KR101526882B1 - Continuous mass-production apparatus for precursor of secondary battery by co-precipitation method - Google Patents

Abstract

The present invention relates to a precursor continuous mass production apparatus for a secondary cell using a coprecipitation reaction, and according to the present invention, the synthesized precursor can be grown by sequentially moving the growth space, thereby enabling mass production of precursors of homogeneous particles continuously.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a continuous mass production apparatus for a secondary battery using a coprecipitation reaction,

The present invention relates to an apparatus for continuously producing a precursor for a secondary battery, and more particularly, to a system for continuously producing a precursor for a secondary battery, which is capable of continuously growing a synthesized precursor in a growth space, And a continuous mass production device for a battery precursor.

As a method of producing the cathode active material for a secondary battery, there are a solid phase reaction method and a wet method.

The solid-phase reaction method is a process of mixing and pulverizing several constituent raw powders several times. However, such a process has a problem in that the composition is uneven, the possibility of impurities is high during the grinding, and a large amount of energy is consumed since it has to be sintered at a high temperature.

The wet process is divided into spray pyrolysis and coprecipitation. The spray pyrolysis method is a method of dissolving a constituent material in a solvent and generating a droplet of a certain size and instantly firing to obtain a metal oxide. As a cathode active material for a secondary battery, Repeated cycles can easily disintegrate the crystal structure and shorten the lifetime of the battery.

The coprecipitation method is a method of synthesizing and growing a metal hydroxide precursor by controlling the pH after dissolving the constituent materials in a solvent.

However, when the metal hydroxide precursor is prepared by the conventional coprecipitation method, it is necessary to wait for a long time of about 5 to 30 hours until the synthesis and the growth process are completed after putting the constituent materials into one reactor, There is a problem that this is difficult.

Meanwhile, Korean Patent Laid-Open No. 10-2011-0063360 is known as a conventional technique related to the production of a precursor for a secondary battery.

DISCLOSURE Technical Problem The present invention has been conceived to solve the problems of the prior art as described above, and it is an object of the present invention to provide a precursor for a secondary battery using a coprecipitation method, in which a precursor synthesized in a synthesis space grows successively in a growth space, A precursor continuous mass production apparatus for a secondary cell using a coprecipitation reaction capable of continuously mass-producing precursors grown in a continuous manner.

In order to accomplish the above object, there is provided an apparatus for continuous mass production of a precursor for a secondary battery using a coprecipitation reaction, comprising: a synthesis chamber in which raw materials, sodium hydroxide and ammonia are introduced to synthesize precursors; At least two growth chambers in which precursors synthesized in the synthesis chamber are introduced and grown; A stirrer installed in at least one of the synthesis chamber and at least one of the at least two growth chambers, for agitating the introduced raw material, sodium hydroxide, ammonia or the precursor; And a heater installed in at least one of the synthesis chambers and the at least two growth chambers to regulate the temperature.

Herein, the two or more growth chambers are sequentially installed at a lower position in the next stage of the synthesis chamber, and the synthesis chamber and the growth chambers are connected by a transfer pipe which is opened and closed by a valve, The grown precursor can move to the next stage chamber.

In addition, the two or more growth chambers are sequentially installed at the next stage of the synthesis chamber, and the synthesis chamber and the growth chambers are connected by a pump and a transfer pipe so that the synthesized and grown precursor Stage chamber.

In addition, the at least two growth chambers are connected to the synthesis chamber by a pump and a transfer pipe, respectively, so that the precursor synthesized in the synthesis chamber through the operation of the pump can sequentially move to the respective growth chambers.

The raw material may include nickel sulfate, cobalt sulfate, manganese sulfate, or aluminum nitrate.

In order to accomplish the above object, there is provided a continuous mass production apparatus for a precursor for a secondary battery using a coprecipitation reaction, comprising: a production chamber having a space inside; A partition wall dividing a space inside the production chamber into a composite space in which a precursor is synthesized and a plurality of growth spaces in which the synthesized precursor is grown; An agitator which stirs the raw material, sodium hydroxide, and ammonia, which are installed in at least one of the synthesis space and the plurality of growth spaces, into the synthesis space, or agitates the precursor introduced into the growth space; And a heater installed in at least one of the plurality of growth spaces and the plurality of growth spaces to adjust the temperature. The precursor synthesized in the synthesis space may be grown by sequentially moving the plurality of growth spaces.

