Method for producing hydroxides for precursors of cathode materials for rechargeable batteries - Patents.com

Abstract

The present invention generally relates to hydroxides for precursors of cathode materials for rechargeable batteries. In particular, the present invention relates to a method for producing aqueous slurries containing hydroxides of at least one metal element, such as Ni, Co, and / or Mn. The aqueous slurries can then be used to make precursors for lithium transition metal oxides for various applications, particularly for rechargeable batteries.

Description

[Technical Field]

[0001] The present invention generally relates to hydroxides for precursors of cathode materials for rechargeable batteries. In particular, the present invention relates to a method for producing aqueous slurries containing hydroxides of at least one metal element, such as Ni, Co, and / or Mn. The aqueous slurries can then be used to make precursors for lithium transition metal oxides for various applications, particularly for rechargeable batteries. [Background technology]

[0002] Lithium-ion secondary batteries typically include a negative electrode (anode), an electrolyte, and a positive electrode (cathode) that includes a lithium transition metal oxide as an active material capable of intercalating and deintercalating lithium. The lithium transition metal oxides are generally prepared from transition metal hydroxides, oxides, or oxyhydroxides that result from a co-precipitation process that involves mixing a metal salt solution with an alkaline solution in the presence of a complexing agent.

[0003] Automotive applications are expected to become increasingly mainstream in the lithium-ion battery market in the future. To be competitive, batteries for automotive applications must be manufactured at the lowest possible cost. The majority of the cost comes from the active materials, and the cost of precursors is reflected in the cost of the active materials. Providing these precursors through more efficient and / or cheaper processes, ideally without compromising their quality, can help reduce costs and promote market acceptance of lithium-ion secondary batteries.

[0004] In view of the above, there is a constant need for further improvements in the precursor manufacturing process. Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention aims to provide an improved method for making materials that can then be used directly / indirectly as precursors to lithium transition metal cathode materials for positive electrodes. [Means for solving the problem]

[0006] Viewed from a first aspect, the present invention can provide a method for producing a first aqueous slurry containing first hydroxide or oxyhydroxide particles of at least one element, the at least one element including at least one of Ni, Co, and Mn. The first aqueous slurry, or the first hydroxide or oxyhydroxide particles, can be used as a source of seed particles in a second hydroxide precipitation process, which can ultimately be used as a precursor to a lithium transition metal cathode material for a positive electrode. Such a method according to the present invention includes continuously supplying a first stream of a metal salt solution containing one or more elements to a reaction vessel; continuously feeding a second stream of an aqueous solution of one or more alkali hydroxides to the reaction vessel; Aqueous ammonia, i.e., aqueous ammonia (NH 3(aq) continuously feeding a third stream of mixing the first, second, and third streams to obtain a first aqueous slurry in a reaction vessel; The method further includes continuously removing a fourth stream of the first aqueous slurry from the reaction vessel; In the method, the first aqueous slurry has a pH value of at most 13.0 and at least 12.0, the pH value being measured on a sample of the first aqueous slurry at 20°C; NH in the first aqueous slurry 3(aq) The supply of the third stream is controlled so that the concentration is at least 1.0 g / L and at most 5.0 g / L to limit the growth of the first hydroxide or oxyhydroxide particles to a median particle size D50 in the range of at least 0.7 μm and at most 3.0 μm.

[0007] The hydroxide or oxyhydroxide particles of one or more elements according to the present invention have a composition that can be represented by the following general formula: Me-O x (OH) 2-x , where 0≦×≦2, and Me includes at least one of Ni, Co, and Mn, and optionally at least one other element such as an impurity such as Na, S, etc. According to the present invention, the disclosed NH 3(aq) The disclosed pH value combined with the concentration can provide stable nucleation and controllable growth of the first hydroxide or oxyhydroxide to a target size, so that the first aqueous slurry contains the first hydroxide or oxyhydroxide with a controllable particle size, which can serve as an excellent seed source for the subsequent precipitation process. Because the first hydroxide or oxyhydroxide is prepared by a steady-state reaction, it provides an efficient and repeatable method for preparing seed particles even on an industrial scale.

[0008] In the preparation of the first aqueous slurry, a pH value higher than 13.0 may result in small, potentially fragile crystal nuclei, and therefore the slurry may risk gelling. A pH value lower than 12.0 may result in inefficient nucleation and / or uncontrollable growth of the first hydroxide or oxyhydroxide. A pH value of at least 12.5 is more preferred, and at least 12.6 is even more preferred. The pH value is within the range of 12.0-13.0, but should be in the range of 1.0 g / L to 5.0 g / L of NH 3 . 3(aq) The concentration can effectively result in first hydroxide or oxyhydroxide particles having a median particle size D50 in the range of 0.7 to 3.0 μm. More preferably, NH 3(aq) The concentration is at least 1.0 g / L and at most 4.0 g / L, which, when combined with the disclosed pH values, allows for a desired median particle size D50 of the first hydroxide or oxyhydroxide ranging from at least 0.7 μm to at most 2.0 μm. Even more preferably, the NH 3(aq)The concentrations are at least 2.0 g / l and at most 4.0 g / l, which, when combined with the disclosed pH values, can result in a desired median particle size D50 of the first hydroxide or oxyhydroxide ranging from at least 1.0 μm to at most 2.0 μm.

[0009] Within the concept of the first aspect according to the present invention, the conditions used in the method, such as temperature and mixing settings, may be further adjusted to optimize the resulting first aqueous slurry. Some embodiments are described in the detailed description.

[0010] As mentioned above, the resulting first aqueous slurry according to the present invention can serve as an excellent seed source for subsequent precipitation. Accordingly, a second aspect of the present invention provides a method for producing a second hydroxide or oxyhydroxide particle of one or more elements, the one or more elements including at least Ni, Co, and Mn. The second hydroxide or oxyhydroxide particle can ultimately be used as a precursor for a lithium transition metal cathode active material for a positive electrode. Such a method according to the present invention includes: a) providing a quantity of a first aqueous slurry comprising first hydroxide or oxyhydroxide particles in a reaction vessel, the first hydroxide or oxyhydroxide having a median particle size D50 in the range of at least 0.7 μm to at most 3.0 μm, preferably the first aqueous slurry and / or the first hydroxide or oxyhydroxide is obtained by a method according to the first aspect of the invention disclosed in the present disclosure; b) a fifth stream of a metal salt solution containing one or more elements, and optionally an aqueous ammonia solution (NH 3(aq) a seventh stream of the above-mentioned condensed water to the reactor vessel; c) establishing or maintaining conditions in the reaction vessel to cause the one or more elements to precipitate from the metal salt solution as hydroxides on the first hydroxide or oxyhydroxide to obtain a second aqueous slurry in the reaction vessel comprising second hydroxide or oxyhydroxide particles of the one or more elements.

