Apparatus and method for manufacturing lithium secondary battery positive electrode active material precursor

Abstract

The present invention relates to an apparatus and a method for manufacturing a lithium secondary battery positive electrode active material precursor, the apparatus for manufacturing a lithium secondary battery positive electrode active material precursor comprising: a reactor for adding a reaction raw material to generate a reaction product; the stirrer is used for stirring the reaction raw materials; the solid-liquid separation part is arranged between the side wall of the reactor and the stirrer and is used for performing solid-liquid separation in the reaction product; and a filtrate discharge port, which is disposed at the upper part of the solid-liquid separation means, and which separates and discharges the filtrate to the outside of the reactor.

Description

Technical Field

[0001] The present embodiment relates to a lithium secondary battery, and more particularly to an apparatus and method for manufacturing a positive electrode active material precursor for a lithium secondary battery. Background Art

[0002] As the depletion of fossil fuels and the environmental pollution caused by the use of fossil fuels have increasingly attracted social attention, environmentally friendly energy has attracted more and more attention as a solution. Among the environmentally friendly energy, electric energy has attracted increasing attention, especially lithium secondary batteries.

[0003] The application range of lithium secondary batteries has expanded not only to small electronic devices and portable IT equipment, but also to electric vehicles and energy storage systems. As the application range of lithium secondary batteries expands, the development of new materials for achieving high capacity and high power becomes increasingly important. In the composition of lithium secondary batteries, the positive electrode active material is manufactured by precursors made of metal oxides of various component systems such as nickel, cobalt, and manganese.

[0004] Various methods have been proposed to prepare the positive electrode active material, but the co-precipitation method using polymetallic salts such as nickel, cobalt, manganese, aluminum or zirconium as starting materials is the most economical and feasible method.

[0005] Furthermore, a batch-type device utilizes the coprecipitation method to produce precursors. To control particle growth and shape, this batch-type device typically requires approximately 20 hours to fill the reaction volume to the time required to add the raw material (input source), 1RT. This ensures that approximately 10% of the reaction weight of the precursor is produced, based on 1RT.

[0006] As described above, conventional batch devices utilize only 70 to 80% of the reactor's internal volume as reaction volume, and only about 10% of the reactants are produced as precursors, resulting in a relatively low productivity of precursors per unit batch.

[0007] Furthermore, conventional batch-type systems experience continuous volume changes during the reaction, significantly impacting the synthesized precursors with the changing flow patterns within the reactor. Furthermore, these systems suffer from issues such as poor productivity per batch, reproducibility issues when subdividing batches, and uneconomical management costs. Summary of the Invention

[0008] Technical problems to be solved

[0009] The technical problem to be solved by the present invention is to provide a device for manufacturing precursors of positive electrode active materials for lithium secondary batteries, which improves the productivity of the precursors. As the flow phenomena inside the reactor change, the impact on the synthesized precursors is minimized, the relative productivity of each batch of production is increased, the reproducibility problem of batch subdivision is solved, and it is economical.

[0010] Another technical problem to be solved by the present invention is to provide a method for manufacturing a precursor of a positive electrode active material for a lithium secondary battery having the aforementioned advantages.

[0011] Technical Solution

[0012] According to one embodiment of the present invention, a device for manufacturing a positive electrode active material precursor for a lithium secondary battery may include: a reactor for adding reaction raw materials to generate a reaction product; a stirrer for stirring the reaction raw materials; a solid-liquid separation component, the solid-liquid separation component being arranged between the side wall of the reactor and the stirrer and being used to perform solid-liquid separation in the reaction product; and a filtrate discharge port, the filtrate discharge port being arranged at the upper portion of the solid-liquid separation component and being used to separate and discharge the filtrate to the outside of the reactor. In one embodiment, the solid-liquid separation component includes a lower portion, a middle portion, and an upper portion, and the cross-sectional area of ​​the lower portion may gradually decrease from top to bottom.

[0013] In one embodiment, the solid-liquid separation component may include a plurality of solid-liquid separation components. In one embodiment, the plurality of solid-liquid separation components may be arranged relative to each other. In one embodiment, the manufacturing apparatus may include a filtrate discharge auxiliary unit for assisting in moving the filtrate provided by the plurality of solid-liquid separation components to the filtrate discharge unit.

[0014] In one embodiment, the reactors may be connected in parallel in plurality. In one embodiment, the filtrate outlet may be arranged to slope downward the further away from the reactor.

[0015] In one embodiment, a lithium secondary battery positive electrode active material precursor manufacturing device relates to a lithium secondary battery positive electrode active material precursor manufacturing device composed of multiple reactors including a first reactor and a second reactor, the first reactor may include: a first stirrer, the first stirrer is used to stir the added reaction raw materials; and a discharge port, the discharge port is used to discharge part of the reactants of the reaction raw materials, the second reactor may include: a second stirrer, the second stirrer is used to stir the reactants flowing into the first reactor; a solid-liquid separation component, the solid-liquid separation component is arranged between the side wall of the first reactor and the second stirrer, and is used to perform solid-liquid separation in the reaction product; and a filtrate discharge port, the filtrate discharge port is arranged on the upper part of the solid-liquid separation component, and is used to separate and discharge the filtrate to the outside of the reactor, the manufacturing device may include a second reactor, the second reactor is arranged on the side of the first reactor, and is arranged at a position lower than the first reactor.

