Method for producing particulate (oxy)hydroxide, particulate (oxy)hydroxide and method for using the same

Abstract

The present invention relates to a method for producing a particulate (oxy)hydroxide of TM, wherein the TM is metallic and the TM comprises at least 60 mol % nickel, said method comprising the steps of: (a) providing an 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, and an α- or β-amino acid or an alkali metal salt thereof in the range of 0.01 to 0.05 mol % relative to TM, an aqueous solution (β) containing an alkali metal hydroxide, and optionally an aqueous solution (γ) containing ammonia; (b) combining solution (α) and solution (β), and, if applicable, solution (γ), in a stirred tank reactor at a pH value in the range of 10.0 to 13.0, thereby producing solid particles of nickel-containing hydroxide, the solid particles being slurried; Includes:

Description

[Technical Field]

[0001] The present invention relates to a method for producing a particulate (oxy)hydroxide of TM, wherein the TM is metallic and the TM comprises at least 60 mol % nickel, said method comprising the steps of: (a) providing an 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, and an α- or β-amino acid or an alkali metal salt thereof in the range of 0.01 to 0.05 mol % relative to TM, an aqueous solution (β) containing an alkali metal hydroxide, and optionally an aqueous solution (γ) containing ammonia; (b) combining solution (α) and solution (β), and, if applicable, solution (γ), in a stirred tank reactor at a pH value in the range of 10.0 to 13.0, thereby producing solid particles of nickel-containing hydroxide, the solid particles being slurried; Includes: [Background technology]

[0002] Lithium-ion secondary batteries are state-of-the-art devices for energy storage. Many applications have been considered, ranging from small devices such as mobile phones and laptop computers to car batteries and other e-mobility batteries. Various battery components, such as electrolytes, electrode materials, and separators, play important roles in battery performance. Cathode materials have received particular attention. Several materials have been proposed, such as lithium iron phosphate, lithium cobalt oxide, and lithium nickel cobalt manganese oxide. Although extensive research has been conducted, solutions found to date still require improvement.

[0003] The electrode material is crucial for the performance of lithium-ion batteries. Lithium-containing mixed transition metal oxides, spinel or layer structure mixed oxides, in particular lithium-containing mixed oxides of nickel, manganese, and cobalt, are of particular interest (see, for example, EP 1 189 296). However, not only the stoichiometry of the electrode material but also other properties such as morphology and surface properties are important.

[0004] The corresponding mixed oxides are generally produced using a two-stage process. In the first stage, a sparingly soluble compound of the transition metal(s) is prepared by precipitation from a solution, e.g., a carbonate or hydroxide. This sparingly soluble salt is often also called a precursor. In the second stage, the precipitated salt of the transition metal(s) is mixed with a lithium compound, e.g., Li2CO3, LiOH, or Li2O, and calcined at high temperatures, e.g., 600-1100 °C.

[0005] Existing lithium-ion batteries have room for improvement, especially in terms of energy density. To achieve this, cathode active materials must have high specific capacities. This can be achieved, for example, by ensuring the cathode active material particles have a regular shape. Typically, the morphology of the precursor is converted to the morphology of the cathode active material during calcination unless it changes significantly.

[0006] WO 2012 / 095381 and WO 2013 / 117508 disclose processes for precipitating hydroxides or carbonates, in which a vessel with compartments is used. A large amount of energy is introduced into each compartment(s). However, it is difficult to carry out the process on a commercial scale.

[0007] During upscaling, it has been observed that the process of creating the precursor is very sensitive to changes in pH. Small changes in pH can have a significant effect on the precursor's properties, such as particle size. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] EP 1 189 296 [Patent Document 2] WO 2012 / 095381 [Patent Document 3] WO 2013 / 117508 Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention was to provide a method for producing a precursor of a cathode active material for a lithium-ion battery having a high volumetric energy density and excellent cycling stability. More specifically, an object of the present invention was therefore to provide a battery starting material suitable for producing a lithium-ion battery having a high volumetric energy density and excellent cycling stability. A further object of the present invention was to provide a method by which a suitable starting material for a lithium-ion battery can be prepared. Furthermore, an object of the present invention was to provide a method for producing a precursor that is not sensitive to changes in pH value.

[0010] Without wishing to be bound by any theory, it can be assumed that the lithiation process depends on the particle size, porosity, and specific surface area of ​​the precursor. An object of the present invention was to provide a method for producing a precursor that can be lithiated in a very efficient manner. More specifically, an object of the present invention was therefore to provide a starting material for a battery that can be lithiated in a very efficient manner. [Means for solving the problem]

[0011] We have therefore found the method defined at the outset, which hereinafter is also referred to as the method of the invention or the method according to the invention. The method of the invention may be carried out as a batch process or as a continuous or semi-continuous process. A continuous process is preferred. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 shows a stirred tank reactor. [Figure 2] FIG. 2 is a diagram showing the radial direction of a primary particle. [Figure 3] Figure 3 shows top-view SEM images of C-TM-OH.1 (left), TM-OH-2 (middle), and TM-OH.3 (right). [Figure 4] Figure 4 shows cross-sectional SEM images of C-TM-OH.1 (left) and TM-OH.3 (right). [Figure 5] Figure 5 shows top-view and cross-sectional SEM images of C-TM-OH.6 (left) and TM-OH.7 (right). DETAILED DESCRIPTION OF THE INVENTION

[0013] The method of the present invention includes at least two steps (hereinafter also referred to as step (a) and step (b)), which may include substeps. The method of the present invention will be described in more detail below.

[0014] The method of the present invention is a method for producing a particulate (oxy)hydroxide of TM, wherein the TM is metallic and the TM comprises at least 60 mol % nickel, said method comprising the steps of: (a) providing an 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, and an α- or β-amino acid or an alkali metal salt thereof in the range of 0.01 to 0.05 mol % relative to TM, an aqueous solution (β) containing an alkali metal hydroxide, and optionally an aqueous solution (γ) containing ammonia; (b) combining solution (α) and solution (β), and, if applicable, solution (γ), in a stirred tank reactor at a pH value in the range of 10.0 to 13.0, thereby producing solid particles of nickel-containing hydroxide, the solid particles being slurried; Includes:

[0015] In one embodiment of the present invention, the average particle size (D50) determined by laser diffraction is in the range of 2 to 20 μm, preferably 3 to 16 μm, more preferably 5 to 12 μm.

[0016] In one embodiment of the present invention, the precursor of the present invention has a particle size distribution, [(D90)-(D10)] divided by (D50), in the range of 0.35 to 2, preferably 0.35 to 0.5 or 0.8 to 1.4.

[0017] TM is a compound represented by the general formula (I) (Ni a Co b Mn c ) 1-d M d (I) (wherein a is in the range of 0.7 to 0.99, preferably 0.83 to 0.92, b is 0 or in the range of 0.01 to 0.2, preferably 0.03 to 0.15; c is in the range of 0 to 0.2, preferably 0.03 to 0.15; d is in the range of 0 to 0.1, preferably 0.003 to 0.03; M is at least one of Al, Mg, Ti, Mo, Nb, Ta, W, and Zr; b+c>0, a+b+c=1) It is a combination of metals.