[0011] According to the present invention, the disclosed seed slurry, i.e., the first aqueous slurry, combined with the disclosed precipitation process, contributes to stable and / or controlled growth of the second hydroxide or oxyhydroxide on the seeds, i.e., on the first hydroxide or oxyhydroxide particles, without further nucleation and aggregation, such that the second aqueous slurry contains hydroxide or oxyhydroxide particles with a homogeneously distributed second hydroxide or oxyhydroxide having the desired particle size and excellent sphericity with a narrow particle size distribution range. The excellent sphericity and narrow particle size distribution range of the second hydroxide or oxyhydroxide according to the present invention remain in the cathode material when used as a precursor for the cathode material. In other words, the cathode material also has excellent sphericity. The spherical cathode material has a favorable relationship to tap density.

[0012] Typically, in known manufacturing methods, hydroxides for cathode material precursors are prepared by a two-step in-situ coprecipitation process: a first step, a nucleation process, to generate particles, and a second step, a particle growth process, to grow the nuclei generated in the nucleation process. Because the nucleation process is fast, i.e., new nuclei are generated quickly, and the reaction conditions for the growth process are different from those for the nucleation process, one issue with these types of manufacturing methods is process controllability. There is a potential risk of simultaneous nuclei growth and generation during the transition from the nucleation process to the growth process. Therefore, there is a risk that the particle size distribution of the formed nuclei will be largely non-uniform. A further problem can be the difficulty of reproducibly repeating the process, as the amount of nuclei generated can easily change, thus changing the overall reaction time between preparation processes for hydroxides of the same size and metal content.

[0013] In the first and second aspects of the present invention, it is possible to separate the nucleation and particle growth reactions, separating the individual processes, which is advantageous for process control. Because there is no need to change from the nucleation process to the growth process in the production of hydroxide, both processes may be carried out with greater reproducibility and predictability, thus resulting in improved production scalability compared to the two-stage in situ co-precipitation process.

[0014] Following the concept of the first and second aspects of the present invention, there is further provided a third aspect of the present invention, which is a method for producing hydroxide or oxyhydroxide powder of one or more elements, the method comprising the steps of: I) providing an aqueous slurry according to the second aspect of the present invention; II) separating the hydroxide or oxyhydroxide from a liquid fraction of the aqueous slurry; and III) drying the separated hydroxide or oxyhydroxide.

[0015] There is also provided a fourth aspect of the present invention, which is the use of the aqueous slurry according to the second aspect of the present invention or the hydroxide powder or oxyhydroxide powder according to the third aspect of the present invention for producing a positive electrode active material for a secondary battery.

[0016] There is further provided a fifth aspect of the present invention, which is a method for producing a positive electrode active material using hydroxide or oxyhydroxide particles produced according to the first and second aspects of the present invention.

[0017] Various embodiments according to the present invention are disclosed in the claims and in this specification. The embodiments and examples listed in the claims and in the specification can be freely combined with each other unless otherwise expressly stated. Throughout this specification, when any numerical range is provided, the range also includes the endpoints unless otherwise expressly stated. [Brief explanation of the drawings]

[0018] For reference, figures are attached to provide a better understanding of the teachings of the present invention.

[0019] [Figure 1] FIG. 1 shows a scanning electron microscope (SEM) image of the particles obtained from the process of Example 1.1. [Figure 2] FIG. 2 shows an SEM image of the particles obtained from the process of Example 1.2. [Figure 3] FIG. 3 shows an SEM image of the particles obtained from the process of Example 1.3. [Figure 4] FIG. 4 shows an SEM image of the particles obtained from the process of Example 2.2. [Figure 5] FIG. 5 shows an SEM image of the particles obtained from the process of Example 2.3. [Figure 6] FIG. 6 shows an SEM image of the particles obtained in Comparative Example 1, 2 hours after the start of the process. DETAILED DESCRIPTION OF THE INVENTION

[0020] In the following detailed description, preferred embodiments are described in detail to enable the practice of the invention. Although the invention is described with reference to these specific preferred embodiments, it will be understood that the invention is not limited to these preferred embodiments. On the contrary, the invention includes numerous alternatives, modifications, and equivalents that will become apparent in light of the following detailed description and the accompanying drawings.

[0021] When used in the present specification and claims, the term "comprising" should not be interpreted as being limited to the means listed thereafter, nor does it exclude other elements or steps. This term must be interpreted as specifying the presence of the mentioned structure, integer, step, or component, but does not preclude the presence or addition of one or more other structures, integers, steps, or components, or groups thereof. Thus, the scope of the expression "a composition comprising components A and B" is not limited to a composition consisting only of components A and B. This means that, in the context of the present invention, the only relevant components in the composition are A and B. Thus, the terms "comprising" and "including" encompass the more restrictive terms "consisting essentially of" and "consisting of."

[0022] The term "positive electrode active material" (also known as cathode active material) as used herein and in the claims is defined as a material that is electrochemically active within a positive electrode or cathode. An active material should be understood to be a material that can capture and release Li-ions when subjected to a voltage change over a period of time.

[0023] As used in this disclosure, the term "cathode" is defined as a material that includes a cathode active material in addition to other components that are not electrochemically active, particularly a conductive agent such as a binder, such as carbon black or PVDF.

[0024] As used herein, "concentration of NH3(aq)" or like terms means the concentration of ammonia in an aqueous solution.

[0025] In a first aspect, the present invention provides a method for producing a first aqueous slurry comprising first hydroxide or oxyhydroxide particles of at least one element, the at least one element comprising at least one of Ni, Co, and Mn. The first aqueous slurry or the first hydroxide or oxyhydroxide particles may be used as a source of seed particles in a precipitation process of a second hydroxide or oxyhydroxide, which can ultimately be used as a precursor to a lithium transition metal cathode material for a positive electrode. Such a method according to the present invention comprises: continuously supplying a first stream of a metal salt solution containing one or more elements to a reaction vessel; continuously feeding a second stream of an aqueous solution of one or more alkali hydroxides to the reaction vessel; Aqueous ammonia, i.e., aqueous ammonia (NH 3(aq) continuously feeding a third stream of mixing the first, second, and third streams to obtain a first aqueous slurry in the reaction vessel, the method further comprising continuously removing a fourth stream of the first aqueous slurry from the reaction vessel; In the method, the first aqueous slurry has a pH value of at most 13.0 and at least 12.4, the pH value being measured on a sample of the first aqueous slurry at 20°C; NH in the first aqueous slurry 3(aq) The third flow is controlled so that the concentration is at least 1.0 g / L and at most 5.0 g / L to limit the growth of the first hydroxide or oxyhydroxide particles to a median particle size D50 in the range of at least 0.7 μm and at most 3.0 μm.