[0016] In one embodiment, the manufacturing apparatus may include a recovery unit connected from the second reactor toward the first reactor for recovering a portion of the filtrate. In one embodiment, multiple second reactors may be connected in parallel. In one embodiment, the solid-liquid separation unit includes a lower portion, a middle portion, and an upper portion, and the cross-sectional area of ​​the lower portion may gradually decrease from top to bottom.

[0017] In one embodiment, the solid-liquid separation component may include multiple solid-liquid separation components. In one embodiment, the manufacturing apparatus may include a filtrate discharge auxiliary unit configured to assist in moving the filtrate provided by the multiple solid-liquid separation components to the filtrate discharge unit. In one embodiment, the solid-liquid separation component includes a starting volume region and a reaction volume region, wherein the reaction volume region may be 70 to 90% of the internal volume of the reactor. In one embodiment, the internal volume of the solid-liquid separation component may be less than 20% of the entire reaction volume region.

[0018] According to another embodiment of the present invention, a method for manufacturing a positive electrode active material precursor for a lithium secondary battery may include: adding a reaction raw material including a mixed metal salt solution and an alkaline solution to a reactor and stirring the reaction raw material with a stirrer to generate a reaction product including precursor particles; a step of separating solids and liquids in the reaction product by disposing a device between the reactor and the stirrer during the generation of the reaction product; and a step of discharging the remaining filtrate during the solid-liquid separation step. In one embodiment, in the step of separating solids and liquids in the reaction product by disposing a device between the reactor and the stirrer during the generation of the reaction product, the step of separating solids and liquids may be performed by multiple solid-liquid separation components.

[0019] In one embodiment, the manufacturing method may include: before the step of separating solids and liquids in the reaction product, which is disposed between the reactor and the mixer during the reaction product generation process, generating reactants from the reaction raw materials in an additional reactor. In one embodiment, the step of separating solids and liquids in the reaction product, which is disposed between the reactor and the mixer during the reaction product generation process, may also include steps performed in parallel in multiple reactors.

[0020] Beneficial effects

[0021] According to one embodiment of the present invention, a device for manufacturing a precursor of a positive electrode active material for a lithium secondary battery is provided. Since the reactor includes a pipe-shaped structure with a solid-liquid separation function, the productivity of the precursor is improved by solid-liquid separation and filtrate separation and discharge during the reaction. As the flow phenomenon inside the reactor changes, the impact on the synthesized precursor is minimized, the relative productivity of each batch of production is increased, the reproducibility problem of batch subdivision is solved, and it is economical.

[0022] According to another embodiment of the present invention, a method for manufacturing a positive electrode active material precursor for a lithium secondary battery having the aforementioned advantages is provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 A device for manufacturing a positive electrode active material precursor for a lithium secondary battery according to one embodiment of the present invention is shown.

[0024] Figures 2a to 2c Show respectively Figure 1 Cross-sectional views when cutting along lines AA', BB', and CC'.

[0025] Figure 3 A device for manufacturing a positive electrode active material precursor for a lithium secondary battery according to yet another embodiment of the present invention is shown.

[0026] Figure 4 A device for manufacturing a positive electrode active material precursor for a lithium secondary battery according to yet another embodiment of the present invention is shown.

[0027] Figure 5 A device for manufacturing a positive electrode active material precursor for a lithium secondary battery according to yet another embodiment of the present invention is shown.

[0028] Figures 6a to 6c The cross sections of the positive electrode materials using the precursors produced according to the examples and comparative examples of the present invention are shown.

[0029] Figure 7a and Figure 7b The following are photos of precursor synthesis results generated according to the examples and comparative examples of the present invention. DETAILED DESCRIPTION

[0030] The terms "first," "second," and "third" are used to describe various parts, components, regions, layers, and / or segments, but these parts, components, regions, layers, and / or segments should not be limited by these terms. These terms are only used to distinguish one part, component, region, layer, and / or segment from another part, component, region, layer, and / or segment. Therefore, a first part, component, region, layer, and / or segment described below could also be described as a second part, component, region, layer, and / or segment without departing from the scope of the present invention.

[0031] The terms used herein are for the purpose of describing specific embodiments only and are not intended to limit the present invention. Unless the context clearly indicates otherwise, the singular forms used herein are intended to include the plural forms. As used in the specification, "comprising" may specifically refer to a certain characteristic, field, integer, step, action, element and / or component, but does not exclude the existence or addition of other characteristics, fields, integers, steps, actions, elements, components and / or groups.

[0032] If a part is described as being "on" another part, then the other part may be directly on the other part or there may be another part therebetween. If a part is described as being "directly on" another part, then there may not be another part therebetween.