In this case, the precursors that are sequentially lowered in height are formed in the partition walls so that the precursors synthesized in the synthesis space can be sequentially transferred to the neighboring growth spaces when the precursors reach the hole height.

In addition, the synthesis space and the growth spaces are connected by a pump and a transfer pipe, so that the synthesized and grown precursor can move to the next stage space through the operation of the pump.

According to the present invention, the synthesis chamber and the growth chamber are continuously connected, or a plurality of spaces in the production chamber are partitioned so that the precursor is synthesized in the first synthesis space, and the synthesized precursor moves homogeneously So that continuous mass production is possible without having to wait for a long time until synthesis and growth are completed in one reaction vessel.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view for explaining a precursor continuous mass production apparatus for a secondary battery using a coprecipitation reaction according to a first embodiment of the present invention; FIG.
2 is a view for explaining a precursor continuous mass production apparatus for a secondary battery using a coprecipitation reaction according to a second embodiment of the present invention.
3 is a view for explaining a precursor continuous mass production apparatus for a secondary battery using a coprecipitation reaction according to a third embodiment of the present invention.
4 is a view for explaining a precursor continuous mass production apparatus for a secondary battery using a coprecipitation reaction according to a fourth embodiment of the present invention.
5 is a view for explaining a precursor continuous mass production apparatus for a secondary battery using a coprecipitation reaction according to a fifth embodiment of the present invention.
FIG. 6 is a view for explaining a concept of a device for continuously producing precursors by combining a plurality of production chambers shown in FIG. 4 and FIG. 5; FIG.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, some configurations which are not related to the gist of the present invention may be omitted or compressed, but the configurations omitted are not necessarily those not necessary in the present invention, and they may be combined by a person having ordinary skill in the art to which the present invention belongs. .

≪ Embodiment 1 >

1 is a view for explaining a precursor continuous mass production apparatus for a secondary cell (hereinafter referred to as a precursor continuous production apparatus) using the coprecipitation reaction according to the first embodiment of the present invention. As shown in FIG. 1, the precursor continuous production apparatus according to the first embodiment of the present invention comprises a synthesis chamber 10 and a plurality of growth chambers 20.

The synthesis chamber 10 installed at the frontmost side is provided with a synthesis space 12 on the inner side and a heater 13 for temperature control is provided around the synthesis chamber 10. The synthesis space 12 is provided with a stirrer 14 operated by a motor 15. The material introduction part 11 is inserted into the synthesis space 12 so that the raw material solution, the sodium hydroxide solution and the ammonia solution are introduced from the outside, Lt; / RTI > The temperature measurement unit 16 for measuring the temperature of the synthesis space 12 and the PH measurement unit 17 for measuring the hydrogen ion concentration are also provided in the synthesis space 12. [ In addition, at the upper end of the synthesis chamber 10, a water discharge port 18 through which the reacted wastewater is discharged is provided.

The growth chamber 20 has a basic configuration similar to the synthesis chamber 10. In other words, a growth space 22 is provided inside the growth chamber 20, and a heater 23 is provided around the growth chamber 20 for temperature control. A stirrer 24 operated by a motor 25 is provided in the growth space 22 and the material input portion 21 is connected to the growth space 22 so that sodium hydroxide solution and ammonia solution are injected from the outside have. A temperature measurement unit 26 for measuring the temperature of the growth space 22 and a PH measurement unit 27 for measuring the hydrogen ion concentration are provided in the growth space 22. [ Likewise, a full water outlet 28 is provided at the top of the growth chamber 20.

The plurality of growth chambers 20 are installed so as to be sequentially lowered to the next stage of the synthesis chamber 10. Further, the synthesis chamber 10 and the next-stage growth chamber 20 are connected by a transfer pipe 30 and a valve 32. A transfer pipe 30 is connected from the lower end of the synthesis chamber 10 to the upper end of the growth chamber 20 at the next stage and a valve 32 is provided at one point of the transfer pipe 30. Likewise, the adjacent growth chambers 20 are connected to the conveying pipe 30.

A process for continuously producing a precursor for a secondary battery using the precursor continuous production apparatus according to the first embodiment described above will now be described.