[0026] During the course of the manufacturing process, the precipitated hydroxides may be partially oxidized depending on the manufacturing process atmosphere, and therefore the aqueous slurry may contain oxyhydroxides. Note that atmospheric conditions are not required to achieve the claimed invention.

[0027] According to such methods of the present invention, the disclosed NH 3(aq) The disclosed pH value, combined with the concentration, contributes to stable nucleation and controllable growth of the first hydroxide or oxyhydroxide. Thus, the first aqueous slurry contains a first hydroxide or oxyhydroxide with a controllable particle size, which can serve as an excellent seed source for the subsequent precipitation process. Because the first hydroxide or oxyhydroxide is prepared by a steady-state reaction, it provides an efficient and repeatable manufacturing method for preparing seed particles even on an industrial scale. As will be understood by those skilled in the art, the pH value can be measured using a pH meter, such as a 780 Metrohm meter. As will be understood by those skilled in the art, the NH3(aq) concentration can be measured using a commercially available titration device, such as a Metrohm 848 Titrino Plus.

[0028] In this method, the continuous flow supply and continuous flow removal are commonly known as continuous mode, which in this case is continuous precipitation in the art and may be implemented by using a continuous stirred tank reactor (CSTR) with an overflow or other similar system known to those skilled in the art. The mixing step involved in continuous mode facilitates the chemical reaction in the reaction vessel to reach a steady state (i.e., a normal state) to obtain the first aqueous slurry. The time required to reach a steady state depends on the effective volume and total flow rate of the reactor, as known to those skilled in the art. Therefore, the time will vary depending on the actual application and can be applied by those skilled in the art without undue burden.

[0029] To control the growth of the first hydroxide or oxyhydroxide, it may be beneficial to control the mixing of the first aqueous slurry in the reaction vessel. According to some embodiments, the mixing step is carried out using a stirring power, which is controlled by the mixing of the first aqueous slurry to keep the particles separated, i.e., to prevent agglomeration. 3 at least 15 kW per m of the first aqueous slurry, preferably 3more preferably at least 20 kW per m of the first aqueous slurry 3 At least 25kW per

[0030] According to some embodiments, the first aqueous slurry in the reaction vessel may have a temperature of at least 40°C and at most 80°C, preferably at least 45°C and at most 65°C, more preferably at least 50°C and at most 60°C.

[0031] According to some embodiments, a non-oxidizing gas atmosphere is maintained within the reaction vessel, the non-oxidizing gas preferably being N2 or Ar, or a mixture of N2 and Ar.

[0032] According to some embodiments, the NH 3 in the first aqueous slurry in the reaction vessel 3(aq) The concentration is at least 1.0 g / L and at most 4.0 g / L, limiting the median particle size D50 of the first hydroxide or oxyhydroxide to a range of at least 0.7 μm and at most 2.0 μm. According to some embodiments, the NH 3 in the first aqueous slurry in the reaction vessel 3(aq) The concentration is at least 2.0 g / l and at most 4.0 g / l, limiting the median particle size D50 of the first hydroxide or oxyhydroxide to a range of at least 1.0 μm and at most 2.0 μm.

[0033] The target median particle size d50 can be achieved by adjusting the conditions of the method according to the first aspect of the invention. According to some embodiments, the method comprises reducing the median particle size d50 of the first hydroxide or oxyhydroxide by: Decreasing the ratio of the amount of the first stream to the amount of the second stream to increase the pH value of the first aqueous slurry; and / or The ratio of the amount of the third stream to the sum of the amounts of the first and second streams is decreased to reduce the amount of NH 3 in the aqueous slurry. 3(aq) Decreasing the concentration, and / or This is achieved by increasing the stirring power required.

[0034] According to some embodiments, the method comprises increasing the median particle size d50 of the first hydroxide or oxyhydroxide by: increasing the ratio of the amount of the first stream to the amount of the second stream to decrease the pH of the first aqueous slurry; and / or Increasing the ratio of the amount of the third stream to the sum of the amounts of the first and second streams to increase the amount of NH 3 in the first aqueous slurry. 3(aq) Increasing the concentration, and / or This is achieved by reducing the stirring power required.

[0035] According to some embodiments of the first aspect of the present invention, at least one element in the first hydroxide or oxyhydroxide particles is Ni with a content x, where 5.0 mol%≦x%, preferably x≧60.0 mol%, more preferably x≧80.0 mol%, Co having a content y, where 0≦y≦30.0 mol%, and Mn with a content z, where 0≦z≦85.0 mol%, and Al having a content q, where 0≦q≦10.0 mol%, and one or more additional elements in a content r, the additional elements being from the list B, Ba, Ca, Ce, Cr, Fe, La, Mg, Mo, Nb, Si, Sr, Ti, Y, V, W, Zn, Na, S, and Zr, and 0≦r≦5.0 mol%, x, y, z, q, and r are the contents, expressed in mole percent, of the at least one element in the first hydroxide or oxyhydroxide relative to the total molar content, where x+y+z+q+r=100 mole percent, and the values ​​x, y, z, q, and r are measured by inductively coupled plasma (ICP) techniques. It will be understood that the formula ≧0 also includes the absence of an element.

[0036] As mentioned above, the resulting first aqueous slurry according to the present invention can serve as an excellent seed source for subsequent precipitation. Therefore, the present invention also provides a method according to a second aspect of the present invention for producing a second aqueous slurry containing second hydroxide or oxyhydroxide particles of one or more elements, the one or more elements including at least Ni, Co, and Mn. The second hydroxide or oxyhydroxide particles can ultimately be used as a precursor to a lithium transition metal cathode active material for a positive electrode. Such a method according to the present invention includes: a) providing a quantity of a first aqueous slurry comprising first hydroxide or oxyhydroxide particles in a reaction vessel, the first hydroxide or oxyhydroxide having a median particle size D50 in the range of at least 0.7 μm to at most 3.0 μm, preferably the first aqueous slurry and / or the first hydroxide or oxyhydroxide is obtained by a method according to the first aspect of the invention disclosed in the present disclosure; b) providing a fifth stream of a metal salt solution containing one or more elements to the reaction vessel; c) adding to the reaction vessel a sixth stream of one or more aqueous alkali hydroxides, and optionally an aqueous ammonia solution (NH 3(aq) providing a seventh stream of d) establishing or maintaining conditions in the reaction vessel to cause the one or more elements to precipitate from the metal salt solution as hydroxides on the first hydroxide or oxyhydroxide to obtain a second aqueous slurry in the reaction vessel comprising second hydroxide or oxyhydroxide particles of the one or more elements.