[0033] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Dictionary-defined terms should be interpreted as having the same meaning as that in the relevant technical literature and disclosed herein, and should not be interpreted in an idealized or overly formal sense.

[0034] Hereinafter, embodiments of the present invention will be described in detail. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments, but is defined only by the scope of the claims.

[0035] Figure 1 A device 10 for producing a positive electrode active material precursor for a lithium secondary battery according to one embodiment of the present invention is shown.

[0036] Reference Figure 1 According to an embodiment of the present invention, a lithium secondary battery positive electrode active material precursor manufacturing device 10 includes: a reactor RA, which is used to add reaction raw materials to generate reaction products; a stirrer 12, which is used to stir the reaction raw materials; a solid-liquid separation component 13, which is arranged between the side wall of the reactor RA and the stirrer 12, and is used to perform solid-liquid separation in the reaction product; and a filtrate discharge port 14, which is arranged at the upper part of the solid-liquid separation component 13, and is used to separate and discharge the filtrate to the outside of the reactor RA.

[0037] The reaction raw materials are substances used to manufacture positive electrode active material precursors, and may include substances such as metal salt solutions, pH regulators, and chelating agents. The metal salt solution is an aqueous solution of transition metals containing lithium secondary battery positive electrode active materials, and metal salt substances such as sulfates, nitrates, or acetates may be used. Specifically, as a non-limiting example, the metal salt solution may be an aqueous sulfate solution including cobalt, nickel, or manganese.

[0038] As a non-limiting example, the pH adjuster can be any one of NaOH, KOH, and mixtures thereof. In addition, as a non-limiting example, the chelating agent can be any one of an aqueous ammonia solution, an aqueous ammonium sulfate solution, or mixtures thereof.

[0039] The metal salt solution, pH adjuster, and chelating agent, serving as the reaction raw materials, can be added to the reactor RA via a first inlet 11a, a second inlet 11b, and a third inlet 11c. In one embodiment, at least one of the first inlet 11a, the second inlet 11b, and the third inlet 11c is shared, and an inert gas can be introduced therein to facilitate the reaction. As a non-limiting example, the inert gas can be nitrogen, argon, or a mixture thereof.

[0040] In the reactor RA, the metal salt solution and the pH adjuster are added to the reactor to react and be consumed, thereby generating primary particles. The chelating agent can cause the primary particles to agglomerate to generate secondary particles. The reactor RA can be controlled to uniformly distribute the reactants within the reactor RA.

[0041] The stirrer 12 configured in the reactor RA can stir the reaction raw materials. Specifically, the stirrer 12 is a component that generates fluid flow and increases the mixing degree of the reaction substances. The stirred reaction raw materials stir each other and react and are consumed, and precursor particles and reaction filtrate are generated, which exist in the reactor RA in a homogeneous form. Specifically, the metal salts and pH regulators added as reaction raw materials can react with each other in the reactor and be consumed. For example, after mixing metal salts such as metal sulfates and pH regulators such as sodium hydroxide, they can react with each other to generate metal hydroxides and sodium sulfate and be consumed.

[0042] In one embodiment, the reactor RA may include at least one baffle (not shown) for inducing eddies. Specifically, the baffle may be a component that acts as an obstacle to the flow of fluid within the reactor RA, facilitates mixing of reactants by forming eddies, and assists in uniform distribution of the secondary precursor particles in the reactants.

[0043] In one embodiment, the reactor RA may include a starting volume region (between the bottom surface of the RA and the BB' line) and a reaction volume region (between the bottom surface of the RA and the AA' line). The starting volume region refers to the volume that can show the fluid flow effect at the moment of reaction. It is the region where the raw material starts to react due to the vortex caused by the agitator 12 and other components after the raw material is filled in the reactor RA. The reaction volume region refers to the region where the reaction starts from the starting volume region, the reactants are continuously increased and discharged, and the region where the raw material reacts with volume changes, and the flow changes inside the reactor RA affect the growth of the precursor. The higher the proportion of the reaction volume region, the higher the precursor yield can be.

[0044] In one embodiment, the reaction volume area may be 70 to 90% of the internal volume of the reactor. Specifically, the reaction volume area may be 80 to 90% of the internal volume of the reactor. Due to the guaranteed reaction volume area, the precursor yield is greatly increased in a single reaction.

[0045] The solid-liquid separation component 13 is disposed between the sidewall of the reactor RA and the agitator 12 and is used to separate the solid and liquid in the reaction product. Specifically, the solid-liquid separation component 13 can be disposed circumferentially along the sidewall of the reactor RA. The solid and liquid separated by the solid-liquid separation component 13 can be precursor particles and filtrate, respectively, from the reaction product obtained through the coprecipitation reaction.

[0046] In one embodiment, a solid-liquid separation component 13 may be configured to replace the aforementioned baffles. For example, in a conventional device, baffles may be relatively arranged at four locations, but the present invention may configure a solid-liquid separation component 13 to replace at least one of the baffles.

