) was initiated. The molar feed ratio of ammonia to TM was kept constant at 0.35. During step (e), the temperature was kept constant at 55 °C. The pH value was adjusted to 11.5 and kept constant at this value until the end of step (e.1). The ratio of the reactor volume (3.2 L) to the total feed flow rate (equivalent to residence time) was started at 33 h, and the feed was increased during the synthesis to achieve a residence time of 5 h. The agitator rotation speed was gradually reduced during the batch, reaching a final agitator rotation speed of 780 rpm (2.25 W / L). The agitator profile was designed to achieve an average specific energy input of 3.7 W / L during step (e.1). Mother liquor was continuously removed from the tank reactor to increase the solids content. The total duration of step (e.1) was 20 hours, and the resulting slurry in the reactor had a total solids content of 304 g / L. After completion of the batch, all feed streams were stopped, and the resulting suspension from the reactor and clarifier was discharged into a stirred suspension buffer vessel. The particles in the suspension had an average particle size (d50) of 7.3 μm and a span of 0.53.

[0185] Process (f.1) 2.3 liters of deionized water was added to the third stirred tank reactor of the cascade and heated to 55°C under stirring at 500 rpm (0.68 W / L). Next, 83 g of solution (γ2.1) and 940 g of the suspension from step (e.1) were added to the tank reactor. The initial solids content of the resulting slurry was 76 g / L.

[0186] Process (g.1) The agitator speed was adjusted to 800 rpm (1.9 W / L), and the simultaneous addition of solutions (α2.1), (β2.1), and (γ2.1) was initiated. During step (g.1), the temperature was kept constant at 55 °C. During step (g.1), the molar feed ratio between ammonia and TM was kept at 0.35. The pH was adjusted to 11.5 in the first hour and kept constant throughout step (g.1). The ratio of the reactor volume (3.2 L) to the total feed flow rate (corresponding to the residence time) began at 33 hours. The feed was then increased during step (g.1) to achieve a 5-hour equivalent residence time. The feed profile was designed to achieve an average residence time of 5.8 hours. The agitator speed was gradually reduced during step (g.1), reaching a final agitator speed of 550 rpm (0.7 W / L) and an average of 1.4 W / L. The mother liquor was continuously removed from the tank reactor through a clarifier to increase the solids content. The total duration of step (g.1) was 21.2 hours. A slurry with a solids content of 347 g / L was obtained. All feed streams were stopped, and the resulting suspension from the reactor and clarifier was discharged into a stirred suspension buffer vessel.

[0187] process: The slurry from step (g.1) was filtered, and the resulting filter cake was washed with deionized water and then with an aqueous solution of sodium hydroxide (1 kg of 25 wt % aqueous sodium hydroxide per kg of solid hydroxide).

[0188] The filter cake was dried in a cabinet dryer at 120 °C for 12 hours to obtain the mixed metal (oxy)hydroxide P-CAM.1. P-CAM.1 had an average particle size (D50) of 14.4 μm, a span of 0.23, and a BET specific surface area of ​​19.2 m. 2 / g. The average shape factor was 0.991. The pore volume measured by N2 adsorption was 0.048 ml / g.

[0189] Oxy-P-CAM.1 The P-CAM.1 of the present invention was heated in a phosphorus oven at 450°C for 2 hours under flowing air to obtain the mixed metal oxide oxy-P-CAM.1. The average particle size (D50) of the oxy-P-CAM.1 of the present invention was 14.3 μm, the span was 0.23, and the BET specific surface area was 97.6 m. 2 / g. The average shape factor was 0.990. The pore volume measured by N2 adsorption was 0.211 ml / g.

[0190] I.2 Preparation of Comparative (Oxy)hydroxylated CP-CAM.1 and Comparative Dehydrated Oxy-CP-CAM.1 Steps (a.1), (b.1), (c.1), and (d.1) were repeated.