[0037] The disclosed seed slurry, i.e., first aqueous slurry, combined with the disclosed precipitation process, contributes to the stable growth of second hydroxides on the seeds, i.e., on the first hydroxide or oxyhydroxide particles, without further nucleation and aggregation, such that the second aqueous slurry contains second hydroxides or oxyhydroxides with a homogeneously distributed desired particle size, and the second hydroxide or oxyhydroxide particles have excellent sphericity with a narrow particle size distribution range, which ultimately provides multiple benefits to rechargeable batteries, as discussed above.

[0038] According to some embodiments, step a) providing a quantity of a first aqueous slurry comprising first hydroxide or oxyhydroxide particles in a reaction vessel comprises carrying out a method according to the first aspect of the present invention.

[0039] According to some embodiments, the first hydroxide or oxyhydroxide has a median particle size D50 in the range of up to 2.0 μm, more preferably up to 1.0 μm. Smaller seed particle sizes may contribute to higher densification and / or better sphericity of the core of the second hydroxide or oxyhydroxide particles.

[0040] According to some embodiments, establishing or maintaining conditions in the reaction vessel that cause precipitation in step c) comprises an aqueous ammonia solution (NH3) that acts as an ammonium ion donor. (aq) a seventh stream of the sulphur dioxide gas mixture, the seventh stream being a sulphur dioxide gas mixture, and the seventh stream being a sulphur dioxide gas mixture.

[0041] Precipitation is terminated when the second hydroxide or oxyhydroxide particles reach a specified target particle size.

[0042] Further optimized conditions can be applied. According to some embodiments, the sixth stream is controlled so that the second aqueous slurry in the reaction vessel has a pH value of at most 12.2, preferably at least 10, more preferably at most 12.1, and at least 11.0, where the pH value of the second aqueous slurry is the pH value measured on a sample of the second aqueous slurry at 20°C. The disclosed pH value preferably contributes to the particle size such that the hydroxide particle growth reaction occurs over the nucleation reaction, few new nuclei are generated in the aqueous slurry, and metal hydroxides having a specific particle size are formed.

[0043] According to some embodiments, the seventh stream is NH in a second aqueous slurry. 3(aq) The concentration is controlled to be at least 1.0 g / L and at most 20.0 g / L, more preferably at least 1.5 g / L and at most 15 g / L.

[0044] According to some embodiments, b) and c) are continued until a target median particle size D50 of the second hydroxide or oxyhydroxide particles in the second aqueous slurry is obtained and / or until a predetermined maximum solids content of the second aqueous slurry is obtained.

[0045] According to some embodiments, step c) comprises applying a stirring power requirement to the second aqueous slurry, the stirring power requirement being equal to m of the second aqueous slurry. 3 per m3 of second aqueous slurry, preferably at most 40 kW per m3 of second aqueous slurry. 3 5 kW, and / or the stirring power required is m 3 at least 5 kW per m of the second aqueous slurry, preferably 3 At least 10 kW per

[0046] According to some embodiments, step c) comprises maintaining the temperature of the second aqueous slurry in the reaction vessel at at least 45° C., preferably at least 75° C., more preferably at least 80° C. A temperature of at least 80° C. or higher has been found to prevent undesirable cracking of the second hydroxide or oxyhydroxide particles.

[0047] According to a second aspect of the present invention, the one or more elements in the second hydroxide or oxyhydroxide are: Ni with a content b, where 5.0 mol%≦b≦99.0 mol%, Co having a content c, where 0≦c≦30.0 mol%, Mn with a content d, where 0≦d≦85.0 mol%; Al having a content e, where 0≦e≦10.0 mol%, and one or more additional elements in a content f, the additional elements being from the list B, Ba, Ca, Ce, Cr, Fe, La, Mg, Mo, Nb, Si, Sr, Ti, Y, V, W, Zn, Na, S and Zr, with 0≦f≦5.0 mol%, b, c, d, e, and f are the contents, expressed in mole percent, of one or more elements in the second hydroxide or oxyhydroxide relative to the total molar content, where b + c + d + e + f = 100 mole percent, and the values ​​x, y, z, q, and r are measured by inductively coupled plasma (ICP) techniques. It is understood that the formula ≧0 also includes the absence of an element. Preferably, x ≠ b, and alternatively, x > b and / or b ≧ 60.0 mole percent, d ≦ 30.0 mole percent, (b + d) ≧ 1.0 mole percent, and / or d ≧ 50.0 mole percent, f ≦ 3.0 mole percent.

[0048] According to some preferred embodiments of the second aspect of the present invention, in step a) a first aqueous slurry is prepared in a reaction vessel having a volume V(1) and an effective volume V(2), the first aqueous slurry comprising hydroxide or oxyhydroxide particles having a median particle size d50=D1. 、a first aqueous slurry having a solids content SG(1), expressed as weight of hydroxide or oxyhydroxide particles per volume of the first aqueous slurry, and a volume V(1) is provided into the reaction vessel according to Equation 1:

[0049]

number

[0050] SG(2) is the target solids content of the second aqueous slurry expressed as weight of hydroxide or oxyhydroxide particles per volume of the second aqueous slurry, and D2 is the target median particle size D50 of the second hydroxide or oxyhydroxide particles expressed in μm.

[0051] According to some preferred embodiments according to the second aspect of the present invention, the fifth stream is provided at a flow rate expressed as volume per unit time, the metal salt solution has a concentration of one or more elements expressed in moles per unit of volume, the mathematical product of the flow rate and the concentration is continuously increased during a period (T1-T2), preferably an aqueous slurry of seed particles is provided in the reaction vessel, the concentration of the one or more elements in the metal salt solution is kept constant during the period T1-T2, and the flow rate of the metal salt solution (in L / h) at time t within the period T1-T2 is represented by the following formula:

[0052]

number

[0053] where m1 is the mass (grams) of seed particles provided in the reaction vessel, G(t) is the growth rate of hydroxide or oxyhydroxide particles at instant t (μm / hour), where the value of G(t) is not zero, Δt is the time period T1-T2 expressed in hours (h), D'50 is the median particle size of the seed particles expressed in μm, and M Me is the molar mass of one or more elements (grams / mol), and c Me is the concentration (grams / L) of one or more elements in the metal salt solution, and MMe(OH)2 is the molar mass (grams / mol) of the hydroxide or oxyhydroxide of one or more elements. Preferably, the value of G(t) is less than or equal to 2 μm / hr, more preferably less than or equal to 1.5 μm / hr.

[0054] Within the concept of the third aspect of the present invention, there is also provided a method for producing hydroxide or oxyhydroxide powder of one or more elements, the method comprising the steps of: I) providing an aqueous slurry according to the production method of the present invention described above; II) separating the hydroxide or oxyhydroxide particles from the liquid fraction of the aqueous slurry; and III) drying the separated hydroxide or oxyhydroxide particles.

