KR20220159228A - Apparatus comprising multi reactors for cathode active material precursor preparing of lithium ion secondary battery, and cathode active material precursor of lithium ion secondary battery prepared from it - Google Patents

Abstract

The present invention relates to a cathode active material precursor manufacturing device for lithium ion secondary battery, and a cathode active material precursor for lithium ion secondary batteries manufactured therefrom. The cathode active material precursor manufacturing device includes a plurality of reactors (10a, 20a, 30a), wherein the reactors are sequentially installed to have a constant height difference from a reaction starting point; or includes a plurality of reactors (10a, 20a, 30a), wherein the reactors have the same height and enable a product produced in a preceding reactor to be moved to a following reactor by external pressure. The manufacturing device according to the present invention can set the composition of an injected metal solution and the concentration of caustic soda and ammonia differently by setting a height difference for each reactor or arranging several reactors with a pressure difference, allowing continuous synthesis without stopping the reaction. Thus, the quality of a precursor can be improved. In addition, it can be expected to make it easier for workers to drive and manage operations, and productivity can be enhanced.

Description

Apparatus for manufacturing a cathode active material precursor of a lithium ion secondary battery including a plurality of reactors, and a cathode active material precursor of a lithium ion secondary battery prepared therefrom PRECURSOR OF LITHIUM ION SECONDARY BATTERY PREPARED FROM IT}

The present invention relates to an apparatus for manufacturing a cathode active material precursor for a lithium ion secondary battery including a plurality of reactors, and a cathode active material precursor for a lithium ion secondary battery prepared therefrom. It relates to an apparatus for manufacturing a cathode active material precursor for a lithium ion secondary battery, which consists of several arrangements using a pressure difference, and a cathode active material precursor for a lithium ion secondary battery manufactured therefrom.

The key components of a lithium ion secondary battery are cathode materials, anode materials, separators, and electrolytes. Among them, the material with the highest ratio and the most important is the cathode material. As for the positive electrode material, the NCM three-component system mainly containing nickel (Ni)-cobalt (Co)-manganese (Mn) as main components is attracting the most attention. This is because it has the advantages of high capacity of Ni, excellent electrochemical performance of Co, and stability of Mn.

In order to manufacture such a cathode material, the synthesis of a precursor must be performed first, and a common synthesis method is a coprecipitation method using an aqueous metal solution, a chelating agent, and a precipitating agent. In addition, by using the co-precipitation method, a precursor having a core-shell structure is composed of Ni and Co having high capacity in the core and Mn, a material having stability, is added to the shell. synthesize It is known that the positive electrode active material precursor having such a core-shell structure has excellent stability because it has a shell layer.

However, the composition of the core and the shell are usually different from each other, and when there is a rapid change in the composition, another problem may occur in which the stability of the shell layer is lowered due to this compositional difference.

In general, the production of a cathode active material precursor having a core-shell structure is synthesized using a batch reactor. In this case, there is a problem in that the synthesis must be stopped every time the synthesis step of the core layer and the shell layer is performed, and equipment and equipment The downside is that it is complex. Therefore, efforts have been made to solve these disadvantages by using a continuous stirred tank reactor (CSTR).

For example, in Korean Patent Registration No. 10-2008875, a concentration gradient precursor is prepared using a concentration gradient precursor manufacturing apparatus (see FIG. 1) in which the materials of the first supply tank and the second supply tank are mixed in advance in a mixer and then introduced into the reactor. In the method, two supply tanks (Q1, Q2) for storing metal solutions with different composition ratios, a plurality of mixers (Q3) for mixing metal solutions with different composition ratios input from these two supply tanks (Q1, Q2) And a concentration gradient precursor manufacturing apparatus including a plurality of reactors (A, B, C, D) connected to a plurality of mixers (Q3) in a 1: 1 correspondence and receiving a mixed metal solution from the mixer (Q3). presented.

Although the above patent includes a plurality of reactors (A, B, C, D), separate supply tanks (Q1, Q2) for supplying metal solutions with different composition ratios, and a plurality of mixers (Q3, Q4) for mixing them Since it must be included separately, the manufacturing apparatus is complicated, and this has a disadvantage in that the process efficiency is lowered.