[0191] Process C-(e.2) After that, simultaneous feeding of solutions (α2.1), (β2.1), and (γ2.1) was initiated. The molar feed ratio of ammonia to TM was kept constant at 0.35. During step (g), the temperature was kept constant at 55 °C. The pH was adjusted to 11.5 and maintained at this value until the end of step C-(e.2). The agitation speed was adjusted to 1200 rpm (6.3 W / L). The ratio of the reactor volume (3.2 L) to the total feed flow rate (corresponding to the residence time) started at 33 h and was increased during the synthesis to a residence time of 5 h. The agitator rotation speed was gradually reduced during the batch, with the final agitator rotation speed reaching 550 rpm (0.7 W / L). The agitator profile was designed to achieve an average specific energy input of 2.4 W / L during step C-(e.2). Mother liquor was continuously removed from the tank reactor to increase the solids content. The total duration of step C-(e.2) was 20 hours, and the total solids content of the resulting slurry in the reactor was 304 g / L. After completion of the batch, all feed streams were stopped, and the final suspension from the reactor and clarifier was discharged into a stirred suspension buffer vessel. The mean particle size (d50) of the particles in the suspension was 14.3 μm, with a span of 0.38. Neither steps (f) nor (g) were performed.

[0192] process: The slurry from step C-(e.2) was filtered, and the resulting filter cake was washed with deionized water and then with an aqueous solution of sodium hydroxide (1 kg of 25 wt. % aqueous sodium hydroxide per kg of solid hydroxide).

[0193] The filter cake was dried in a cabinet dryer at 120°C for 12 hours to obtain mixed metal (oxy)hydroxide CP-CAM.2. CP-CAM.2 had an average particle size (D50) of 14.2 μm, a span of 0.35, and a BET specific surface area of ​​21.2 m. 2 / g. The average shape factor was 0.972. The pore volume determined by N2 adsorption was 0.029 ml / g.

[0194] Oxy-CP-CAM.2 CP-CAM.2 was heated in a phosphorus oven at 450 °C for 2 hours under flowing air to obtain the mixed metal oxide oxy-P-CAM.2. The comparative precursor oxy-P-CAM.2 had an average particle size (D50) of 14.0 μm, a span of 0.35, and a BET specific surface area of ​​95.5 m. 2 / g. The average shape factor was 0.971. The pore volume measured by N2 adsorption was 0.082 ml / g.

[0195] Table 1 summarizes the properties of the inventive and comparative precursors.

[0196] [Table 1]

[0197] II. Preparation of Inventive and Comparative Cathode Materials II.1 Calcination and post-treatment of the precursor of the present invention 30 g of oxy-P-CAM.1 was mixed with LiOH monohydrate (molar ratio Li / metal = 1.04), 133 mg of TiO2, and 122 mg of ZrO2 in a grinder for 15 minutes. The resulting mixture was loaded into a sagger and transferred to a phosphorus oven. The temperature was increased to 750 °C at 2 °C / min under oxygen flow, held at 750 °C for 8 hours, and then allowed to cool naturally under oxygen flow. The resulting powder was then deagglomerated in a grinder and sieved.

[0198] 30 g of the powder was added to 15 ml of deionized water, stirred for 2 min, and then immediately filtered through a Buchner funnel to remove the water. The wet filter cake was then dried under reduced pressure at 120 °C under a N2 atmosphere for 10 h.

[0199] The resulting powder was dry-coated with boric acid by mixing 30 g of the resulting powder, mixing medium, and 30 mg of boric acid in a roller mill at low speed for 40 minutes. The dried powder was loaded into a sagger and heat-treated in a phosphorus oven. The phosphorus oven was heated to 300°C under an oxygen atmosphere for 2 hours and then allowed to cool naturally. CAM.1 of the present invention was obtained, with a D50 of 14.3 μm, a span of 0.22, and an average shape factor of 0.993. The pore volume of CAM.1 was 0.0044 ml / g.

[0200] II.2 Preparation of comparative cathode active materials The comparative oxide oxy-C-PCAM.2 was similarly processed to yield C-CAM.2 with a (D50) of 14.0 μm, a span of 0.34, and an average shape factor of 0.975. The pore volume of C-CAM.2 was 0.0031 ml / g.