[0055] During the course of the manufacturing process, the hydroxide or oxyhydroxide particles from the aqueous slurry may be further partially oxidized.

[0056] A precursor containing Ni, Co, and Mn in a molar ratio of x:y:z may be prepared in mixed form by a precipitation reaction using the following steps: (1) continuous precipitation of seed particles according to the first embodiment of the present invention, followed by batch precipitation of mixed hydroxides in a reactor with NaOH and mixed metal salts under controlled pH according to the second embodiment of the present invention; (2) removal and filtration of the precursor suspension; and (3) drying of the filtered wet cake. In step (1), the mixed salts may be mixed sulfates, and the pH may typically be 11-12. Effective precursor drying is typically carried out above 100°C for a specific time to remove most of the moisture. The typical moisture content after drying is less than 1 wt. % and can be measured by the well-known Karl Fischer titration method (ASTM D6869) at 250°C. Before drying, the precursor has a pure or ideal hydroxide crystal structure (with space groups P-3m1).

[0057] The dried hydroxide or oxyhydroxide particles according to the present invention, i.e., hydroxide or oxyhydroxide powder, can be used to prepare a positive electrode active material. The hydroxide or oxyhydroxide powder can be mixed with a lithium source to obtain a mixture. The mixture is sintered at a temperature of 650°C to 1000°C. Optionally, a heat treatment at a temperature of 105°C to 750°C can be carried out before mixing.

[0058] The present invention therefore also relates to the use of an aqueous slurry comprising hydroxide or oxyhydroxide particles obtainable by the method according to the first aspect of the present invention, and to the use of a hydroxide or oxyhydroxide powder obtainable by the second aspect of the present invention for producing a positive electrode active material for a secondary battery. [Example]

[0059] The present invention will be further illustrated with reference to some examples and comparative examples. In all examples, the pH value refers to the value measured from the sample at a temperature of 20°C. Furthermore, in all processes of the examples, unless otherwise indicated, a reducing atmosphere was ensured by applying a flow of nitrogen gas into the reaction vessel during the precipitation reaction.

[0060] Measurement methods used in the examples NH 3(aq) Concentration analysis NH of the example sample 3(aq) Concentrations were measured by endpoint titration using a Metrom 848 Titrino Plus instrument. Samples were prepared by adding 1 milliliter of sample solution, 30-40 ml of deionized water, and 1 ml of 1 M NaOH to a titration vessel. The samples were titrated to the endpoint with 0.1 M HCl.

[0061] pH analysis The pH values ​​of the samples were measured with a 780 Metrohm meter calibrated with pH 7 and pH 13 standards. The pH was measured from the samples by cooling them to 20°C, lowering a pH electrode into the sample, and waiting until the pH reading was uniform.

[0062] Solids content analysis To measure the solids content of the precipitated hydroxide in the aqueous slurry, a sample taken from the aqueous slurry (reaction mixture in the examples) was mixed thoroughly, and 10-30 ml of the mixed sample was pipetted onto a filter paper, which was then washed and filtered on a weighed 0.8 μm membrane. The filtered membrane was rinsed with DI water and then dried. The dried membrane was weighed, from which the solids content, expressed as the weight of dry hydroxide per liter of aqueous slurry in g / l, was calculated.

[0063] surface area analysis The specific surface area (SA) of the example samples was measured by the Brunauer-Emmett-Teller (BET) method using Quantachrome Monosorb. The powder sample was placed in a sample tube and heated at 90°C for 2 hours under nitrogen (N2) gas before measurement to remove adsorbed species. The sample was then degassed at room temperature for 5 minutes. The instrument performs a nitrogen adsorption test at 77K. By obtaining the nitrogen adsorption / desorption isotherm, the total specific surface area of ​​the sample in m2 / g is derived.

[0064] Tapped Density Analysis Tapped density (TD) measurements of the example samples were carried out by mechanically tapping a graduated measuring cylinder (100 ml) containing the sample (having a mass W, approximately 60-120 g). After observing the initial powder volume, further volume (cm 3 The measuring cylinder was mechanically tapped for 15 min so that no change in viscosity (V) or mass (W) was observed. TD was calculated as TD = W / V. TD measurements were performed on a J. Engelsmann Stamping volumeter STAV II instrument.

[0065] Particle Size Distribution (PSD) Analysis PSD was measured using a Malvern Mastersizer 3000 with a Hydro MV wetting and dispersion unit after dispersing sample particles in aqueous media. Sufficient ultrasonic irradiation and stirring were applied, and appropriate surfactants were added to improve the dispersion of the metal hydroxide powder. The mean particle sizes D10, D50, and D90 are the particle diameter values ​​at 10%, 50%, and 90% of the cumulative distribution, and the span value is (D90 - D10) / D50.

[0066] Metal content analysis The metal content of the hydroxides was measured by inductively coupled plasma-optical emission spectroscopy (ICP-OES) using an Agilent ICP 720-OES instrument. One gram of powder sample from each example was dissolved in 50 mL of high-purity hydrochloric acid in an Erlenmeyer flask. The flask was covered with a watch glass and heated on a hot plate at 380 °C until the sample was completely dissolved. After cooling to room temperature, the solution and the Erlenmeyer flask's rinse water were transferred to a 250 mL volumetric flask. The volumetric flask was then filled to the 250 mL mark with deionized (DI) water, followed by thorough homogenization. An appropriate amount of the solution was pipetted and transferred to a 250 mL volumetric flask for a second dilution. The volumetric flask was then filled to the 250 mL mark with the internal standard solution and 10% hydrochloric acid, followed by homogenization. Finally, this solution was used for ICP-OES measurement. The contents of metals such as Ni, Mn, and Co are expressed as mole percent of the total metal content in the measured hydroxide.

[0067] Example 1.1 An aqueous slurry of metal hydroxide was prepared according to the following process.

[0068] An initiating solution was prepared by adding 100 L of DI water and 1.0 L of 220 g / L aqueous ammonia solution (NH3(aq)) to a 200 L reactor, adjusting the reactor temperature to 55°C, and maintaining this temperature throughout the process. A 5.5 M NaOH solution was added to adjust the pH value of the initiating solution in the reactor to 12.6-12.8.

[0069] Next, a 2 M NiSO solution was added at a feed rate of 30 L / h, 220 g / L NH(aq) at a feed rate of 0.52 L / h, and a 5.5 M NaOH solution were added continuously to the reactor. The solution was heated to approximately 35 kW / m 3 The mixture was mixed using a mixer with a stirring power of 1000 rpm, and the pH in the reactor was maintained at 12.6-12.8 by adding NaOH solution to establish and maintain the precipitation reaction, thereby preparing an aqueous slurry reaction mixture. 3(aq) The concentration was maintained at about 2 g / L. The reaction was carried out in a continuous mode. When the reaction reached a steady state about 24 hours after initiation, the reactant, i.e., an aqueous slurry of nickel hydroxide, NiOH, having a D50 of 1.2 μm (i.e., seed particles), was collected from the overflow of the reaction vessel.