In addition, in Korean Patent Publication No. 2020-0063406, the main body 10, the upper part of which is opened and closed through attachment and detachment, is composed of a plurality of parts inside the main body 10, but is arranged in a row, and the reaction liquid 30 is accommodated and the counter electrode 52 ) is installed, the reaction chamber 100 to which the reference electrode 51 is attached to the side, the palladium sheet 20 for being supported in the reaction liquid 30, and the palladium sheet 20 are placed, and the reaction liquid 30 A moving member 200 for moving the palladium sheet 20 placed so as to be supported on the moving member 200, a moving path member 300 providing a moving path for the moving member 200, and a power transmission member transmitting power to the moving member 200. , including a power supply 60 for applying voltage to the electrodes 51 and 52 and a solution injection member 70 for injecting the copper precursor-containing solution 71 or the platinum precursor-containing solution 72 into the reaction solution 30 A continuous reactor type core-shell catalytic electrode manufacturing apparatus (see FIG. 2) is presented.

In the above patent, the reaction liquid 30 is accommodated in the first, second, and third reaction chambers 110, 120, and 130, respectively, and the reaction liquid 30 of the first reaction chamber 110 is a palladium sheet 20 It is a solution for reducing and coating with copper, the reaction solution 30 of the second reaction chamber 120 is a solution for coating platinum on the palladium sheet 20 coated with copper, and the third reaction chamber 130 The reaction solution 30 of the presented a solution (eg, water) for cleaning the palladium sheet 20 coated with platinum.

However, in the technologies known so far related to manufacturing devices using continuous reactors, including the prior patents, the devices and processes are still very complicated, so that the stability to maintain the structure of the cathode active material precursor having a core-shell structure is poor. There are falling problems.

Therefore, in line with the development of electric vehicles, the importance of cathode active materials is increasing more than ever, and the development of a manufacturing device with a new structure that can stably manufacture cathode active material precursors that can meet the needs of an era in which demand is rapidly increasing is essential. It is an urgent situation.

KR 10-2008875 B1 KR 10-2020-0063406 A

Therefore, in the present invention, a plurality of reactors are used, but a lithium ion secondary capable of securing structural stability of a precursor having a core-shell structure according to a composition change of a core layer and a shell layer by arranging adjacent reactors with a level difference of a certain height. Its purpose is to provide a manufacturing apparatus for a battery cathode active material precursor.

In addition, in the present invention, a plurality of reactors are used, but the core-shell structure according to the composition change of the core layer and the shell layer is obtained by arranging a structure in which products can be moved using a pressure difference while having the same height between adjacent reactors. An object of the present invention is to provide an apparatus for manufacturing a precursor of a cathode active material for a lithium ion secondary battery capable of ensuring structural stability of the precursor.

In addition, an object of the present invention is to provide a precursor of a cathode active material for a lithium ion secondary battery using a manufacturing apparatus having the above characteristics.

An apparatus for manufacturing a precursor of a cathode active material for a lithium ion secondary battery according to a first embodiment of the present invention includes a plurality of reactors 10a, 20a, and 30a, and the reactors 10a, 20a, and 30a are sequentially formed from the reaction starting point. It can be installed to have a certain height difference.

In addition, the apparatus for manufacturing a precursor of a cathode active material for a lithium ion secondary battery according to the second embodiment of the present invention includes a plurality of reactors 110a, 120a, and 130a, and the reactors 10a, 20a, and 30a have the same height. It may be to allow the product produced in the preceding reactor to move to the following reactor by external pressure.

In the manufacturing apparatus according to the first embodiment of the present invention, the difference in height between the sequentially installed reactors is made by installing such that the height of the outlet of the precipitate synthesized in the preceding reactor and the inlet of the subsequent reactor into which the precipitate flows are different. desirable.

In addition, in the manufacturing apparatus according to the first and second embodiments of the present invention, in the plurality of reactors, including a raw material inlet for manufacturing a cathode active material precursor of a lithium ion secondary battery, each reactor has a different composition ratio It is characterized by being able to control the content of raw materials so that they can be input.

In addition, the cathode active material precursor of the lithium ion secondary battery manufactured according to the first and second embodiments of the present invention preferably has a core-shell structure.