[0201] III. Cathode Active Material Testing III.1 Cathode fabrication Positive electrode: PVDF binder (polyvinylidene fluoride, Solef® 5130) was dissolved in NMP (Merck) to prepare a 7.5 wt% solution. For electrode fabrication, the binder solution (3 wt%), graphite (SFG6L, 2 wt%), and carbon black (Super C65, 1 wt%) were suspended in NMP. After mixing using a planetary centrifugal mixer (ARE-250, Thinky Corp.; Japan), either the present invention's CAM.1 or C-CAM.2 (94 wt%) was added, and the suspension was stirred again to obtain a lump-free slurry. The solids content of the slurry was adjusted to 65%. This slurry was coated onto Al foil using a KTF-S roll-to-roll coater (Mathis AG). All electrodes were calendered before use. The thickness of the cathode material was 70 μm, with a coating weight of 15 mg / cm. 2 All electrodes were dried at 105°C for 7 hours before cell assembly.

[0202] III.2 Electrolyte Production A base electrolyte composition (EL Base 1) containing 12.7 wt.% LiPF, 26.2 wt.% ethylene carbonate (EC), and 61.1 wt.% ethyl methyl carbonate (EMC), based on the total weight of the base electrolyte composition, was prepared. 2 wt.% vinylene carbonate (VC) was added to this base electrolyte formulation (EL Base 2).

[0203] III.3 Test Cell Fabrication - Coin-Shaped Half Cell A coin-shaped half-cell (20 mm diameter, 3.2 mm thick) was assembled using the cathode and lithium metal prepared in II.1.1 as the working and counter electrodes, respectively, and sealed in an Ar-filled glove box. The cathode, anode, and separator were then stacked in the order cathode / / separator / / Li foil to form a half-coin cell. Then, the EL base 1 described above (III.2) was introduced into the 0.15 mL coin cell.

[0204] III.4 Evaluation of cell performance The initial performance, C-rate performance, and cycle performance were measured as follows: The coin half-cells were tested at room temperature over a voltage range of 4.3 V to 2.8 V as described in II.3. For the first cycle, the initial lithiation was performed in CC-CV mode. That is, a constant current (CC) of 0.1 C was applied until 4.3 V was reached, followed by a CV step until the current dropped to 0.01 C. For the C-rate test, the charge / discharge rate was adjusted accordingly. For the cycle test, the constant current was maintained at 1 C until 100 cycles were reached. The results are summarized in Table 2.

[0205] [Table 2]

Claims

1. 1. A process for producing particulate (oxy)hydroxides or oxides of Tm, wherein Tm represents a metal, Tm comprises nickel and at least one metal selected from cobalt and manganese, and the nickel content of Tm is at least 80 mol %, said process being carried out in a cascade of at least three stirred tank reactors and comprising the following steps: (a) providing an aqueous solution (α1) containing a water-soluble salt of Ni and optionally at least one metal selected from cobalt and manganese, an aqueous solution (β1) containing an alkali metal hydroxide, and an aqueous solution (γ1) containing a complexing agent selected from ammonia, glycine, tartrate, citrate, and oxalate; (b) combining in a first stirred tank reactor solution (α1), solution (β1), and, where applicable, solution (γ1), at a pH value in the range of 11.0 to 13.5 and with an average energy input in the range of 8 to 20 W / l, thereby producing slurried solid particles of hydroxide of TM; (c) transferring the particles from step (b) as a slurry to a second stirred tank reactor; (d) providing an aqueous solution (α2) containing a water-soluble salt of Ni and at least one metal selected from Co and Mn, an aqueous solution (β2) containing an alkali metal hydroxide, and optionally an aqueous solution (γ2) containing a complexing agent selected from ammonia, glycine, tartrate, citrate, and oxalate; (e) combining in said second stirred tank reactor solution (α2), solution (β2) and, where applicable, solution (γ2) at a pH value ranging from 10.5 to 12.0 and with an average specific energy input ranging from 2 to 8 W / l, which is 0.20 to 0.75 times lower than in step (b), thereby growing solid particles of hydroxide of TM; (f) transferring the particles from step (e) as a slurry to a third stirred tank reactor; (g) combining solution (α2), solution (β2) and, if applicable, solution (γ2) in said third stirred tank reactor at a pH value in the range of 10.5 to 12.0; Including, The method, wherein the average specific energy input in step (g) is in the range of 0.5 to 2 W / l, which is 0.20 to 0.75 times lower than in step (e), and the pH value is determined at 23°C.