First, the control means (not shown) activates the heater 13 of the synthesis chamber 10 to heat the synthesis space 12 to a predetermined temperature. The operation of the heater 13 is adjusted based on the temperature measured at the temperature measuring unit 16. [

Then, the raw material solution, the sodium hydroxide [NaOH] solution and the ammonia [NH ₄ OH] solution are injected through the material input portion at the predetermined ratio.

The raw materials are controlled differently depending on the characteristics of the precursor to be produced. A raw material metal selected from nickel sulfate [NiSO ₄ ], cobalt sulfate [CoSO ₄ ], manganese sulfate [MnSO ₄ ] or aluminum nitrate [Al (NO ₃ ) ₃ ] is dissolved in ultrapure water.

The sodium hydroxide [NaOH] solution is added as a co-precipitant for the synthesis of the precursor, and the ammonia [NH ₄ OH] solution is added to regulate the hydrogen ion concentration in the synthesis space 12. The injection timing and amount of the ammonia solution are controlled by the control means (not shown) according to the hydrogen ion concentration measured by the PH measuring unit.

When the raw material solution and the sodium hydroxide solution are introduced into the synthesis space 12 at a predetermined temperature and at a predetermined rate in the PH atmosphere and the stirrer 14 is rotated by the operation of the motor 15, And the precursor seed is synthesized. Synthesis of the precursor takes place in a relatively short time.

The precursor seed can be grown even in the synthesis chamber 10 by continuously supplying the sodium hydroxide solution and the ammonia solution and operating the agitator 14 after the synthesis of the precursor.

However, in the present invention, only the synthesis of the precursor is performed in the synthesis chamber 10, and the growth of the precursor is performed in the growth chambers 20 connected to the synthesis chamber 10.

That is, when the raw material solution, the sodium hydroxide solution and the ammonia solution are put into the synthesis space 12 of the synthesis chamber 10 and the precursor is synthesized by the operation of the agitator 14, the control means (not shown) Open.

Therefore, the precursor synthesized in the synthesis chamber 10 and deposited is transported to the next growth chamber 20 along the transport pipe 30 connected to the bottom of the synthesis space 12. At this time, since the growth chamber 20 installed at the next stage of the synthesis chamber 10 is installed at a lower position than the synthesis chamber 10, the precursor can be moved due to the height difference even without a separate pumping process.

The heater 23 is operated through the control of the control means (not shown) in the growth chamber 22 of the growth chamber 20 to form a predetermined temperature atmosphere. After the precursor synthesized from the preceding synthesis chamber 10 is introduced , And a sodium hydroxide solution as a co-infiltrant is further added through the material input portion 21 and agitated to grow uniformly.

Similarly, in the growth chamber 20, the heater 23 is operated in accordance with the values measured by the temperature measuring unit 26 and the PH measuring unit 27, and the ammonia solution for pH adjustment is supplied.

The precursors grown for a predetermined time in the growth chamber 20 are transferred to the next-stage growth chamber 20 along the transfer pipe 30, and are continuously grown while repeating the same process. By filtering and drying the solution collected through the plurality of growth chambers 20 and collecting through the growth chamber 20 at the last stage, the precursor is collected, and the cathode active material for the secondary battery is obtained by performing a predetermined firing process.

In the first synthesis chamber 10, raw materials, sodium hydroxide and ammonia are added to synthesize the precursors, and when the precursors are synthesized, the precursors are immediately synthesized Stage growth chamber 20, so that it is possible to produce a homogeneous precursor. In other words, since a series of processes [input of raw materials - transfer - growth - transfer ... growth - collection] can be continuously performed through the synthesis chamber 10 and the plurality of growth chambers 20, It is possible to carry out the synthesis while continuously introducing the raw materials, sodium hydroxide and ammonia into the synthesis chamber 10, so that mass production is possible.

On the other hand, the time for growing the precursor seed in each growth chamber 20 can be determined according to the number of the growth chambers 20 installed.

≪ Embodiment 2 >

FIG. 2 is a view for explaining an apparatus for continuously mass production of a precursor for a secondary battery using a coprecipitation reaction (hereinafter referred to as a precursor continuous production apparatus) according to a second embodiment of the present invention.

The precursor continuous production apparatus according to the second embodiment also comprises a synthesis chamber 10 and a plurality of production chambers 20 as in the first embodiment. However, in the first embodiment, the precursor synthesized according to the drop is transferred to the next-stage growth chamber 20. In the second embodiment, the chambers 10 and 20 are provided with different height differences So that the precursor can be transported by the operation of the pump 31 even if it is connected.