[0070] Example 1.2 (Particle Growth Process) An initiating solution was prepared by charging a reaction vessel with a working volume of 8.75 L with 6 L of DI water, 55 mL of 220 g / L NH3(aq), and 1.56 L of a 130 g / L aqueous slurry containing the seed particles obtained in Example 1.1, adjusting the temperature inside the reaction vessel to 85°C and maintaining this temperature throughout the process.

[0071] Next, 120 g / L of a metal sulfate solution containing Ni, Mn, and Co (stoichiometric molar ratio of Ni:Mn:Co=65:15:20), 220 g / L of NH3(aq), and 230 g / L of NaOH solution were added, and the reaction temperature was approximately 30 kW / m for the first 30 hours. 3 The stirring power requirement is about 20 kW / m for the rest of the process. 3The precipitation reaction was carried out with stirring at a required stirring power of 1000 kJ / min. The feed rate of the metal sulfate solution was 450 mL / h for the first 2 hours and 980 mL / h for the remainder of the process. During the reaction, the feed rate of the NaOH solution was adjusted to maintain the pH value of the reaction mixture in the reactor at a constant 11.8 ± 0.1, and the feed rate of NH3(aq) was adjusted to maintain the NH3 concentration in the reaction mixture at 2-3 g / L. Reactor samples of the reaction mixture were taken every 2 hours, and the D50 values ​​were measured from them. The process was stopped when the D50 value of the sample reached the target value of approximately 3.9 μm. The duration of the process was 36 hours. During the process, a portion of the liquid fraction of the reaction mixture was pumped out of the reactor using a concentrator. The solids content of the reaction mixture in the reactor vessel was approximately 800 g / L at the end of the process.

[0072] Example 1.3 (Particle Growth Process) An initiating solution was prepared by charging a reaction vessel with a working volume of 8.75 L with 6 L of DI water, 350 mL of 220 g / L NH3(aq), and 515 mL of an 800 g / L aqueous slurry containing the grown seed particles obtained in Example 1.2, adjusting the temperature inside the reaction vessel to 85°C and maintaining this temperature throughout the process.

[0073] Next, 120 g / L of a metal sulfate solution containing Ni, Mn, and Co (stoichiometric molar ratio of Ni:Mn:Co=65:15:20), 220 g / L of NH3(aq), and 230 g / L of NaOH solution were added, and the reaction was continued for the first 6 hours at approximately 30 kW / m 3 The stirring power requirement is approximately 20 kW / m for the remainder of the process. 3 The precipitation reaction was carried out with stirring at a required stirring power of 0.4 μm / h. The feed rate of the metal sulfate solution was 600 mL / h at the beginning and was continuously increased according to the following formula 1 to reach 3700 mL / h at the end of the process, maintaining a constant particle growth rate of 0.4 μm / h.

[0074]

number

[0075] During the reaction, the supply rate of the NaOH solution was adjusted so as to stably maintain the pH value of the reaction mixture in the reaction vessel at 11.8±0.1, and the NH3 (aq) concentration in the reaction mixture was adjusted so as to stably maintain 12.0±1 g / L. 3(aq) The feed rate of 10.2 μm was adjusted. Samples of the reaction mixture were taken every 2 hours and the D50 was measured therefrom. The process was stopped when the D50 of the sample reached the target value of approximately 10.2 μm. The duration of the process was 15 hours. A portion of the liquid fraction of the reaction mixture was pumped out of the reactor during the process by using a concentrator. The solids content of the reaction mixture, which was an aqueous slurry containing hydroxide particles in the reactor vessel, was approximately 780 g / L at the end of the process.

[0076] Example 2.2 (Particle Growth Process) A starting solution was prepared by charging a reaction vessel with a working volume of 8.75 L with 6 L of DI water, 55 mL of 220 g / L NH3(aq), and 410 mL of a 130 g / L aqueous slurry containing the seed particles obtained in Example 1.1, adjusting the temperature inside the reaction vessel to 85° C. and maintaining this temperature throughout the process. A slurry of seed particles of Ni(OH)2 with a D50 of 1.2 μm was prepared as described above.

[0077] Next, 120 g / L of a metal sulfate solution containing Ni, Mn, and Co (stoichiometric molar ratio of Ni:Mn:Co=94:03:03), 220 g / L of NH3(aq), and 230 g / L of NaOH solution were added, and the reaction temperature was approximately 33 kW / m for the first 30 hours. 3 The stirring power requirement is approximately 30 kW / m for the remainder of the process. 3 The precipitation reaction was carried out while mixing at a required stirring power of 10 ... (aq) The NaOH solution was added by adjusting the feed rate of . Reactor samples of the reaction mixture were taken every 2 hours and the D50 was measured therefrom. The process was stopped when the D50 of the reactor sample reached the target value of 5.0 μm. The duration of the process was 48 hours. A portion of the liquid fraction of the reaction mixture was pumped out of the reactor during the process. The solids content of the reaction mixture, which was an aqueous slurry containing grown seeds in the reactor vessel, was approximately 440 g / L at the end of the process.

[0078] Example 2.3 (Particle Growth Process) An initiating solution was prepared by charging a reaction vessel with a working volume of 8.75 L with 6 L of DI water, 350 mL of 220 g / L NH3(aq), and 447 mL of a 440 g / L aqueous slurry containing the seed particles obtained in Example 2.2, adjusting the temperature inside the reaction vessel to 85°C and maintaining this temperature throughout the process.

[0079] Next, 120 g / L of a metal sulfate solution containing Ni, Mn, and Co (stoichiometric molar ratio of Ni:Mn:Co=94:03:03), 220 g / L of NH3(aq), and 230 g / L of NaOH solution were added, and the reaction was continued for the first 6 hours at approximately 30 kW / m 3 The stirring power requirement is approximately 20 kW / m for the remainder of the process. 3The precipitation reaction was carried out while mixing at a required stirring power of 1000 μm. The feed rate of the metal sulfate solution was 540 mL / h at the start and continuously increased according to Equation 1 disclosed above to 1900 mL / h at the end of the process, maintaining a constant particle growth rate of 0.5 μm / h. During the reaction, the feed rate of the NaOH solution was adjusted so that the pH value of the reaction mixture in the reactor was maintained constant at 11.7 ± 0.1, and the feed rate of NH3(aq) was adjusted so that the NH3 concentration in the reaction mixture was maintained constant at 12.0 ± 1 g / L. Reactor samples of the reaction mixture were taken every two hours, and the D50 values ​​were measured therefrom. The reaction was stopped when the D50 value of the reactor sample reached the target value of approximately 10.0 μm. The duration of the process was 11 hours. During the process, an external concentrator was used to pump a portion of the liquid fraction of the reaction mixture out of the reactor, and the solids content of the reaction mixture in the reactor was approximately 180 g / L at the end of the process.