In the manufacturing apparatus according to the first and second embodiments of the present invention, the first precipitate synthesized in the first reactors 10a and 110a among the plurality of reactors is for preparing the core layer of the cathode active material precursor can

In addition, in the manufacturing apparatus according to the first and second embodiments of the present invention, among the plurality of reactors, reactors 20a, 30a, and 120a sequentially installed at the rear of the first reactors 10a and 110a , The precipitates synthesized in 130a) are the shell layer of the cathode active material precursor, and the shell layer is preferably formed in two or more layers.

In each embodiment, the shell layer is made of Ni:Co:Mn, and each shell layer formed of two or more layers may be designed to have a different composition, so that according to the volume change that may occur during drying of the precursor, stability can be achieved.

In addition, the present invention provides a cathode active material precursor of a lithium ion secondary battery manufactured using any one of the manufacturing apparatuses according to the first embodiment and the second embodiment.

In the manufacturing apparatus according to the present invention, synthesis may not be stopped when the composition is changed from the core layer to the shell layer, as in a conventional batch reactor.

In addition, by arranging several reactors with a height difference or a pressure difference for each reactor, the content ratio of metal solution, caustic soda, and ammonia, which are raw materials used in precursor manufacturing, can be set differently in each reactor, so that the reaction can be continuously performed without stopping. can be synthesized to improve the quality of the precursor.

In addition, the effect of facilitating operation and management of workers can be expected, and productivity can be increased.

1 is a concentration gradient precursor manufacturing apparatus according to Patent Document 1,
2 is a core-shell catalyst electrode manufacturing apparatus according to Patent Document 2,
Figure 3 is a manufacturing apparatus for a lithium ion secondary battery cathode active material precursor according to a first embodiment of the present invention, a manufacturing apparatus having a plurality of reactors having a stepped structure,
4 is a manufacturing apparatus for a lithium ion secondary battery cathode active material precursor according to a second embodiment of the present invention, which arranges a plurality of reactors to have the same height, but shows a manufacturing apparatus including a pressure control device using a pump. .

Hereinafter, the present invention will be described in more detail.

Terms used in this specification are used to describe specific embodiments and are not intended to limit the present invention. As used herein, the singular form may include the plural form unless the context clearly indicates otherwise. Also, when used herein, "comprise" and/or "comprising" specifies the presence of the recited shapes, numbers, steps, operations, elements, elements, and/or groups thereof. and does not exclude the presence or addition of one or more other shapes, numbers, operations, elements, elements and/or groups.

The present invention relates to a manufacturing apparatus for a cathode active material precursor for a lithium ion secondary battery, and a cathode active material precursor for a lithium ion secondary battery manufactured using the manufacturing apparatus.

Referring to FIG. 3 showing a manufacturing apparatus for a cathode active material precursor for a lithium ion secondary battery according to a first embodiment of the present invention, the manufacturing apparatus 100 according to the present invention includes a plurality of reactors 10a, 20a, and 30a. Including, the reactors (10a, 20a, 30a) may be installed to have a constant height difference sequentially from the reaction starting point (A).

The difference in height between the sequentially installed reactors is determined when the height of the outlet of the precipitate synthesized in the preceding reactor is higher than the inlet of the rear reactor into which the precipitate is introduced.

That is, referring to FIG. 3, the precipitate synthesized in the first reactor 10a (hereinafter referred to as the first precipitate) passes through the outlet 14a to the second reactor 20a through the first pipe 15a. When introduced, the first precipitate synthesized in the first reactor 10a is separated from the inlet 26a of the second reactor 20a in height compared to the outlet 14a of the first reactor 10a. It can effectively move to the reactor (20a).

This applies equally to the arrangement of the third reactor 30a in the second reactor 20a and the fourth reactor 40a in the third reactor 30a, that is, the outlet 24a of the second reactor 20a. ), the inlet 36a of the third reactor 30a is also installed to have a certain height difference (step difference), and the inlet 46a of the receiver 40a compared to the outlet 34a of the third reactor 30a is also constant. It is desirable to install so that there is a height difference (step difference).

By having the height difference, each of the reactors 10a, 20a, and 30a can be positioned with a certain level difference, so that the product (precipitate) synthesized in the preceding reactor can efficiently move to the following reactor, while the receiver 40a ) has the effect of enabling continuous reaction without stopping the reaction until the final product is reached.