[0018] The method of the present invention is a method for producing particulate (oxy)hydroxides of TM. In the context of the present invention, "(oxy)hydroxide" refers to hydroxide and includes not only stoichiometrically pure hydroxide but also, in particular, compounds having anions other than hydroxide ions, such as oxide ions and carbonate ions, or anions derived from the transition metal starting material, such as acetate or nitrate and particularly sulfate, in addition to transition metal cations and hydroxide ions. Oxide ions may be due to partial oxidation, for example, uptake of oxygen during drying. Carbonates may occur when technical grade alkali metal hydroxides are used.

[0019] Furthermore, in embodiments where sulfates are used as starting materials, sulfates can also be present as impurities, for example, in a proportion of 0.001 to 1 mol%, preferably 0.01 to 0.5 mol%. Such sulfates are disregarded in the context of the present invention.

[0020] In one embodiment of the present invention, the precipitated (oxy)hydroxide of TM has the formula TMO x (OH) y (CO3) t (where 0 ≦ x < 1, 1 < y ≦ 2.2, 0 ≦ t ≦ 0.3, preferably 0.005 ≦ t ≦ 0.05).

[0021] Certain elements are ubiquitous. For example, sodium, copper, and chloride are detected in very small proportions in virtually all inorganic materials. In the context of the present invention, cations or anions present in a proportion of less than 0.02 mol% are disregarded. Thus, a mixed hydroxide obtained according to the method of the present invention containing less than 0.02 mol% of sodium is considered to be sodium-free in the context of the present invention.

[0022] The process of the present invention is carried out in a stirred tank reactor, including carrying out the process as a batch reactor, in a stirred tank reactor, in a continuous stirred tank reactor, or in a cascade of at least two continuous stirred tank reactors, for example, a cascade of 2 to 4 continuous stirred tank reactors. It is preferred to carry out the process of the present invention in a continuous stirred tank reactor. The continuous stirred tank reactor contains at least one overflow system that allows for continuous (or interval) removal of slurry (or mother liquor) from the continuous stirred tank reactor.

[0023] In embodiments where the stirred vessel is a continuous stirred-tank reactor or a cascade of at least two stirred-tank reactors, each stirred-tank reactor(s) has an overflow system. The slurry contains the precipitated mixed metal hydroxide of TM and a mother liquor. In the context of the present invention, the mother liquor comprises the water-soluble salts present in the solution and, optionally, further additives. Examples of possible water-soluble salts include alkali metal salts of the transition metal counterions, such as sodium acetate, potassium acetate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, sodium halides, potassium halides, and the corresponding ammonium salts, such as ammonium nitrate, ammonium sulfate, and / or ammonium halides. Most preferably, the mother liquor comprises sodium sulfate, ammonium sulfate, and ammonia.

[0024] In one embodiment of the invention, the process is carried out in a vessel equipped with a clarifier, where the mother liquor is separated from the precipitated mixed metal hydroxides of TM and the mother liquor is removed.

[0025] In step (a), various solutions are provided: an 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, and an α- or β-amino acid or an alkali metal salt thereof in the range of 0.01 to 0.05 mol % relative to TM; an aqueous solution (β) containing an alkali metal hydroxide, and An aqueous solution (γ) optionally containing ammonia. Preferably, the invention is carried out without the use of a solution (γ).

[0026] In step (a), an aqueous solution (solution (α)) containing a water-soluble salt of Ni and at least one metal selected from Co and Mn is provided. The choice of salt reflects the composition of the TM, with the molar content of nickel being at least 60% relative to the TM. If applicable, solution (α) contains at least one further metal selected from Ti, Zr, Mo, W, Al, Mg, Nb, and Ta.

[0027] Solution (α) further contains 0.01 to 0.05 mol % of an α- or β-amino acid or an alkali metal salt thereof relative to the TM. Examples of α-amino acids include cysteine, proline, asparagine, leucine, aspartic acid, lysine, phenylalanine, α-alanine (hereinafter abbreviated as alanine), valine, and serine, and an example of a β-amino acid is β-alanine. Examples of alkali metal salts include sodium salts and potassium salts. Partially neutralized α- or β-amino acids are also possible. For example, sodium salts of alanine, glycine, and serine are preferred. Without wishing to be bound by any theory, it is assumed that such amino acids form complexes with one of the TMs, such as nickel.

[0028] Even more preferably, the α-amino acid is selected from glycine and its sodium and potassium salts.

[0029] Alpha-alanine may be provided as L-alanine or racemic alanine, or as partially racemized L-alanine. Glycine is a preferred amino acid.

[0030] Solution (α) can be prepared by dissolving a water-soluble salt of TM, such as the sulfate salt, in water and then adding an amino acid selected from glycine, alanine, and serine, or an alkali metal salt thereof, in the amount specified above. It is also possible to dissolve a water-soluble salt of TM, such as the sulfate salt, in water in the presence of the α- or β-amino acid or its alkali metal salt. However, such solution (α) is preferably formed by combining an aqueous solution of the α- or β-amino acid or its alkali metal salt with an aqueous solution of a water-soluble salt(s) of TM, e.g., immediately before combining freshly formed solution (α) with solution (β) and, if applicable, solution (γ). This formation can also be performed as a premix in a Y-nozzle.

[0031] The term water-soluble salts of nickel or metals other than nickel 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. Water-soluble salts of nickel and cobalt are preferably Ni 2+ and Co 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.

[0032] Solution (α) may have a pH value in the range of 2 to 5. It is preferable not to add ammonia to solution (α).

[0033] 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 include lithium hydroxide, preferably potassium hydroxide, and a combination of sodium hydroxide and potassium hydroxide, and even more preferably sodium hydroxide.

[0034] Solution (β) may contain a certain amount of carbonate, for example 0.1 to 2% by mass relative to the amount of the respective alkali metal hydroxide, which is added intentionally or by aging of the solution or the respective alkali metal hydroxide.

[0035] Solution (β) may have a hydroxide concentration ranging from 0.1 to 12 mol / l, preferably from 6 to 10 mol / l.

[0036] The pH value of the solution (β) is preferably 13 or higher, for example 14.5.

[0037] In one embodiment of the present invention, an aqueous solution (γ) is provided. The solution (γ) contains ammonia. The solution (γ) may have a pH value in the range of 8 to 10 and an ammonia concentration in the range of 1 to 25.

[0038] In one embodiment of the present invention, aqueous solutions (α) and (β), and, where applicable, aqueous solution (γ), have a temperature in the range of 10 to 75° C. before being mixed in a stirred tank reactor.

[0039] In step (b), aqueous solution (α) and aqueous solution (β), and, where applicable, aqueous solution (γ), are combined in a stirred tank reaction at a pH value in the range of 10.0 to 13.0, thereby producing solid particles of nickel-containing hydroxide, which are slurried.