[0080] Example 3.1 (Seed particle preparation process) The reaction mixture 3(aq) An aqueous slurry of metal hydroxide was prepared according to a process similar to that of Example 1.1, except that the concentration was maintained at approximately 2.5 g / L between values ​​of 2.3 and 2.8 g / L. When the reaction reached a steady state approximately 24 hours after initiation, the reactant, i.e., an aqueous slurry of nickel hydroxide having a D50 of 1.5 μm (i.e., seed particles), was collected from the overflow of the reaction vessel.

[0081] Example 4.1 (Seed Particle Preparation) An initiating solution was prepared by adding 3.4 L of DI water and 33 mL of 220 g / L NH3(aq) to a 3.65 L reactor, adjusting the reactor temperature to 85°C, and maintaining this temperature throughout the process. A 220 g / L NaOH solution was added to adjust the pH value of the initiating solution in the reactor to 12.7-12.9.

[0082] A 120 g / L metal sulfate solution containing Ni, Mn, and Co (stoichiometric molar ratio, Ni:Mn:Co 25:73:02) at a feed rate of 300 mL / h, 220 g / L NH(aq) at a feed rate of 13 mL / h, 40 g / L ascorbic acid at a feed rate of 60 mL / h, and 220 g / L NaOH solution at a feed rate of 214 mL / h were continuously added to the reactor. The solutions were heated to approximately 20 kW / m. 3 The reaction mixture was mixed using a mixer having a stirring power requirement of 12.9±0.1, and the pH value of the reaction mixture was kept stable at 12.9±0.1 to prepare an aqueous reaction mixture slurry. 3(aq) The concentration was maintained at approximately 1.5-2.0 g / L. The reaction was carried out in a continuous mode. When the reaction reached a steady state approximately 10 hours after initiation, the reactant, i.e., an aqueous slurry of Ni, Mn, and Co hydroxides (i.e., seed particles) with a D50 of 1.8 μm, was collected from the overflow of the reaction vessel.

[0083] Comparative Example 1 An initiating solution was prepared by adding 2.2 L of DI water, 120 mL of 220 g / L NH3(aq), and 30 mL of 220 g / L NaOH solution to a 3.65 L reactor, adjusting the reactor temperature to 65° C. and maintaining this temperature throughout the process. The pH value of the initiating solution in the reactor was 12.9.

[0084] Next, a 120 g / L metal sulfate solution containing Ni, Mn, and Co (stoichiometric molar ratio of Ni:Mn:Co, 65:15:20) at a feed rate of 500 mL / h, 220 g / L NH3(aq) at a feed rate of 56 mL / h, and 220 g / L NaOH solution at a feed rate of 304 mL / h were added continuously to the starting solution. The solution was heated to approximately 13.8 kW / m for the first 2 hours. 3 The stirring power required for the remaining reaction was approximately 6.4 kW / m 3 The mixture was mixed using a mixer at a stirring power of 11.9±0.1 to prepare an aqueous slurry as a reaction mixture. After the reaction started, the pH value of the reaction mixture was kept stable at 11.9±0.1, and the NH 3(aq)The concentration was maintained at 8-10 g / L. Samples of the reaction mixture were taken every 2 hours and the D50 was measured from them. The process was stopped when the D50 of the sample reached the target value of 10.2 μm. The duration of the process was 46 hours. A portion of the liquid fraction of the reaction mixture was pumped out of the reactor during the process using an external concentrator.

[0085] FIG. 6 shows an SEM image of the particles obtained from 2 hours after the start of the process of Comparative Example 1, when the nucleation process was completed, i.e., when almost no new nuclei were produced, when the D50 of the aqueous slurry was measured to be 3.90.

[0086] Comparative Example 2 An initiating solution was prepared by adding 2.2 L of DI water, 150 mL of 220 g / L NH3(aq), and 25 mL of 220 g / L NaOH solution to a 3.65 L reactor, adjusting the reactor temperature to 65° C. and maintaining this temperature throughout the process. The pH value of the initiating solution in the reactor was 11.4.

[0087] Next, a 120 g / L metal sulfate solution containing Ni, Mn, and Co (stoichiometric molar ratio, Ni:Mn:Co 82:12:6) at a feed rate of 545 mL / h, 220 g / L NH3(aq) at a feed rate of 45 mL / h, and 220 g / L NaOH solution at a feed rate of 327 mL / h were continuously added to the starting solution. Approximately 5.8 kW / m was generated during the reaction. 3 The solution was mixed using a mixer having a stirring power requirement of 11.7±0.1 to prepare an aqueous slurry as a reaction mixture. After the reaction started, the pH value of the reaction mixture was kept stable at 11.7±0.1, and the NH 3(aq) The concentration was maintained at 7.5-8.5 g / L. Samples of the reaction mixture were taken every 2 hours and the D50 was measured from them. The process was stopped when the D50 of the sample reached the target value of 11.5 μm. The duration of the process was 23 hours. A portion of the liquid fraction of the reaction mixture was removed from the reactor using a pump during the process.

[0088] Dried products of the examples The reaction mixtures, i.e., aqueous slurries of metal hydroxides obtained in Example 1.3, Example 2.3, Comparative Example 1, and Comparative Example 2, were filtered and washed with 220 g / L NaOH solution and hot DI water. The filter cakes were dried in an oven at 120° C. for 12 hours.

[0089] Summary of Examples Some of the reaction conditions and characteristics of the aqueous slurries obtained in the examples are shown in Table 1. Some of the characteristics of the dried hydroxides obtained in Example 1.3, Example 2.3, Comparative Example 1, and Comparative Example 2 are shown in Table 2.

[0090] [Table 1]

[0091] [Table 2]

Claims

1. 1. A method for producing a first aqueous slurry comprising first hydroxide or oxyhydroxide particles of at least one element for use as a seed particle source in a second hydroxide precipitation process, wherein the at least one element comprises at least one of Ni, Co, and Mn; continuously supplying a first stream of a metal salt solution containing the one or more elements to a reaction vessel; continuously feeding a second stream of an aqueous solution of one or more alkali hydroxides to the reaction vessel; Aqueous ammonia solution (NH ３（ａｑ） continuously feeding a third stream of mixing the first, second, and third streams to obtain the first aqueous slurry containing the first hydroxide or oxyhydroxide particles in the reaction vessel; 1. The method of claim 1, further comprising continuously removing a fourth stream of said first aqueous slurry from said reaction vessel, the first aqueous slurry has a pH value of at most 13.0 and at least 12.0, the pH value being measured on a sample of the first aqueous slurry at 20°C; providing the third stream is NH in the first aqueous slurry ３（ａｑ） wherein the concentration is controlled to be at least 1.0 g / l and at most 5.0 g / l to limit the growth of the first hydroxide or oxyhydroxide particles to a median particle size D50 ranging from at least 0.7 μm to at most 3.0 μm.