In addition, although the manufacturing apparatus according to the first embodiment of the present invention is shown in FIG. 3 and includes only three reactors 10a, 20a, and 30a, the reactors are not limited to three and may be added according to a predetermined purpose. It may be, and the number is not particularly limited.

The number of reactors is determined according to the structure of the finally prepared lithium ion secondary battery cathode active material precursor, and the precursor according to the present invention preferably has a core-shell structure.

Therefore, in the first reactor 10a located first from the reaction starting point A, the core layer of the cathode active material precursor is prepared, and the reactors 20a, which are sequentially installed at the rear of the first reactor 10a, 30a) is for preparing the shell layer of the cathode active material precursor.

The cathode active material precursor according to the present invention has a core-shell structure, but the shell layer is preferably formed of at least two or more layers.

Therefore, it can be said that the number of reactors is determined according to the structure of the shell layer. For example, in the case of manufacturing a cathode active material precursor composed of a core layer and two shell layers, three reactors are required, and in the case of manufacturing a cathode active material precursor composed of a core layer and three shell layers, four reactors are required.

At this time, the core layer is preferably made of Ni and Co.

The first reactor 10a for preparing the core layer includes an inlet 11a for injecting a precipitant, an inlet 11b for injecting a chelating agent, and an inlet 11c for injecting the first aqueous solution of metal, each having a predetermined content. It is made by injecting rain.

The first metal aqueous solution is composed of Ni and Co, and it is preferable to use ammonia as a chelating agent and caustic soda as a precipitant. After the reaction raw materials are introduced through the inlets and synthesis starts in the first reactor 10a, when the water level rises and overflow begins, the precipitate formed in the first reactor 10a passes through the outlet 14a of the first reactor. Through this, it passes to the inlet 26a of the second reactor 20a.

In each of the reactors 10a, 20a, and 30a, baffles 12a, 22a, and 32a and agitators 13a, 23a, and 33a, which are dispersing devices that generate up and down vortexes, are installed in order to uniformly disperse the precipitate generated in the reactor. include That is, it can be said to be a dispersing device for better mixing of the reactants up and down by generating vortexes inside each of the reactors 10a, 20a, and 30a, and also for better mixing in all directions so that the reaction occurs better. Preferably, 4 to 6 baffles 12a, 22a, and 32a are installed along the circumferential direction inside each of the reactors 10a, 20a, and 30a.

When the first precipitate is introduced through the inlet 26a of the second reactor 20a, the precipitant inlet 21a of the second reactor 20a, the inlet 21b for injecting the chelating agent, and the second metal aqueous solution Through the inlet (21c) for introducing the raw materials at a predetermined content ratio, respectively. Raw materials introduced in the second reactor 20a react with the core layer formed by the first precipitate to form a shell layer (referred to as a first shell layer), thereby generating a precipitate (referred to as a second precipitate).

The precipitant added is caustic soda, the chelating agent is ammonia, and the second metal aqueous solution for forming the shell layer is preferably composed of Ni, Co, and Mn.

The shell layer is made of Ni:Co:Mn, and the content ratio of Ni:Co:Mn is differently controlled in the composition of the first shell layer and the second shell layer constituting the shell layer to have a multi-layered shell layer. It is preferable to have.

In addition, after synthesis starts in the second reactor 20a, when the water level rises and overflow begins, the second precipitate formed in the second reactor 20a passes through the outlet 24a of the second reactor to the third reactor ( It passes to the inlet 36a of 30a).

When the second precipitate is introduced through the inlet 36a of the third reactor 30a, in the third reactor 30a, the precipitant inlet 31a and the chelating agent are introduced in the same way as in the second reactor 20a. Ni, Co, and Mn raw materials are inputted as caustic soda, ammonia, and the second metal aqueous solution at a predetermined content ratio, respectively, through the inlet 31b and the inlet 31c through which the second metal aqueous solution is introduced.

The raw materials introduced in the third reactor 30a react with the core-shell layer formed by the second precipitate to form an additional shell layer (referred to as the second shell layer) to form a precipitate (core-shell structure precursor), , the synthesis is terminated by overflowing to the inlet 46a of the receiver 40 through the outlet 34a of the third reactor.