[0040] During step (b), aqueous solutions (α) and (β) are fed to the reactor. Preferably, aqueous solutions (α) and (β) are fed to the reactor such that the stoichiometry of the TM metal on the one hand and the hydroxide ions on the other hand is "correct," i.e., the stoichiometry matches the stoichiometry of the respective hydroxides to be precipitated. In another embodiment of the invention, the stoichiometry is adjusted so that the hydroxide is present in excess, for example, 1-5 mol % relative to the hydroxide.

[0041] In one embodiment of the invention, the aqueous solutions (α) and (β), and, if applicable, (γ), are fed into a stirred-tank reactor through separate inlets, and in one embodiment of the invention, at least one inlet is located directly above the vortex caused by stirring.

[0042] In one embodiment of the invention, the aqueous solutions (α) and (β), and, where applicable, (γ), are introduced into said stirred vessel via two inlets, for example two pipes whose outlets are arranged adjacent to each other, for example in parallel, or via a Y-mixer.

[0043] In a preferred embodiment of the present invention, the at least two inlets are designed as a coaxial mixer comprising two coaxially arranged pipes through which the aqueous solutions (α) and (β) are introduced into the stirred-tank reactor. In one embodiment of the present invention, step (b) is carried out by using two or more coaxially arranged pipes through which the aqueous solutions (α) and (β), and, if applicable, (γ), are introduced into the stirred-tank reactor. In another embodiment of the present invention, the introduction step is carried out by using exactly one system of coaxially arranged pipes through which the aqueous solutions (α) and (β), and, if applicable, (γ), are introduced into the stirred-tank reactor.

[0044] In a preferred embodiment, the aqueous solutions (α) and (β) are fed into a stirred tank reactor via coaxial nozzles.

[0045] In embodiments in which a cascade of at least two continuous stirred-tank reactors is used, aqueous solutions (α) and (β), and, where applicable, solution (γ), are fed to the most upstream stirred-tank reactor.

[0046] The stirred tank reactor(s) used in the present invention comprise a stirrer. Such a stirrer can be selected from pitched blade turbines, Rushton turbines, cross-arm stirrers, dissolver blades, and propeller stirrers. The stirrer can be operated at a rotational speed resulting in an average energy input in the range of 0.1 to 10 W / L, preferably in the range of 1 to 7 W / L.

[0047] Additionally, the stirred tank reactor(s) used in the present invention may contain one or more, for example, 1 to 4, baffles.

[0048] In one embodiment of the present invention, step (b) may be carried out at a temperature ranging from 20 to 90° C., preferably from 30 to 80° C., more preferably from 35 to 75° C. This temperature is determined in a stirred tank reactor.

[0049] In one embodiment of the invention, step (b) has a duration in the range of 10 minutes to 10 hours. In embodiments where the method of the invention is carried out as a continuous process, the duration refers to the average residence time.

[0050] In one embodiment of the present invention, step (b) can be carried out at atmospheric pressure. In another embodiment, step (b) can be carried out at slightly elevated pressure, for example, 10 to 100 mbar above atmospheric pressure.

[0051] Step (b) can be carried out in air, in an inert gas atmosphere, such as a noble gas or nitrogen atmosphere, or in a reducing gas atmosphere. Examples of reducing gases include CO and SO. It is preferable to carry out the step in an inert gas atmosphere.

[0052] In one embodiment of the invention, the process of the invention is carried out in a stirred tank reactor equipped with a clarifier, where the mother liquor is separated from the precipitated TM hydroxide and the mother liquor is removed.

[0053] In one embodiment of the present invention, step (b) is carried out in two substeps (b1) and (b2), with substep (b1) being carried out at a pH value 0.2 to 2.0 units higher than that of substep (b2). In other words, the pH value in substep (b2) is 0.2 to 2.0 units lower than that of substep (b1). The lowering of the pH value can be achieved, for example, by adding less ammonia in substep (b2) than in substep (b1), or by selecting a higher ratio of alkali metal hydroxide to TM in substep (b1) compared to substep (b2), or by adding an acid, such as sulfuric acid. However, the pH value in substep (b2) is still at least 10.0. Preferably, the duration of substep (b2) is longer than that of substep (b1).

[0054] In one embodiment of the present invention, substeps (b1) and (b2) are carried out such that the solid from substep (b1) is separated and used as the solid seed for substep (b2). In another embodiment, substeps (b1) and (b2) are carried out such that the slurry obtained from substep (b1) is used in situ for substep (b2).

[0055] In one embodiment of the invention, substeps (b1) and (b2) are carried out such that an α- or β-amino acid or its respective alkali metal salt is added in both substeps or in at least one substep, such as substep (b2). The latter embodiment can be achieved by carrying out substep (b1) by combining solution (α') containing a water-soluble salt of TM but not an amino acid or its respective alkali metal salt with solution (β) and optionally solution (γ), followed by combining solution (α) with solution (β) and optionally solution (γ) in substep (b2).

[0056] In another embodiment of the invention, step (b) is carried out at a pH value that varies by at most 0.2 units, so that the pH value remains essentially constant during step (b).

[0057] By carrying out the method of the present invention, an aqueous slurry is formed. The method of the present invention is highly robust against undesired changes in pH value. From the aqueous slurry, particulate mixed hydroxide can be obtained by a solid-liquid separation process, such as filtration, spray drying, or drying under an inert gas or air. When dried under air, partial oxidation occurs to obtain a mixed (oxy)hydroxide of TM.

[0058] The precursors obtained according to the method of the present invention are excellent starting materials for cathode active materials suitable for fabricating batteries with the highest volumetric energy density.

[0059] Another aspect of the present invention relates to a precursor, hereinafter also referred to as the precursor of the present invention, which is a particulate (oxy)hydroxide of TM, wherein TM comprises at least 70 mol % of nickel, said (oxy)hydroxide has an average particle size (D50) in the range of 2 to 20 μm, TM comprises 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, said (oxy)hydroxide contains C as organic carbon in the range of 500 ppm to 1 wt %, and at least 60 vol % of the secondary particles consist of agglomerates of essentially radially oriented primary particles.

[0060] To quantify organic carbon, total carbon is typically converted to carbon dioxide by heat treatment under an oxygen atmosphere and CO2 is measured by infrared spectroscopy.

[0061] The organic carbon is preferably glycine, alanine or serine, or an alkali metal salt thereof.

[0062] The fraction of radially oriented primary particles can be determined, for example, by SEM (scanning electron microscopy) of cross sections of at least five secondary particles.

[0063] "Essentially radially oriented" does not require perfect radial orientation, but includes a deviation G from perfect radial orientation of up to 5 degrees in SEM analysis.

[0064] Furthermore, at least 60% of the secondary particle volume is filled with radially oriented primary particles, and preferably only a small inner portion of the particle volume, e.g., at most 40%, preferably at most 20%, is filled with non-radially oriented, e.g., randomly oriented, primary particles.