[0047] The solid-liquid separation component 13 is disposed within the reactor RA, and can suppress the flow of reactants generated by the reaction of the raw materials, and can achieve continuous solid-liquid separation during the co-precipitation reaction, thereby greatly improving the productivity of the reactants such as each batch of precursors. Specifically, the function of the solid-liquid separation component 13 is to suppress the flow of fluid inside the structure to guide solid-liquid separation, and to act as a vortex generator outside the structure on the fluid flow generated by the stirrer 12 to assist in achieving homogenization. More specifically, at the initial stage of the reaction, after abundant particle nuclei are generated at the starting volume in the reactor RA, when the reaction volume is reached, solid-liquid separation is performed within the solid-liquid separation component 13, and the upper phase filtrate can be discharged.

[0048] Since the solid-liquid separation component 13 is arranged in the reactor RA, the solid-liquid separation of the reactants generated in the reactor RA during the reaction is carried out in real time in the solid-liquid separation component 13 and the separated reaction filtrate is removed, thereby ensuring additional reaction volume. By repeatedly performing the above process in real time, the solid-liquid ratio of the total particles generated in the reactor RA can be increased. Specifically, since the solid-liquid separation component 13 is further arranged in the reactor RA, along with ensuring additional reaction volume, it has the advantages of improving the productivity of reaction products such as positive electrode active material precursors, improving the sphericity of the positive electrode active material precursors, and ensuring the crystal orientation of the positive electrode active material precursors. Therefore, by using the positive electrode active material precursor to make the positive electrode active material and then generating an oriented crystal phase, high-performance positive electrode active materials can be produced.

[0049] A filtrate outlet 14 for separating and discharging the filtrate to the outside of the reactor RA can be disposed above the solid-liquid separation component 13. The filtrate outlet 14 is disposed above the solid-liquid separation component 13 and can discharge liquid filtrate other than the solid precursor particles from the reactants separated in the solid-liquid separation component 13. Specifically, the flow of the reactants generated within the reactor RA is suppressed within the solid-liquid separation component 13, causing the solid precursor particles with a higher specific gravity in the reactants to move downwardly toward the bottom of the solid-liquid separation component 13, while the relatively light reaction filtrate is concentrated in the upper portion of the solid-liquid separation component 13.

[0050] At this point, the filtrate is removed and discharged to the outside in real time through filtrate outlet 14, ensuring the reaction volume of the corresponding area, thereby guiding the continuous growth of the precursor particles and ultimately significantly increasing the precursor yield in a single reaction. Specifically, after the filtrate reaches the effective reaction volume for the target precursor particle formation state, an amount corresponding to the volume generated by the added raw materials overflows the solid-liquid separation component 13 through filtrate outlet 14, allowing the filtrate to be discharged.

[0051] In one embodiment, the filtrate outlet 14 can be configured to tilt downward as it moves away from the reactor RA. Since the filtrate outlet 14 is tilted at a predetermined angle, the remaining filtrate can be easily discharged to the outside. In one embodiment, the filtrate outlet 14 can be angled within a range of 0 to 90°, specifically 15 to 90°, and more specifically 45 to 90°, based on the extension of the sidewall of the reactor RA and a direction perpendicular to the extension. This range facilitates filtrate discharge.

[0052] In one embodiment, the filtrate outlet 14 can be connected to a filtrate storage (not shown) for storing the filtrate. A lithium secondary battery positive electrode active material precursor manufacturing device can be provided, and the filtrate can be stored in the filtrate storage, which is economical because the stored filtrate is reused.

[0053] Figures 2a to 2c Show respectively Figure 1 Front view when cutting along lines AA', BB', and CC'.

[0054] Reference Figures 2a to 2c , Figure 2a Show cutting Figure 1 The front view of the AA' line is shown, and the AA' line specifically includes the upper portion 13T of the solid-liquid separation component and the filtrate discharge port 14. Figure 2b Show cutting Figure 1 The front view of the BB' line is shown, and the BB' line is specifically the lower part 13B of the solid-liquid separation component. Figure 2c Show cutting Figure 1 The CC' line is a front view of the solid-liquid separation component, and the CC' line is specifically the middle part 13M of the solid-liquid separation component.

[0055] The solid-liquid separation component 13 includes an upper part 13T, a middle part 13M and a lower part 13B, and the cross-sectional area of ​​the lower part 13B can be gradually reduced from top to bottom. The function of the solid-liquid separation component 13 is to prevent the flow of reactants formed by the stirrer 12 from being transmitted to the interior of the solid-liquid separation component. At this time, the cross-sectional area of ​​the lower part 13B of the solid-liquid separation component gradually decreases from top to bottom, thereby effectively suppressing the influence of the flow formed by the stirrer 12. Specifically, the cross-sectional area of ​​the lower part 13B of the solid-liquid separation component gradually decreases from top to bottom, forming a weak negative pressure in the lower part 13B of the solid-liquid separation component, pulling the precursor settled inside the solid-liquid separation component 13 to the reactor RA to induce further reaction, which can improve the productivity of the synthesized precursor.