The finally obtained cathode active material precursor has a structure consisting of a core layer and two shell layers, and the two shell layers are preferably composed of different compositions.

For example, when the shell layer is composed of two layers, it is preferable to include a higher Mn content in the second shell layer than in the first shell layer in the shell layer composed of Ni:Co:Mn. That is, stability, which is an advantage of Mn, can be increased by including a higher Mn content than the first shell layer in the second shell layer located at the outermost part of the cathode active material precursor.

On the other hand, referring to FIG. 4 showing an apparatus for manufacturing a cathode active material precursor of a lithium ion secondary battery according to the second embodiment, which is another embodiment of the present invention, the manufacturing apparatus of the present invention includes a plurality of reactors 110a, 120a, and 130a ), wherein the reactors (110a, 120a, 130a) have the same height, but are characterized in that the product produced in the preceding reactor can be moved to the following reactor by the external pressure (170a, 270a, 370a) have

That is, the precursor manufacturing apparatus according to the first embodiment of FIG. 3 arranges a plurality of reactors to have a constant height difference, whereas the precursor manufacturing apparatus according to the second embodiment of FIG. 4 has a height difference between the plurality of reactors. Product movement between reactors without being applied has a difference in performing a method of applying physical force using external pressure.

Therefore, in the manufacturing apparatus according to FIG. 4, each of the reactors 110a, 120a, 130a and the receiver 140 have the same configuration as in FIG. 3, and the raw materials used for manufacturing the core layer and the shell layer are also the same.

Referring to FIG. 4, the plurality of reactors 110a, 120a, and 130a and the receiver 140 are arranged to have the same height, and the first reactor 110a located first from the reaction starting point A' is for preparing the core layer of the cathode active material precursor, and the reactors 120a and 130a sequentially installed at the rear of the first reactor 110a are for preparing the shell layer of the cathode active material precursor.

However, after the reaction raw materials are introduced through each inlet and synthesis starts in the first reactor 110a, when the water level rises and overflow begins, the precipitate formed in the first reactor 110a flows through the outlet 114a of the first reactor. It passes through the first pipe 115a to the inlet 126a of the second reactor 120a. At this time, a pump device 170a is installed to apply physical force to the first pipe 115a with external pressure so that the precipitate generated in the preceding reactor moves to the subsequent reactor using the pump pressure.

The first reactor 110a for preparing the core layer includes an inlet 111a for injecting a precipitating agent, an inlet 111b for injecting a chelating agent, and an inlet 111c for injecting the first aqueous solution of metal, each having a predetermined content. It is made by injecting rain.

The core layer is preferably made of Ni and Co.

The first metal aqueous solution is composed of Ni and Co, and it is preferable to use ammonia as a chelating agent and caustic soda as a precipitant.

In each of the reactors 110a, 120a, and 130a, baffles 112a, 122a, and 132a and agitators 113a, 123a, and 133a, which are dispersing devices that generate up and down vortices for uniform dispersion of the precipitate generated in the reactor, are installed. include That is, it can be said to be a dispersing device for better mixing of the reactants up and down by creating a vortex inside the reactors 110a, 210a, and 130a, and also for better mixing in all directions so that the reaction occurs better. It is preferable that 4 to 6 baffles 112a, 122a, and 132a are installed along the circumferential direction inside each of the reactors 110a, 210a, and 130a.

When the first precipitate is introduced through the inlet 126a of the second reactor 120a, the precipitant inlet 121a of the second reactor 120a, the inlet 121b for injecting the chelating agent, and the second aqueous metal solution Through the inlet (121c) for introducing the raw materials at a predetermined content ratio, respectively. Raw materials introduced in the second reactor 120a react with the core layer formed by the first precipitate to form a shell layer (referred to as a first shell layer), thereby generating a precipitate (referred to as a second precipitate).

In addition, after synthesis starts in the second reactor 120a, when the water level rises and overflow begins, the second precipitate formed in the second reactor 120a exits the outlet 124a of the second reactor and flows through the second pipe. It passes to the inlet 136a of the third reactor 130a through 125a. At this time, a pump device 270a is installed to apply physical force to the second pipe 125a so that the second precipitate generated in the second reactor 120a moves to the third reactor 130a.