[0065] In one embodiment of the present invention, TM is a compound of general formula (I) (Ni a Co b Mn c ) 1-d M d (I) (wherein a is in the range of 0.7 to 0.99, preferably 0.83 to 0.92, b is 0 or in the range of 0.01 to 0.2, preferably 0.03 to 0.15; c is in the range of 0 to 0.2, preferably 0.03 to 0.15; d is in the range of 0 to 0.1, preferably 0.003 to 0.03; M is at least one of Al, Mg, Ti, Mo, Nb, Ta, W, and Zr; b+c>0, a+b+c=1) It is a combination of metals.

[0066] In one embodiment of the present invention, the precursor of the present invention has a total pore / penetration volume in the range of 0.033-0.1 ml / g, preferably 0.035-0.07 ml / g, 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.

[0067] The precursor of the present invention has an average secondary particle size D50 in the range of 2 to 20 μm, preferably 3 to 16 μm, and even more preferably 5 to 12 μm.

[0068] In one embodiment of the present invention, the precursor of the present invention is 2 to 70 m 2 / g, preferably 4 to 50m 2 / g, which can be determined by nitrogen adsorption after outgassing the sample at 200°C for 30 minutes and beyond, according to DIN ISO 9277:2010.

[0069] In one embodiment of the present invention, the precursor of the present invention has a particle size distribution, [(D90)-(D10)] divided by (D50), in the range of 0.35 to 2, preferably 0.35 to 0.5 or 0.8 to 1.4.

[0070] In one embodiment of the present invention, the precursor of the present invention has a bimodal particle size distribution with a first maximum in the range of 3 to 7 μm ("smaller particles") and a second maximum in the range of 11 to 17 μm ("larger particles"). Even more preferably, the total volume of the smaller particles is in the range of 10 to 25% of the total volume of the larger particles.

[0071] In one embodiment of the present invention, the precursor particles of the present invention exhibit a structure of multiple concentric rings, for example, at least 10 rings, preferably up to 200 rings. Such concentric rings are detected when cross-sections of such particles are analyzed by SEM. This structure can be compared to the growth rings of a tree, each of which has an intensity ranging from 5 to 500 nm.

[0072] In one embodiment of the present invention, the particles of the precursor of the present invention have a form factor in the range of 0.87 to 0.99.

[0073] The precursor of the present invention is highly suitable for producing cathode active materials with high energy density. Such cathode active materials can be produced by mixing the precursor of the present invention with a lithium source, such as LiO, LiOH, or LiCO, either in its pure or hydrated form, and calcining the mixture at a temperature ranging from 600 to 1000°C. Accordingly, a further aspect of the present invention is a method for using the precursor of the present invention to produce a cathode active material for a lithium ion battery. Another aspect of the present invention is a method for producing a cathode active material for a lithium ion battery (hereinafter also referred to as the calcination method of the present invention), comprising mixing the particulate transition metal (oxy)hydroxide of the present invention with a lithium source and thermally 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, more preferably 0.98 to 1.05.

[0074] In one embodiment of the invention, the precursor of the invention is heated to a temperature in the range of 600-1000°C, and thus dehydrated or "pre-calcined," prior to being mixed with a lithium source. In such an embodiment, the pre-calcined particulate transition metal (oxy)hydroxide is mixed with a lithium source, and the mixture is heat-treated at a temperature in the range of 600-1000°C. Preferably, the ratio of the pre-calcined precursor of the invention to the lithium source is selected so that the molar ratio of Li to TM is in the range of 0.95:1 to 1.2:1, more preferably 0.98 to 1.05.

[0075] 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 “thermal treatment” and “heat treatment” are used interchangeably in the context of the present invention.

[0076] In one embodiment of the present invention, in the firing of the present invention, the obtained mixture is heated to 600 to 900° C. at a heating rate of 0.1 to 10° C. / min.

[0077] 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 increased to 650 to 800° C., and then kept at 650 to 800° C. for 10 minutes to 10 hours.

[0078] 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 them. A rotary kiln has the advantage that the material produced therein is very homogenized. In the roller hearth kiln and the pusher kiln, different reaction conditions for different processes can be set very easily. In laboratory-scale experiments, box furnaces, tube furnaces, and split-tube furnaces are also possible.

[0079] 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.

[0080] In one embodiment of the present invention, the calcination of the present invention is carried out under a gas flow, such as air, oxygen, and oxygen-enriched air. Such a gas flow is also called a forced gas flow. Such a gas flow is represented by the general formula Li 1+x TM 1-x O2 per kg of material, 0.5-15 m 3 The gas flow can have a specific flow rate in the range of 1 / h. The volume is determined under normal conditions (298 Kelvin and 1 atmosphere). The gas flow is useful for removing gaseous decomposition products such as water and carbon dioxide.

[0081] In one embodiment of the present invention, the calcination of the present invention has a duration ranging from 1 hour to 30 hours, preferably from 10 hours to 24 hours. The time at temperatures above 600°C counts the heating and holding time, but the cooling time is ignored in this context.

[0082] A further aspect of the present invention is a cathode comprising at least one particulate electrode active material according to the present invention. These are particularly useful for lithium-ion batteries. Lithium-ion batteries comprising at least one cathode according to the present invention exhibit good cycling behavior / stability. An electrode comprising at least one particulate cathode active material according to the present invention is also referred to below as a cathode according to the present invention or a cathode according to the present invention.

[0083] In particular, the cathode of the present invention comprises: (1) at least one particulate electrode active material of the present invention; (2) carbon in a conductive state, and (3) a binder material, also called binder or binder (3), and preferably (4) Current collector Contains:

[0084] In a preferred embodiment, the cathode of the present invention comprises, based on the sum of (1), (2), and (3), (A) 80 to 98 mass % of the particulate electrode active material of the present invention; (B) 1 to 17 mass% carbon; (C) 1 to 15 mass% of a binder Contains:

[0085] The cathode according to the present invention may contain additional components, such as, but not limited to, a current collector, such as aluminum foil, and may further contain conductive carbon and a binder.

[0086] The cathode according to the present invention contains a conductively modified carbon, also referred to simply as carbon (2), which can be selected from soot, activated carbon, carbon nanotubes, graphene, and graphite, and combinations of at least two of the above.

[0087] Suitable binders (3) 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] Another preferred binder (3) is polybutadiene.

[0093] Other suitable binders (3) are selected from polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyimides and polyvinyl alcohol.

[0094] In one embodiment of the present invention, the binder (3) 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:

[0095] The binder (3) can be a crosslinked or non-crosslinked (co)polymer.

[0096] In a particularly preferred embodiment of the present invention, the binder (3) is selected from halogenated (co)polymers, in particular fluorinated (co)polymers. Halogenated or fluorinated (co)polymers are understood to mean (co)polymers containing 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.