[0056] In one embodiment, the internal volume of the solid-liquid separation component 13 can be less than 25% of the reaction volume area. Specifically, the internal volume of the solid-liquid separation component 13 can meet less than 20% of the entire reaction volume area. The internal volume ratio of the aforementioned solid-liquid separation component 13 is a value calculated based on the reaction design standard of 1 reaction time (RT) in the range of 5 to 20 hours. For example, if 1 RT is 5 hours, the internal volume of the solid-liquid separation component 13 can be 15 to 25%. If 1 RT is 10 hours, the internal volume of the solid-liquid separation component 13 can be 5% to 15%. It can be seen that in the coprecipitation reaction, the shorter the reaction time (RT), the higher the productivity. When the reaction time (RT) is set to be shorter, when 1 RT is 5 hours, the internal volume of the solid-liquid separation component can be less than 20% of the total reactor volume.

[0057] By ensuring that the internal volume of the solid-liquid separation component 13 falls within the aforementioned range, the proportion of the reaction volume area can be effectively increased, thereby maximizing the yield of the positive electrode active material precursor. If the internal volume of the solid-liquid separation component 13 exceeds the aforementioned range, the effect of increasing the proportion of the reaction volume area may be insignificant, and it may be difficult to prevent the flow of the formed reactants into the interior of the solid-liquid separation component.

[0058] Figure 3 A device for manufacturing a positive electrode active material precursor for a lithium secondary battery according to yet another embodiment of the present invention is shown.

[0059] Reference Figure 3 In one embodiment, the solid-liquid separation component 13 may include a plurality of solid-liquid separation components. By including a plurality of solid-liquid separation components 13, the ratio of the reaction volume area can be increased, thereby improving the productivity of the precursor particles.

[0060] In one embodiment, multiple solid-liquid separation components 13 can be arranged in opposing positions. Multiple solid-liquid separation components 13 can be arranged in pairs. For example, multiple solid-liquid separation components 13 can be arranged in four opposing positions to replace baffles. The paired arrangement of multiple solid-liquid separation components 13 ensures a stable reaction area, effectively improving solid-liquid separation efficiency and easily securing additional reaction volume, thereby increasing precursor productivity.

[0061] In one embodiment, when multiple solid-liquid separation components 13 are configured, a filtrate discharge assisting portion 14H may also be included. Specifically, the filtrate discharge assisting portion 14H may be configured above the solid-liquid separation component 13 and connected to the filtrate discharge portion 14. More specifically, the filtrate discharge assisting portion 14H is configured to be connected to the filtrate discharge portion 14 and may be a component for facilitating the transfer of filtrate provided by the multiple solid-liquid separation components 13 to the filtrate discharge portion 14.

[0062] In one embodiment, the filtrate discharge auxiliary section 14H can be horizontally connected to the upper end of the solid-liquid separation component 13 as a pipeline. Specifically, the filtrate discharge auxiliary section 14H is a pipeline for transferring the filtrate separated from the upper ends of the multiple solid-liquid separation components 13 to the filtrate discharge section 14. In one embodiment, the filtrate discharge auxiliary section 14H can be a structure in which the area other than the portion in contact with the upper ends of the solid-liquid separation components 13 is sealed. Specifically, the filtrate discharge auxiliary section 14H can be formed as a structure in which the area other than the upper ends of the solid-liquid separation components 13 is sealed to prevent the reactants from flowing in.

[0063] In one embodiment, the auxiliary filtrate discharge section 14H can be a circular or polygonal pipe. It has a donut-shaped structure extending along the outer wall of the reactor and is connected to the respective solid-liquid separation components 13 and filtrate outlet 14. The remaining area can be a sealed structure. Specifically, the edge of the auxiliary filtrate discharge section 14H can correspond to the upper portion 13T of the solid-liquid separation component 13. By including the auxiliary filtrate discharge section 14H, the filtrate discharge pipe can be used to discharge the filtrate without the need for additional components requiring independent power, which has economic advantages.

[0064] Figure 4 FIG. 1 shows a device 10 for producing a positive electrode active material precursor for a lithium secondary battery according to another embodiment of the present invention.

[0065] Reference Figure 4 , the lithium secondary battery positive electrode active material precursor manufacturing device 10" can be composed of multiple reactors. In one embodiment, for a lithium secondary battery positive electrode active material precursor manufacturing device 10" including a first reactor RA1 and a second reactor RA2, a conventional intermittent co-precipitation reactor without a solid-liquid separation component 13 can be included as the first reactor RA1 and a second reactor RA2 including at least one solid-liquid separation component 13 and a filtrate discharge port 14'.

[0066] It may include: a solid-liquid separation component 13, which is arranged between the side wall of the second reactor RA2 and the agitator 12', and is used to perform solid-liquid separation in the reaction products of the reactants provided from the first reactor RA1 through the discharge port 14; and a filtrate discharger 14', which is arranged on the upper part of the solid-liquid separation component 13, and is used to separate and discharge the filtrate to the outside of the second reactor RA2.