2. 10. The method of claim 1, wherein the initial solids content at the start of the stages increases sequentially from step (b) to step (e) to step (g).

3. The particulate (oxy)hydroxide is selected from hydroxides, oxyhydroxides and oxides of TM, where TM is a combination of metals according to general formula (I): (Ni a Co b Mr c ) 1-d M d (I) (wherein a is in the range of 0.80 to 0.97; b is 0 or 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, Sb and Ta; 3. The method of claim 1, wherein a+b+c=1 and b+c>0.

4. 3. The process of claim 1 or 2, wherein step (g) is carried out in a draft tube reactor.

5. 3. The process of claim 1 or 2, wherein in two of steps (b), (e) and (g), mother liquor is removed from the reactor.

6. 3. The method according to claim 1 or 2, comprising an additional step (h) of separating the particulate (oxy)hydroxide by solid-liquid separation and then drying it.

7. 7. The method of claim 6, comprising step (i) heating at a temperature in the range of 400 to 550°C in the absence of a lithium compound.

8. A particulate (oxy)hydroxide of TM having a core-shell structure and a particle size distribution span (D90-D10) / D50 of less than 0.30, wherein the TM comprises nickel and at least one metal selected from cobalt and manganese, the nickel content of the TM is at least 80 mol %, the particles are composed of primary particles, have a core, a shell, and a concentric layer between the core and the shell, and the density of the concentric layer is higher than the density of the core and the shell; The particulate (oxy)hydroxide is N ２ Particulate (oxy)hydroxide with a total pore / interstitial volume in the range of 0.033-0.1 ml / g, as determined by adsorption.

9. A particulate oxide of TM having a core-shell structure and a particle size distribution span (D90-D10) / D50 of less than 0.30, the TM comprising nickel and at least one metal selected from cobalt and manganese, the nickel content of the TM being at least 80 mol %, and the particles being composed of primary particles; The particulate oxide is N ２ Particulate oxide with a total pore / interstitial volume in the range of 0.1-0.5 ml / g, as determined by adsorption.

10. 2 to 120 m ２ 10. A particulate (oxy)hydroxide or oxide according to claim 8 or 9, having a BET specific surface area in the range of 1 / g.

11. 10. A particulate (oxy)hydroxide or oxide according to claim 8 or 9, having an average shape factor of 0.98 or more.

12. TM is a metal combination according to general formula (I), a is in the range of 0.80 to 0.97; b is 0 or 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, Sb and Ta; 10. A particulate (oxy)hydroxide or oxide according to claim 8 or 9, wherein a+b+c=1 and b+c>0.

13. 10. A method for producing a cathode active material for a lithium ion battery, comprising the steps of: mixing the particulate (oxy)hydroxide or oxide according to claim 8 or 9 with a lithium source, and optionally a dopant selected from oxides or (oxy)hydroxides of Nb, Ti, Ta, Zr, Al, Mg, or W; and calcining the resulting mixture at a temperature in the range of 600 to 1000°C.

14. General formula Li １＋ｘ TM １－ｘ O ２ wherein x is in the range of −0.01 to +0.05, the cathode active material having a core-shell structure, a particle size distribution span (D90−D10) / D50 of less than 0.30, a TM comprising nickel and at least one metal selected from cobalt and manganese, and a nickel content of the TM of at least 80 mol %; The cathode active material is N ２ A cathode active material having a total pore / interstitial volume in the range of 0.0035 to 0.01 ml / g, as determined by adsorption.

15. 15. The cathode active material of claim 14, having a second outer shell comprising at least one oxide compound of W or B.

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