[0097] Suitable binders (3) are, in particular, 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.

[0098] The cathode of the present invention may comprise 1 to 15% by weight of binder(s) relative to the cathode active material of the present invention. In another embodiment, the cathode of the present invention may comprise 0.1 to less than 1% by weight of binder(s).

[0099] Also disclosed is a battery containing at least one cathode comprising the cathode active material of the present invention, carbon, and a binder, at least one anode, and at least one electrolyte.

[0100] The cathode embodiment of the present invention has already been described in detail above.

[0101] The anode may contain at least one anode active material such as carbon (graphite), TiO, lithium titanium oxide, silicon, or tin. The anode may further contain a current collector, for example, a metal foil such as copper foil.

[0102] The electrolyte may include at least one non-aqueous solvent, at least one electrolyte salt, and optionally, additives.

[0103] The non-aqueous solvent for the electrolyte may 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.

[0104] 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.

[0105] The molecular weight M of suitable polyalkylene glycols, especially suitable polyethylene glycols, W may be at least 400 g / mol.

[0106] 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.

[0107] 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.

[0108] Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.

[0109] Examples of suitable acyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.

[0110] An example of a suitable cyclic acetal is 1,3-dioxane, and especially 1,3-dioxolane.

[0111] Examples of suitable acyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.

[0112] Examples of suitable cyclic organic carbonates are compounds according to general formulas (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).

[0113] Preferably, R 1 is methyl and R 2 and R 3 are each hydrogen or R 1 , R 2 and R 3 are hydrogen atoms.

[0114] Another preferred cyclic organic carbonate is vinylene carbonate of formula (IV).

[0115] [ka]

[0116] 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.

[0117] The electrolyte further comprises at least one electrolyte salt. Suitable electrolyte salts are, in particular, lithium salts. Examples of suitable lithium salts include 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).

[0118] Preferred electrolyte salts are selected from LiC(CF3SO2)3, LiN(CF3SO2)2, LiPF6, LiBF4, LiClO4, with LiPF6 and LiN(CF3SO2)2 being particularly preferred.

[0119] The battery disclosed in the context of the present invention includes one or more separators by which the electrodes are mechanically separated. Preferred separators are polymer films, particularly porous polymer films, that are unreactive with metallic lithium. Particularly preferred materials for the separator are polyolefins, particularly film-forming porous polyethylene and film-forming porous polypropylene.

[0120] A separator made of polyolefin, particularly polyethylene or polypropylene, can have a porosity in the range of 35 to 45%. Suitable pore sizes are, for example, in the range of 30 to 500 nm.

[0121] In another embodiment of the present invention, the separator 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.

[0122] The battery according to the invention may further comprise a housing which may have any shape, for example a cube, or the shape of a cylindrical disk or can. In one variant, a metal foil configured as a pouch is used as the housing.

[0123] The batteries disclosed below exhibit good cycling stability and low capacity fade.

[0124] The battery disclosed below may include two or more electrochemical cells that are combined with each other, for example, connected in series or in parallel. A series connection is preferred. In such a battery, at least one electrochemical cell contains at least one cathode according to the present invention. Preferably, in the electrochemical cell according to the present invention, the majority of the electrochemical cells contain the cathode according to the present invention. Even more preferably, in the battery according to the present invention, all electrochemical cells contain the cathode according to the present invention.

[0125] 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.

[0126] Brief description of the drawings, Figure 1: A: Mixing vessel B: Stirrer C: Supply of solution (β) D: Supply of solution (γ) E: Supply of solution (α) F: Baffle G: Stirrer's engine. [Example]

[0127] Example General: Powder X-ray diffraction (XRD) data were collected using a laboratory diffractometer (D8 Discover, Bruker AXS GmbH, Karlsruhe). The instrument was set up with a molybdenum X-ray tube. A curved Germanium Johansson primary monochromator was used to monochromatize the characteristic K-alpha radiation. Data were collected in the Bragg-Brentano reflection geometry over the 2θ range of 5.0–50°, applying a step size of 0.019°. A LYNXEYE area detector was used to collect the scattered X-ray signal.

[0128] For XRD measurements, the precursor was ground using an IKA tube mill with an MT40.100 disposable grinding chamber. The powder was placed in a sample holder and flattened using a glass plate.

[0129] Rietveld refinement analysis of the precursor material microstructure was performed using DIFFRAC.TOPAS V6 software (Bruker AXS GmbH), providing access to the corresponding crystallite sizes. During peak fitting, instrumental broadening was taken into account, and the instrumental and sample broadening were separated. The sample contribution was determined using a single Lorentzian profile function defined by the following equation:

[0130]

number

[0131] The proportion and degree of radial orientation of the primary particles was determined based on cross-sectional SEM images of each precursor.

[0132] 2 is a diagram for explaining the radial direction of a primary particle. Brief explanation of FIG.

[0133] The variables in Figure 2 have the following meanings: A: Secondary particles B: Primary particle C: Center of secondary particle D: Center of primary particle E: Radial direction, defined as the direction from the center of a secondary particle to the center of a primary particle F: orientation of the primary particle, defined as the orientation of the eigenvector with the largest eigenvalue of the covariance matrix calculated for the binary mask of the primary particle G: The angle between the orientation of the primary particle and the ideal radial direction.

[0134] For each primary particle, the minimum absolute angle (G) between the radial direction (E) and the long axis direction (F) of the primary particle was determined. Thus, an angle of 0 means that the primary particle is ideally radially oriented, while larger angles indicate less ideal radial orientation. The distribution of primary particle angles G quantifies the degree to which the entire sample is radially oriented. In the case of perfect radial orientation, the distribution is at zero; in the case of completely random orientation, the angle is uniformly distributed between 0 and 90°, with a median and mean of 45°.

[0135] To determine the shape factor and axial ratio of the samples, both properties were first determined for at least 50 individual particles of each sample and then averaged.

[0136] The shape factor of individual particles was calculated from the perimeter and area determined from top-view SEM images. Shape factor = (4π·area) / (perimeter) 2 A perfect sphere has a shape factor of 1.0, but anything that deviates from a perfect sphere has a shape factor less than 1.0.

[0137] To determine the axial ratio of the particle's bounding box, the smallest possible rectangular bounding box was drawn around the top-view SEM image of the particle. The axial ratio was calculated from the lengths a1 and a2 of the two sides (a1 ≥ a2) as follows: a1 / a2.

[0138] For a perfect sphere, the axis ratio of the bounding box is 1.0, but any deviation from a perfect sphere will result in an axis ratio greater than 1.0.

[0139] To quantify the amount of (organic) carbon, 100 mg of material was placed in a disposable ceramic cup. Approximately 0.5 g of iron granules was added to the sample, and the mixture was covered with a layer of approximately 1.5 g of tungsten granules. The sample was heated in a stream of pure oxygen in the induction furnace of an Eltra CS 800 analyzer, converting the carbon in the sample to carbon dioxide, which was then quantified by infrared spectroscopy in the combustion gases.