[0067] In one embodiment, the first reactor RA1 may include: a first stirrer 12 for stirring the added reaction raw materials; an outlet 14 for transferring the reactants generated from the reaction raw materials to the second reactor RA2. The second reactor RA2 may include: a second stirrer 12' for stirring the reactants flowing from the first reactor into the second reactor RA2; a solid-liquid separation component 13 disposed between the sidewall of the second reactor RA2 and the second stirrer 12' for performing solid-liquid separation in the reaction product; and a filtrate outlet 14 disposed above the solid-liquid separation component 13 for separating and discharging the filtrate to the outside of the second reactor RA2. For a detailed description of each component, reference may be made to the aforementioned description of the components of the lithium secondary battery positive electrode active material precursor manufacturing apparatus 10, to the extent not inconsistent.

[0068] Specifically, the lithium secondary battery positive electrode active material precursor manufacturing device 10" is a device including two reactors, wherein a reaction is preliminarily performed in the first reactor RA1, and then an additional reaction including solid-liquid separation can be performed in the second reactor RA2. Due to the reaction including further solid-liquid separation in the second reactor RA2, there is an advantage that the solid content can be increased.

[0069] In one embodiment, the first reactor RA1 may be disposed at a higher position than the second reactor RA2. Since the first reactor RA1 is disposed at a higher position than the second reactor RA2, the reactants generated in the first reactor RA1 can easily move to the second reactor RA2.

[0070] In one embodiment, the apparatus 10″ for producing a precursor of a positive active material for a lithium secondary battery can maintain the same volume of the raw material added to the reactor and the volume of the reaction filtrate in the middle and late stages of the reaction. Specifically, when the reaction volumes of the first reactor RA1 and the second reactor RA2 are both reached, the total volume of the solid-liquid separation component 13 and the reaction filtrate discharged from the filtrate outlet 14 can be the same as the total volume of the raw material added to the first reactor RA1. In this way, the apparatus 10″ for producing a precursor of a positive active material for a lithium secondary battery is not restricted by the limited reaction volume, and has the advantage of being able to gradually increase the solid-liquid ratio and continue the reaction within the required reaction time.

[0071] In one embodiment, a recovery unit 15 may be included, extending from the second reactor RA1 toward the first reactor RA2, to recover reactants that have been concentrated due to an increased solid-liquid ratio. Specifically, the primary reaction stage for forming or growing the reactants into particles through coprecipitation is the first reactor RA1. The recovery unit 15 is used to recycle reactants from the second reactor RA2, where the solid-liquid ratio has increased after solid-liquid separation, back to the first reactor to guide further growth reactions.

[0072] Figure 5 A device 10 ″′ for producing a positive electrode active material precursor for a lithium secondary battery according to yet another embodiment of the present invention is shown.

[0073] Reference Figure 5, a plurality of lithium secondary battery positive electrode active material precursor manufacturing devices 10'' including the aforementioned second reactor RA2 can be connected in parallel. In one embodiment, the lithium secondary battery positive electrode active material precursor manufacturing device 10'' may include: a reactor RA such as the aforementioned second reactor RA2, which is used to add reaction raw materials to generate reaction products; a stirrer 12, which is used to stir the reaction raw materials; a solid-liquid separation component 13, which is arranged between the side wall of the reactor RA and the stirrer 12, for performing solid-liquid separation in the reaction product; and a filtrate discharge port 14, which is arranged at the upper part of the solid-liquid separation component 13, for separating and discharging the filtrate to the outside of the reactor RA. In one embodiment, the lithium secondary battery positive electrode active material precursor manufacturing device 10'' may include a filtrate discharge auxiliary part 14H. Regarding the detailed description of the aforementioned reactor assembly, to the extent not inconsistent with the Figures 1 to 4 same.

[0074] In one embodiment, a plurality of second reactors RA2 are connected on the same line in a parallel structure, and each second reactor RA2 can circulate the reactants whose solid-liquid ratio has increased after solid-liquid separation through the recovery components 15, 15', 15", so as to guide further growth reactions. At this time, the filtrate discharge ports 14, 14', 14" arranged at the upper ends of the solid-liquid separation components 13, 13', 13" can independently discharge the reaction filtrate to the outside. In this way, by configuring a plurality of second reactors RA2 in parallel, the reactants in the plurality of reactors can be homogenized through another reactor, thereby improving productivity. In one embodiment, the lithium secondary battery positive active material precursor manufacturing device 10'" may also include a first reactor RA1, which is configured at a position higher than the plurality of second reactors RA2. Regarding the detailed description of the first reactor RA1, to the extent not inconsistent with the aforementioned Figure 4 same.

[0075] According to another embodiment of the present invention, a method for manufacturing a precursor of a positive electrode active material for a lithium secondary battery includes: a step of adding reaction raw materials including a mixed metal salt solution and an alkaline solution into a reactor and stirring with a stirrer to generate a reaction product including precursor particles; a step of disposing between the reactor and the stirrer during the reaction product generation process to separate the solid and liquid in the reaction product; and a step of discharging the remaining filtrate after performing the solid-liquid separation.