When the second precipitate is introduced through the inlet 136a of the third reactor 130a, in the third reactor 130a, the precipitant inlet 131a and the chelating agent are introduced in the same way as in the second reactor 120a. Ni, Co, and Mn raw materials are inputted as caustic soda, ammonia, and the second metal aqueous solution at a predetermined content ratio, respectively, through the inlet 131b and the inlet 131c through which the second metal aqueous solution is introduced.

The raw materials introduced in the third reactor 130a react with the core-shell layer formed by the second precipitate to form an additional shell layer (referred to as a second shell layer) to form a precipitate (referred to as a third precipitate). Synthesis is terminated by flowing out of the outlet 134a of the third reactor 130a and overflowing to the inlet 146a of the receiver 140 through the third pipe 135a. At this time, a pump device 370a is installed to apply physical force to the third pipe 135a so that the final precipitate (core-shell structure precursor) generated in the third reactor 130a moves to the receiver 140. make it possible

As a result, the final cathode active material precursor prepared according to the present invention has an effect of maintaining volume stability during drying of the precursor by having different compositions even in the shell layer having a multilayer structure.

As described in detail above, in the present invention, in arranging a plurality of reactors for manufacturing a cathode active material precursor of a lithium ion secondary battery having a stable core-shell structure, steps with a constant height difference are used; It was confirmed that this can be achieved by arranging a plurality of reactors at the same height by applying an external physical force.

In addition, when manufacturing a cathode active material precursor of a lithium ion secondary battery having a core-shell structure, the disadvantage of stopping the synthesis when changing the composition from the core layer to the shell layer is eliminated, as well as by arranging a plurality of reactors to manufacture the core layer and the shell layer. Since the composition of the injected metal solution and the concentrations of caustic soda and ammonia can be set differently, the quality of the precursor can be improved because it can be continuously synthesized without stopping the reaction.

In addition, although the preferred embodiments of the present invention have been shown and described above, the present invention is not limited to the specific embodiments described above, and the technical field to which the present invention belongs without departing from the gist of the present invention claimed in the claims. Of course, various modifications are possible by those skilled in the art, and these modifications should not be individually understood from the technical spirit or perspective of the present invention.

Claims (9)

Including a plurality of reactors (10a, 20a, 30a),
The reactors (10a, 20a, 30a) are installed to have a constant height difference sequentially from the reaction start point, a cathode active material precursor manufacturing apparatus of a lithium ion secondary battery. Including a plurality of reactors (110a, 120a, 130a),
The reactors (10a, 20a, 30a) have the same height, the positive electrode active material precursor manufacturing apparatus of a lithium ion secondary battery that allows the product produced in the preceding reactor to move to the subsequent reactor by external pressure. According to claim 1,
The height difference between the sequentially installed reactors is a cathode active material precursor manufacturing device for a lithium ion secondary battery formed by installing a difference in height between the outlet of the precipitate synthesized in the preceding reactor and the inlet of the subsequent reactor into which the precipitate flows. According to claim 1 or 2,
In the plurality of reactors, including a raw material inlet for manufacturing a cathode active material precursor of a lithium ion secondary battery, the content of the raw material can be adjusted so that each reactor can be input at a different composition ratio. Apparatus for manufacturing a precursor of a cathode active material of a lithium ion secondary battery. According to claim 1 or 2,
The cathode active material precursor of the lithium ion secondary battery is a cathode active material precursor manufacturing apparatus of a lithium ion secondary battery having a core-shell structure. According to claim 1 or 2,
The first precipitate synthesized in the first reactors 10a and 110a among the plurality of reactors is a cathode active material precursor manufacturing apparatus for a lithium ion secondary battery for preparing a core layer of a cathode active material precursor. According to claim 1 or 2,
Among the plurality of reactors, the precipitates synthesized in the reactors sequentially installed at the rear of the first reactors 10a and 110a are a shell layer of a cathode active material precursor, and the shell layer may be formed in two or more layers for a lithium ion secondary battery. Cathode active material precursor manufacturing apparatus. According to claim 7,
The shell layer is made of Ni: Co: Mn, and each shell layer formed of two or more layers has a different composition, a cathode active material precursor manufacturing apparatus for a lithium ion secondary battery. A cathode active material precursor for a lithium ion secondary battery manufactured using the manufacturing apparatus according to any one of claims 1 or 2.

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