[0140] To quantify the stability of the corresponding precipitation process, the stability coefficient stab was determined as the maximum change in d50 by increasing the pH of the process by 0.2 pH units.

[0141] Glycine was >99% pure and purchased from Sigma Aldrich.

[0142] Water: Deionized water unless otherwise stated.

[0143] I. Preparation of Precursors of the Invention and Comparative Precursors: I.1 Preparation of comparative precursors C-TM-OH.1, C-TM-OH.4, and precursors of the invention TM-OH.2, TM-OH.3, TM-OH.5, and seed slurry fraction s.1: All experiments were carried out in a 2.4 L stirred tank reactor ("Reactor 1") equipped with baffles and a cross-arm stirrer (see Figure 1).

[0144] The supply tube for solution (α) was 8 cm away from both other tubes, and the tube for solution (γ) was 2.5 cm away from the tube for solution (β). All tubes had an outer diameter of 6 mm and an inner diameter of 2 mm, and they were mounted so that the corresponding outlet was approximately 5 cm below the liquid surface. In the context of the above example, this vessel is also referred to as "Vessel 1." Vessel 1 had a constant nitrogen overflow during all reactions.

[0145] At the start of each example, reactor 1 was filled with 2 liters of water. The temperature was set to 55°C. The stirrer element was turned on and operated constantly at 1000 rpm (revolutions per minute, average energy input 4.5 W / L).

[0146] I.1.1 Preparation of Comparative Precursor C-TM-OH.1 Solution C-(α.1): NiSO4, CoSO4, and MnSO4 (TM.1, molar ratio 83:12:05, total transition metal concentration: 1.65 mol / kg) in water Solution (β.1): 25% by weight NaOH in water Solution (γ.1): 25% by mass ammonia in water Solutions C-(α.1), (β.1), and (γ.1) were simultaneously introduced into reactor 1. The molar ratio of ammonia to TM.1 was adjusted to 0.25. The total volumetric flow rate was set to adjust the average residence time to 5 hours. The flow rate of solution (β.1) was adjusted via a pH control circuit to maintain a constant pH of 11.9 in the stirred vessel. Reactor 1 was operated continuously while maintaining a constant liquid level in the vessel. The hydroxide of TM.1 was recovered from the vessel by free overflow. The resulting slurry contained approximately 120 g / L of hydroxide of TM.1. This slurry was washed with water and an aqueous solution of sodium hydroxide (1 kg of 25% by weight aqueous sodium hydroxide solution per 1 kg of precursor), filtered, and dried at 120 °C for 14 hours. Comparative precursor C-TM-OH.1 was obtained.

[0147] I.1.2 Preparation of the precursor TM-OH.2 of the invention: Solution (α.2): NiSO4, CoSO4, and MnSO4 (TM.2, molar ratio 83:12:05, total transition metal concentration: 1.65 mol / kg) in water, and glycine, molar ratio of glycine to TM.2: 0.01 Solution (β.2): 25% by weight NaOH in water Solution (γ.2): 25% by mass ammonia in water Solutions (α.2), (β.2), and (γ.2) were simultaneously introduced into reactor 1. The molar ratio of ammonia to TM.2 was adjusted to 0.15. The total volumetric flow rate was set to adjust the average residence time to 5 hours. The flow rate of solution (β.2) was adjusted via a pH control circuit to maintain a constant pH value of 11.9 in the stirred vessel. Reactor 1 was operated continuously while maintaining a constant liquid level in the vessel. The hydroxide of TM.2 was recovered from the vessel by free overflow. The resulting slurry contained approximately 120 g / l of hydroxide of TM.2. This slurry was washed with water and an aqueous solution of sodium hydroxide (1 kg of 25% by weight aqueous sodium hydroxide solution per 1 kg of solid hydroxide), filtered, and dried at 120 °C for 14 hours. The precursor TM-OH.2 of the present invention was obtained.

[0148] I.1.3 Preparation of the precursor TM-OH.3 of the invention: Solution (α.3): NiSO4, CoSO4, and MnSO4 (TM.3, molar ratio 83:12:05, total transition metal concentration: 1.65 mol / kg) in water, and glycine, molar ratio of glycine to TM.3: 0.03 Solution (β.3): 25% by weight NaOH in water Solution (γ.3): 25% by weight ammonia in water Solutions (α.3), (β.3), and (γ.3) were simultaneously introduced into reactor 1. The molar ratio of ammonia to ZM.3 was adjusted to 0.15. The total volumetric flow rate was set to adjust the average residence time to 5 hours. The flow rate of solution (β.3) was adjusted via a pH control circuit to maintain a constant pH value of 11.4 in the stirred vessel. Reactor 1 was operated continuously while maintaining a constant liquid level in the vessel. The mixed hydroxide TM.3 was recovered from the vessel by free overflow. The resulting slurry contained approximately 120 g / l of the mixed hydroxide TM.3. The slurry was washed with water and an aqueous solution of sodium hydroxide (1 kg of 25% by weight aqueous sodium hydroxide solution per 1 kg of solid hydroxide), filtered, and dried at 120 °C for 14 hours. The precursor TM-OH.3 of the present invention was obtained.

[0149] SEM images of C-TM-OH.1, TM-OH.2, and TM-OH.3 are shown in Figures 3 and 4.

[0150] [Table 1]

[0151] The organic carbon content corresponds, for example, to the difference in C content between TM-OH.2 and TM-OH.3.

[0152] The orientation of the primary particles is quantified by the angle G between the orientation of the primary particles and the ideal radial direction, as compared above.

[0153] I.1.4 Preparation of pre-calcined precursor of the invention TMO.3: TM-OH.3 was placed in an aluminum crucible and heated to 400 °C under oxygen atmosphere at a heating rate of 1 K / min for 60 min. TMO.3 was obtained. The amount of organic carbon in d-TM.OH.3 was found to be 0.08 wt. % compared to 0.30% in TM-OH.3.

[0154] I.1.5 Preparation of Comparative Precursor C-TM-OH.4 Solution C-(α.4): NiSO4, MnSO4 (TM.4, molar ratio 95:05, total transition metal concentration: 1.65 mol / kg) in water Solution (β.4): 25% by weight NaOH in water Solution (γ.4): 25% by weight ammonia in water Solutions C-(α.4), (β.4), and (γ.4) were simultaneously introduced into reactor 1. The molar ratio of ammonia to TM.4 was adjusted to 0.25. The total volumetric flow rate was set to adjust the average residence time to 5 hours. The flow rate of solution (β.4) was adjusted via a pH control circuit to maintain a constant pH of 11.3 in the stirred vessel. Reactor 1 was operated continuously while maintaining a constant liquid level in the vessel. The mixed hydroxide of TM.4 was recovered from the vessel by free overflow. The resulting slurry contained approximately 120 g / L of the mixed hydroxide of TM.4. This slurry was washed with water and an aqueous solution of sodium hydroxide (1 kg of 25% by weight aqueous sodium hydroxide solution per 1 kg of precursor), filtered, and dried at 120 °C for 14 hours. Comparative precursor C-TM-OH.4 was obtained.