[0076] Regarding the step of adding reaction materials including a metal solution and an alkaline solution to a reactor and stirring them with a stirrer to generate a reaction product including precursor particles, the reaction materials including the aforementioned metal solution, alkaline solution, and chelating agent can be added to the reactor and stirred with a stirrer to generate a reaction product including precursor particles. The detailed descriptions of the reaction materials, the reactor, the stirrer, and the reaction product are the same as those of the aforementioned apparatus for manufacturing a positive electrode active material precursor for a lithium secondary battery, to the extent not inconsistent.

[0077] Regarding the step of separating solid and liquid in the reaction product during the reaction product generation process, the precursor particles and the filtrate in the reaction product can be separated by the solid-liquid separation component arranged in the reactor.

[0078] In one embodiment, in the step of separating the solid and liquid in the reaction product during the reaction product generation process, the step of separating the solid and liquid can be performed by multiple solid-liquid separation components. Multiple solid-liquid separation components can be configured in the reactor. Due to the configuration of multiple solid-liquid separation components, the reaction volume ratio can be increased, thereby improving the productivity of the precursor. Regarding the detailed description of the working principle of the solid-liquid separation component, reference can be made to the solid-liquid separation component to the extent not inconsistent.

[0079] In the step of performing solid-liquid separation, the step of discharging the remaining filtrate is that the filtrate passes through the solid-liquid separation component to suppress the flow of reactants generated in the reactor within the solid-liquid separation component, and the solid precursor particles with a larger specific gravity in the reactants move to the bottom of the solid-liquid separation component, while the relatively light reaction filtrate is concentrated in the upper part of the solid-liquid separation component.

[0080] At this time, the filtrate is removed in real time through the filtrate outlet and discharged to the outside, ensuring the reaction volume of the corresponding area, thereby guiding the continuous growth of the precursor particles, and ultimately greatly increasing the precursor yield in a single reaction. Specifically, for the filtrate, after reaching the effective reaction volume of the target precursor particle formation state, the amount corresponding to the volume generated by the added raw material overflows the solid-liquid separation component through the filtrate outlet, so that the filtrate can be discharged. The detailed description of this is the same as the aforementioned description of the filtrate outlet to the extent not contradictory.

[0081] In one embodiment, the manufacturing method may include: a step of generating reactants from the reaction raw materials in an additional reactor, which is arranged between the reactor and the mixer during the reaction product generation process to separate the solid and liquid in the reaction product. With respect to the additional reactor, the aforementioned manufacturing device for the positive electrode active material precursor of a lithium secondary battery refers to the first reactor RA1. To the extent not contradictory, reference may be made to the description of the first reactor RA1. Since the manufacturing method for the positive electrode active material precursor of a lithium secondary battery includes the step of generating reactants in the additional reactor, after the reactants are generated in the additional reactor, solid-liquid separation is performed in the reactor to concentrate the solid and liquid, thereby improving the productivity of the precursor.

[0082] In one embodiment, the step of separating the solid and liquid in the reaction product, disposed between the reactor and the stirrer during the reaction product generation process, may further include a step performed in parallel in multiple reactors. By disposing multiple reactors including the solid-liquid separation step and performing the reaction in parallel in the multiple reactors, the productivity of the synthesized precursor can be improved.

[0083] The following embodiment is merely one embodiment of the present invention, and the present invention is not limited to the following embodiment.

[0084] <Experimental Example>

[0085] <Cathode Material Formation Based on Precursor Particle Growth>

[0086] Figures 6a to 6c These are cross-sectional particle photographs taken after the precursors produced according to the examples and comparative examples of the present invention were converted into positive electrode materials.

[0087] Reference Figures 6a to 6c , Figure 6a A cross-sectional SEM photograph showing a comparative example of the present invention, taken after converting a precursor generated using a conventional batch device into a positive electrode material, Figure 6b A cross-sectional SEM photograph showing a precursor produced during a cycle process converted into a positive electrode material according to one embodiment of the present invention is shown. Figure 6c This is a cross-sectional SEM photograph of a cathode material obtained by converting a precursor produced by a cyclic concentration process according to one embodiment of the present invention.

[0088] Reference Figure 6a The product shape and cross-section can be confirmed, with Figure 6b and Figure 6c Compared with the sphericity and orientation of Figure 6b and Figure 6c The product can be confirmed to be able to produce high-performance positive electrode active materials with excellent sphericity and crystal orientation.

[0089] <Precursor Synthesis Results>

[0090] Table 1 below shows the precursor synthesis results of Examples and Comparative Examples according to the present invention. The Comparative Example in Table 1 below represents prior art and is a positive electrode active material precursor manufacturing apparatus that does not include a separate solid-liquid separation component and a filtrate discharge port. Example 1 is a lithium secondary battery positive electrode active material precursor manufacturing apparatus that includes a solid-liquid separation component and a filtrate discharge port. Example 2 is a lithium secondary battery positive electrode active material precursor manufacturing apparatus that includes a first reactor that does not include a solid-liquid separation component and a filtrate discharge port, and a second reactor that includes a solid-liquid separation component and a filtrate discharge port.