2. 2. The process of claim 1, wherein the first aqueous slurry in the reaction vessel has a temperature of at least 40°C and at most 80°C, preferably at least 45°C and at most 65°C, more preferably at least 50°C and at most 60°C.

3. 3. The method according to any one of claims 1 to 2, wherein the pH value of the first aqueous slurry in the reaction vessel is at least 12.4, preferably at least 12.6, when the pH value is measured on a sample of the first aqueous slurry at 20°C.

4. The method according to any one of claims 1 to 3, wherein the NH in the first aqueous slurry in the reaction vessel ３（ａｑ） a concentration of at least 1.0 g / l and at most 4.0 g / l that limits the median particle size D50 of the first hydroxide or oxyhydroxide to a range of at least 0.7 μm and at most 2.0 μm; or the NH in the first aqueous slurry in the reaction vessel ３（ａｑ） A method wherein the concentration is at least 2.0 g / l and at most 4.0 g / l, limiting the median particle size D50 of the first hydroxide or oxyhydroxide to a range of at least 1.0 μm and at most 2.0 μm.

5. 5. The method according to claim 1, wherein the mixing step is carried out using a stirring power requirement, and the stirring power requirement is m of the first aqueous slurry. ３ at least 15 kW per m of said first aqueous slurry, preferably ３ more preferably at least 20 kW per m of said first aqueous slurry ３ at least 25 kW per

6. 6. The method according to claim 1, wherein the at least one element in the first hydroxide or oxyhydroxide particles is: Ni with a content x, where 5.0 mol%≦x%; Co having a content y, where 0≦y≦30.0 mol%; Mn having a content z, where 0≦z≦85.0 mol%; Al having a content q, where 0≦q≦10.0 mol%; one or more additional elements in a content r, said additional elements being from the list B, Ba, Ca, Ce, Cr, Fe, La, Mg, Mo, Nb, Si, Sr, Ti, Y, V, W, Zn, Na, S, and Zr, with 0≦r≦5.0 mol%, x, y, z, q, and r are contents expressed in mol % relative to the total molar content of said at least one element in said first hydroxide or oxyhydroxide, and x+y+z+q+r=100 mol %.

7. 7. The method of claim 6, wherein x > 60.0 mol%, preferably x > 80.0 mol%.

8. 1. A method for producing a second aqueous slurry comprising second hydroxide or oxyhydroxide particles of one or more elements, wherein the one or more elements comprise at least one of Ni, Co, and Mn; d) providing a quantity of a first aqueous slurry comprising first hydroxide or oxyhydroxide particles in a reaction vessel, said first hydroxide or oxyhydroxide particles having a median particle size D50 in the range of at least 0.7 μm and at most 3.0 μm, preferably said first aqueous slurry being obtained according to a method according to any one of claims 1 to 7; e) providing a fifth stream of a metal salt solution containing the one or more elements to the reaction vessel; f) providing a sixth stream of one or more aqueous alkali hydroxides to said reaction vessel; g) maintaining conditions in the reaction vessel that cause precipitation of the one or more elements from the metal salt solution as hydroxides on the first hydroxide or oxyhydroxide to obtain the second aqueous slurry in the reaction vessel comprising the second hydroxide or oxyhydroxide particles of the one or more elements.

9. Aqueous ammonia solution (NH ３（ａｑ） 9. The method of claim 8, further comprising feeding a seventh stream of (a) olefin (B) to the reaction vessel.

10. 10. The method according to claim 8 or 9, wherein in step a) providing a quantity of a first aqueous slurry comprises carrying out a method according to any one of claims 1 to 7.

11. 11. The method of claim 9 or 10, wherein step c) comprises: the sixth stream is controlled so that the second aqueous slurry in the reaction vessel has a pH value of at most 12.2, preferably at least 10, more preferably at most 12.1 and at least 11.0, wherein the pH value of the second aqueous slurry is measured on a sample of the second aqueous slurry at 20°C; The seventh stream is a mixture of NH3 in the second aqueous slurry. ３（ａｑ） the concentration being controlled to be at least 1.0 g / l and at most 20.0 g / l, preferably at least 1.5 g / l and at most 15.0 g / l; Applying a stirring power requirement, wherein the stirring power requirement is ３ Maximum 40 kW per m of said second aqueous slurry, preferably ３ and / or the stirring power is at most 35 kW per m of the second aqueous slurry. ３ at least 5 kW per m of said second aqueous slurry, preferably ３ applying at least 10 kW per maintaining a temperature of the second aqueous slurry in the reaction vessel at at least 45°C, preferably at least 75°C, more preferably at least 80°C; The method includes at least one of:

12. 12. The method of claim 1, wherein the one or more elements in the second hydroxide or oxyhydroxide particles are: Ni with a content b, where 5.0 mol%≦b≦99.0 mol%, and Co having a content c, where 0≦c≦30.0 mol%; Mn having a content d, where 0≦d≦85.0 mol%, and Al having a content e, where 0≦e≦10.0 mol%; one or more additional elements with a content f, said additional elements being from the list B, Ba, Ca, Ce, Cr, Fe, La, Mg, Mo, Nb, Si, Sr, Ti, Y, V, W, Zn, Na.S and Zr, with 0≦f≦5.0 mol%, b, c, d, e, and f are contents expressed in mol% relative to the total molar content of said one or more elements in said second hydroxide, and b+c+d+e+f=100 mol%.

13. 13. The method of claim 12, wherein x≠b, alternatively, x>b and / or b≧60.0 mol%, d≦30.0 mol%, (b+d)≧1.0 mol%, and / or d≧50.0 mol%, f≦3.0 mol%.

14. 14. A method for producing hydroxide or oxyhydroxide powder of one or more metallic elements, the method comprising: I) producing an aqueous slurry comprising hydroxide or oxyhydroxide particles of one or more metallic elements according to any one of claims 8 to 13; II) separating the hydroxide or oxyhydroxide particles from a liquid fraction of the aqueous slurry; and III) drying the separated hydroxide or oxyhydroxide particles.

15. 15. A method for producing a cathode active material, comprising: 1) producing a hydroxide or oxyhydroxide powder of one or more elements according to claim 14; 2) mixing the hydroxide or oxyhydroxide powder with a lithium source to obtain a mixture; and 3) sintering the mixture at a temperature between 650°C and 1000°C.

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