[0155] I.1.6 Preparation of the precursor TM-OH.5 of the invention: Solution (α.5): NiSO4 and MnSO4 (TM.5, molar ratio 95:05, total transition metal concentration: 1.65 mol / kg) in water, and glycine, molar ratio of glycine to TM.5: 0.01 Solution (β.5): 25% by weight NaOH in water Solution (γ.5): 25% by mass ammonia in water Solutions (α.5), (β.5), and (γ.5) were simultaneously introduced into reactor 1. The molar ratio of ammonia to TM.5 was adjusted to 0.15. The total volumetric flow rate was set to adjust the average residence time to 5 hours. The flow rate of solution (β.5) was adjusted via a pH control circuit to maintain a constant pH of 10.3 in the stirred vessel. Reactor 1 was operated continuously while maintaining a constant liquid level in the vessel. TM.5 hydroxide was recovered from the vessel by free overflow. The resulting slurry contained approximately 120 g / L of mixed hydroxide of TM.5. This slurry was washed with water and an aqueous solution of sodium hydroxide (1 kg of 25% by weight aqueous sodium hydroxide solution per 1 kg of solid hydroxide), filtered, and dried at 120 °C for 14 hours. TM-OH.5, a precursor of the present invention, was obtained.

[0156] During the preparation of C-TM.OH.4, strong changes in pH value were observed, accompanied by undesirable changes in particle size distribution, whereas a stable process with constant pH value and particle size distribution was observed during the precipitation of TM-OH.5 during the reaction time.

[0157] SEM images of C-TM-OH.4 and TM.OH.5 are shown in Figure 5 .

[0158] [Table 2]

[0159] I.1.7 Preparation of seed slurry fraction s1: Solution C-(α.6): NiSO4, CoSO4, and MnSO4 (TM.6, molar ratio 87:05:08, total transition metal concentration: 1.65 mol / kg) in water Solution (β.6): 25% by weight NaOH in water Solution (γ.6): 25% by mass ammonia in water Process (b1.6) Solution C—(α.6), (β.6), and (γ.6)—were simultaneously introduced into reactor 1. The molar ratio of ammonia to TM.6 was adjusted to 0.2. The total volumetric flow rate was set to adjust the average residence time to 5 hours. The flow rate of solution (β.6) was adjusted by a pH control circuit to maintain a constant pH value of 12.15 in the stirred vessel. Reactor 1 was operated continuously while maintaining a constant liquid level in the vessel. After reactor 1 had been operated for 15 hours, the particle size distribution did not change any further. The collection vessel was then emptied, and seed slurry fraction s1 was collected every 5 hours. This seed slurry fraction s1 had a solids content of 120 g / l, was characterized by a d50 of 4.1 μm, and a span of (d90-d10) / d50=1.69.

[0160] I.2 Preparation of comparative precursor C-TM-OH.6 and precursor of the invention TM-OH.7, steps C-(b2.6) and (b2.7) The following reactions were carried out in Reactor 2, which was similar to Reactor 1 but had a volume of 3.2 liters.

[0161] I.2.1 Preparation of comparative precursor C-TM-OH.6: Reactor 2 was charged with 1.6 L of water containing 61 g of ammonium sulfate and heated to 55 °C under a nitrogen atmosphere. Solution (β.6) was added until the pH reached 12.05. The agitator was set to 1000 rpm, and 320 ml of slurry s1 was added. Solutions C-(α.6), (β.6), and (γ.6) were continuously fed into reactor 2 until the pH of the mother liquor reached 12.05 and the molar ratio of NH3 to TM.6 was 0.55. The mother liquor was separated from the solids and removed from the reactor through a clarifier attached to the top of the reactor. The flow rates of each solution were adjusted to give an average residence time of 5 hours. The agitator speed was kept constant. The particles were allowed to grow to a particle size of approximately 13–14 μm, after which they were filtered, washed with water, dried, and sieved through a 30 μm mesh size sieve. Comparative precursor C-TM-OH.6 was obtained.

[0162] I.2.2 Preparation of the precursor of the invention, TM-OH.7 Solution (α.7): NiSO4, CoSO4, and MnSO4 (TM.7, molar ratio 87:05:08, total transition metal concentration: 1.65 mol / kg) in water, and glycine, molar ratio of glycine to TM.3: 0.03 Solution (β.7): 25% by weight NaOH in water Solution (γ.7): 25% by mass ammonia in water Reactor 2 was charged with 1.6 L of water containing 61 g of ammonium sulfate and heated to 55 °C under a nitrogen atmosphere. Solution (β.7) was added until the pH reached 12.05. The agitator was set to 1000 rpm, and 320 ml of slurry s1 was added. Solutions (α.7), (β.7), and (γ.7) were continuously fed into reactor 2 so that the pH of the mother liquor reached 12.05 and the molar ratio of NH3 to TM.7 was 0.55. The mother liquor was separated from the solids and removed from the reactor through a clarifier attached to the top of the reactor. The flow rates of each solution were adjusted to achieve an average residence time of 5 hours. The agitator speed was kept constant. The particles were allowed to grow to a particle size of approximately 13–14 μm, after which they were filtered, washed with water, dried, and sieved through a 30 μm mesh size sieve. TM-OH.7, the precursor of the present invention, was obtained.

[0163] II. Preparation of Cathode Active Material and Electrode Fabrication II.1 Preparation of Comparative Cathode Active Material C-CAM.1 and Cathode Active Materials CAM.2 and CAM.3 of the Invention: Each precursor was heat-treated at approximately 300 °C. Each pre-calcined material was mixed with LiOH·H2O, Al2O3, and Zr(OH)4 in the following molar ratios: Li:(Ni+Co+Mn) 1.05:1, Al:(Ni+Co+Mn) 0.02:1, and ZrLi:(Ni+Co+Mn) 0.0025:1. The mixture was poured into an alumina crucible and heated to 750 °C for 6 hours at a heating rate of 3 °C / min under an oxygen atmosphere (10 exchanges / h). The resulting cathode active materials were cooled to room temperature at a cooling rate of 10 °C / min and then sieved using a 30 μm mesh. The precursor C-TM-OH.1 yielded comparative cathode active material C-CAM.1, the precursor TM-OH.2 yielded inventive cathode active material CAM.2, and the precursor d-TM.OH.3 yielded CAM.3.

[0164] II.2 Preparation of Comparative Cathode Active Material C-CAM.4 and Cathode Active Material CAM.5 of the Invention: Each precursor was mixed with LiOH·HO in a molar ratio of 1.05:1 Li:(Ni+Co+Mn), poured into an alumina crucible, and heated to 750°C for 6 hours at a heating rate of 3°C / min under an oxygen atmosphere (10 exchanges / h). The resulting cathode active materials were cooled to room temperature at a cooling rate of 10°C / min and then sieved using a 30 μm mesh size. Comparative cathode active material C-CAM.4 was obtained from precursor C-TM-OH.4, and the cathode active material of the present invention CAM.5 was obtained from precursor TM-OH.5.