[0091]

Table 1

[0092] Comparative Example Example 1 Example 2 Reaction residence time (hr / RT) 20 10 10 Total reaction time (hr / batch) 20 30 30 Precursor output (kg / batch) 10 30 60 Monthly output (kg / month) 280 593 1,186

[0093] Figure 7a and Figure 7b The following are photos of precursor synthesis results generated according to the examples and comparative examples of the present invention. Figure 7a The following is a photo of the precursor synthesis result of the comparative example. Figure 7b The following is a photo of the precursor synthesis result of Example 2. Figure 7a and Figure 7b It can be confirmed that the physical properties of the product, such as particle size distribution, particle state, and sphericity, have been improved.

[0094] The present invention can be implemented in various ways and is not limited to the above-described embodiments. A person skilled in the art will appreciate that the present invention can be implemented in other specific ways without changing the technical concept or essential features of the present invention. Therefore, it should be understood that the above-described embodiments are illustrative in all respects and are not restrictive.

Claims

1. A device for producing a precursor of a positive electrode active material for a lithium secondary battery, comprising: A reactor for adding reaction raw materials to generate reaction products; A stirrer, the stirrer is used to stir the reaction raw materials; a solid-liquid separation component, the solid-liquid separation component being disposed between the side wall of the reactor and the stirrer and being used to perform solid-liquid separation in the reaction product; as well as The filtrate discharge port is arranged on the upper part of the solid-liquid separation component and is used to separate and discharge the filtrate to the outside of the reactor.

2. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 1, wherein: The solid-liquid separation component includes a lower part, a middle part and an upper part, and the cross-sectional area of ​​the lower part gradually decreases from top to bottom.

3. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 1, wherein: The solid-liquid separation component includes a plurality of solid-liquid separation components.

4. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 3, wherein: The plurality of solid-liquid separation components are arranged relative to each other.

5. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 1, comprising: The filtrate discharge auxiliary part is used to assist the filtrate provided from the plurality of solid-liquid separation parts to move to the filtrate discharge part.

6. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 1, wherein: A plurality of the reactors are connected in parallel.

7. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 1, wherein: The filtrate discharge port is arranged to be tilted downward as it is further away from the reactor.

8. A device for producing a precursor of a positive electrode active material for a lithium secondary battery, comprising a plurality of reactors including a first reactor and a second reactor, wherein: The first reactor comprises: a first stirrer for stirring the added reaction raw materials; and a discharge port for discharging part of the reactants of the reaction raw materials. The second reactor includes: a second stirrer for stirring the reactants flowing from the first reactor; a solid-liquid separation component disposed between the side wall of the first reactor and the second stirrer for performing solid-liquid separation in the reaction product; and a filtrate discharge port disposed at the top of the solid-liquid separation component for separating and discharging the filtrate to the outside of the reactor. The production apparatus includes a second reactor disposed on the side of the first reactor and at a position lower than the first reactor.

9. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 8, comprising: A recovery component is connected from the second reactor toward the first reactor and is used to recover part of the filtrate.

10. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 8, wherein: A plurality of the second reactors are connected in parallel.

11. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 8, wherein: The solid-liquid separation component includes a lower part, a middle part and an upper part, and the cross-sectional area of ​​the lower part gradually decreases from top to bottom.

12. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 11, wherein: The solid-liquid separation component includes a plurality of solid-liquid separation components.

13. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 12, comprising: A filtrate discharge auxiliary portion is provided for assisting the filtrate provided from the plurality of solid-liquid separation parts to move to the filtrate discharge portion.

14. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 11, wherein: The solid-liquid separation component includes a starting volume area and a reaction volume area, The reaction volume region is 70 to 90% of the reactor interior volume.

15. The device for producing a positive electrode active material precursor for a lithium secondary battery according to claim 11, wherein: The internal volume of the solid-liquid separation component is less than 20% of the entire reaction volume area.

16. A method for manufacturing a precursor of a positive electrode active material for a lithium secondary battery, the method comprising: adding a reaction raw material including a mixed metal salt solution and an alkali solution into a reactor and stirring the mixture with a stirrer to generate a reaction product including precursor particles; A step of being disposed between the reactor and the stirrer during the generation of the reaction product to separate the solid and liquid in the reaction product; as well as The step of performing the solid-liquid separation includes discharging the remaining filtrate.

17. The method for producing a positive electrode active material precursor for a lithium secondary battery according to claim 16, wherein: In the step of separating solid and liquid in the reaction product, which is arranged between the reactor and the stirrer during the reaction product generation process, the step of separating solid and liquid is performed by a plurality of solid-liquid separation components.

18. The method for manufacturing a positive electrode active material precursor for a lithium secondary battery according to claim 16, comprising: Before the step of separating the solid and liquid in the reaction product, the step is arranged between the reactor and the stirrer during the reaction product generation process. A step of generating reactants from the reaction raw materials in an additional reactor.

19. The method for producing a positive electrode active material precursor for a lithium secondary battery according to claim 18, wherein: The step of separating the solid and liquid in the reaction product by being arranged between the reactor and the stirrer during the reaction product generation process also includes a step of being performed in parallel in a plurality of reactors.

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