[0165] II.3 Preparation of comparative cathode active material C-CAM.6 and cathode active material CAM.7 of the present invention: Each precursor was mixed with LiOH·HO, AlO, and Zr(OH) in the following molar ratios: Li:(Ni+Co+Mn) 1.05:1, Al:(Ni+Co+Mn) 0.02:1, and Zr:Li:(Ni+Co+Mn) 0.003:1. The mixture was poured into an alumina crucible and heated to 760°C for 6 hours at a heating rate of 1.3°C / min under an oxygen atmosphere (10 exchanges / h). The resulting materials were cooled to room temperature at a cooling rate of 10°C / min and then sieved through a 30 μm mesh. Precursor C-TM-OH.6 yielded comparative cathode active material C-CAM.6, and precursor TM-OH.7 yielded cathode active material CAM.7.

[0166] II.4 Electrode manufacturing and testing Electrode fabrication and half-cell electrochemical measurements: The electrodes contained 94% of each of the inventive or comparative cathode active materials, 3% carbon black (Super C65), and 3% binder (polyvinylidene fluoride, Solef 5130). The slurry was mixed with N-methyl-2-pyrrolidone and cast onto aluminum foil with a doctor blade. The electrodes were dried in vacuum at 105°C for 6 hours, after which circular electrodes were punched out, weighed, and dried in vacuum at 120°C for 12 hours before being placed in an Ar-filled glove box.

[0167] A coin-type electrochemical cell was assembled in an argon-filled glove box. A 14 mm diameter positive electrode (loading 8.0 ± 0.5 mg cm) was used. -2 The 0.58 mm thick Li foil was separated by a glass fiber separator (Whatman GF / D). A volume of 95 μl of 1 M LiPF in a 3:7 mass ratio of ethylene carbonate (EC):ethyl methyl carbonate (EMC) was used as the electrolyte. The cells were galvanostatically cycled between 3.1 and 4.3 V at room temperature in a Maccor 4000 battery cycler by applying the following C rates:

[0168] [Table 3]

[0169] After charging at the above C rate, all charging steps except the first charge were constant voltage steps (CV * ) for 1 hour or until the current reached 0.02C.

[0170] During resistance measurements (performed every 25 cycles at 25°C), the cell was charged at 0.2 C to a state of charge of 50% of the previous discharge capacity. This was followed by a 30-minute open-circuit step to equilibrate the cell. Finally, a 2.5 C discharge current was applied for 30 seconds, and the resistance was measured. After the current pulse, the cell was again equilibrated at open circuit for 30 minutes and then further discharged at 0.2 C to 3.0 V.

[0171] [Table 4]

Claims

1. 1. A method for producing a particulate (oxy)hydroxide of TM, wherein the TM is metallic and comprises at least 60 mol % nickel, said method comprising the steps of: (a) providing an aqueous solution (α) containing an α-amino acid or a β-amino acid or an alkali metal salt thereof in a molar ratio of 0.01 to 0.05 relative to 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, and an aqueous solution (β) containing an alkali metal hydroxide, and optionally an aqueous solution (γ) containing ammonia; (b) combining solution (α) and solution (β), and, where applicable, solution (γ), in a stirred tank reactor at a pH value in the range of 10.0 to 13.0, thereby producing solid particles of nickel-containing hydroxide, wherein the solid particles are slurried; and The α-amino acid and the β-amino acid are selected from alanine, glycine, and serine.

2. TM is a compound represented by the general formula (I) (Ni a Co b Mr c ) 1-d M d (I) (wherein a is in the range of 0.7 to 0.99; b is in the range of 0.01 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 at least one of Al, Mg, Ti, Mo, Nb, Ta, W, and Zr; b+c>0, a + b + c = 1) The method of claim 1, wherein the metal combination is

3. 3. The method of claim 1, wherein the α-amino acid is selected from glycine and its sodium and potassium salts.

4. 4. The process according to claim 1, wherein the aqueous solutions (α) and (β) are fed into a stirred tank reactor via coaxial nozzles.

5. 5. The method according to any one of claims 1 to 4, wherein step (b) is carried out in two substeps (b1) and (b2), and substep (b1) is carried out at a pH value 0.2 to 2.0 units higher than substep (b2).

6. 5. The method according to claim 1, wherein step (b) is carried out at a pH value that varies by at most 0.2 units.

7. 1. A particulate (oxy)hydroxide of TM, wherein TM comprises at least 70 mol % of nickel, said (oxy)hydroxide having an average secondary particle size (D50) in the range of 2 to 20 μm, TM comprises 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, said (oxy)hydroxide containing C in the range of 500 ppm to 1 mass % as an α-amino acid or a β-amino acid or an alkali metal salt thereof, and at least 60 vol % of the secondary particles consist of agglomerated primary particles, the primary particles being perfectly radially oriented and the primary particles having a deviation from perfect radial orientation of at most 5 degrees.

8. 8. A particulate (oxy)hydroxide according to claim 7, wherein the particles exhibit a plurality of concentric rings detectable by scanning electron microscopy of a cross section of such a particle.

9. TM is a compound represented by the general formula (I) (Ni a Co b Mr c ) 1-d M d (I) (wherein a is in the range of 0.7 to 0.99; b is 0 or in the range of 0.01 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 at least one of Al, Mg, Ti, Mo, Nb, Ta, W, and Zr; a + b + c = 1) 9. The particulate (oxy)hydroxide according to claim 7 or 8, wherein the metal combination is:

10. 10. A particulate (oxy)hydroxide according to any one of claims 7 to 9, having a bimodal particle size distribution with a first maximum in the range of 3 to 7 μm and a second maximum in the range of 11 to 17 μm.

11. A particulate (oxy)hydroxide according to any one of claims 7 to 10, having a shape factor in the range of 0.87 to 0.

99.

12. 12. Use of the particulate (oxy)hydroxide according to any one of claims 7 to 11 for the manufacture of a cathode active material for a lithium ion battery.

13. 12. A method for producing an electrode active material for a lithium ion battery, comprising the steps of: mixing the particulate transition metal (oxy)hydroxide according to any one of claims 7 to 11, or the pre-calcined particulate transition metal (oxy)hydroxide according to any one of claims 7 to 11, with a lithium source; and heat-treating the mixture at a temperature in the range of 600 to 1000°C.

14. (1) at least one electrode active material prepared according to claim 13; (2) carbon in a conductive state; (3) Binder material a cathode comprising:

15. Based on the sum of (1), (2) and (3), (1) 80 to 98 wt. % of a cathode active material; (2) 1 to 17% by weight of carbon; (3) 1 to 15% by mass of a binder material The cathode of claim 14 comprising:

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