That is, the synthesis chamber 10 and the plurality of growth chambers 20 are installed on a flat surface, and the lower portion of the synthesis chamber 10 and the upper portion of the growth chamber 20 of the next stage are connected by a transfer pipe 30, 30). ≪ / RTI > Likewise, the adjacent growth chambers 20 are connected by the transfer pipe 30 and the pump 31.

Therefore, when the precursor seed is synthesized by stirring the raw material solution, the sodium hydroxide solution and the ammonia solution after the synthesis space 12 of the synthesis chamber 10 is maintained at the predetermined temperature atmosphere, the control means (not shown) 31 are operated to transfer the precursor seed synthesized in the synthesis chamber 10 to the growth chamber 20 of the next stage. Thereafter, the temperature and pH atmosphere are maintained by the operation of the heater 23 in the growth chamber 20 and the introduction of the ammonia solution. When the sodium hydroxide solution is introduced and the precursor seed is grown for a predetermined time, The precursor is transported to the next growth chamber 20.

Through the connection of the synthesis chamber 10 and the growth chamber 20 according to the second embodiment, the synthesis and growth of the precursor seeds can be continuously performed, and a homogeneous precursor can be mass-produced.

≪ Third Embodiment >

3 is a view for explaining an apparatus for continuously mass production of a precursor for a secondary battery using a coprecipitation reaction (hereinafter referred to as a precursor continuous production apparatus) according to a third embodiment of the present invention.

The precursor continuous production apparatus according to the third embodiment also comprises a synthesis chamber 10 and a plurality of growth chambers 20. The configurations of the synthesis chamber 10 and the growth chamber 20 are the same as those of the first embodiment.

However, in the third embodiment, each of the chambers 10 and 20 is not connected in a line, and each of the growth chambers 20 is connected to the synthesis chamber 10. That is, a transfer pipe 30 is connected to the lower portion of the synthesis chamber 10, and the transfer pipe 30 is branched and connected to each of the growth chambers 20. A pump 31 is provided on the side of the synthesis chamber 10 in the transfer pipe 30 and a valve 32 is provided in a position where the pump 31 is connected to the growth chamber 20.

Therefore, when the raw material solution, the sodium hydroxide solution, and the ammonia solution are added to the synthesis chamber 10 to synthesize the precursor seed, the control means (not shown) is connected to the first growth chamber 20 of the plurality of growth chambers 20 The pump 31 is operated in a state in which the valve 32 is opened, so that the synthesized precursor seed is transferred and grown.

When synthesis of the precursor seeds in the synthesis chamber 10 is completed, the control means (not shown) opens the valve 32 connected to the second growth chamber 20 and operates the pump 31 to start the second growth chamber 20. [ The precursor seed is transported to the growth chamber 20 for growth.

The precursor seed synthesized in the synthesis chamber 10 may be separately supplied to the growth chamber 20 and collected in the respective growth chambers 20 when the growth is completed. That is, when the precursor seeds synthesized in the last growth chamber 20 have been charged and the precursor seeds synthesized in the first growth chamber 20 are to be introduced again, the first growth chamber 20 has already been pre- After the seed is grown and picked up. Therefore, the precursor for a secondary battery can be continuously produced in the same manner as in the third embodiment.

<Fourth Embodiment>

4 is a view for explaining an apparatus for continuously mass production of a precursor for a secondary battery using a coprecipitation reaction (hereinafter referred to as a precursor continuous production apparatus) according to a fourth embodiment of the present invention. 4, the apparatus for continuously producing precursor according to the fourth embodiment of the present invention includes a production chamber 40 in which an inner space is partitioned into a plurality of spaces 42 and 43 by barrier ribs 41, (42, 43).

On the inner side of the production chamber 40, a partition wall 41 is provided at a predetermined interval to define a space. For the sake of convenience, the frontmost space is called the synthesis space 42, and the subsequent spaces are called the growth space 43.

A heater 45 for temperature control is provided in each of the spaces 42 and 43 and an agitator 46 operated by a motor 47 is provided. In the synthesis space 42, a material input portion 44 into which a raw material solution, a sodium hydroxide solution, and an ammonia solution are introduced is connected to the growth space 43. In the growth space 43, a sodium hydroxide solution and an ammonia solution are introduced, (44) are connected. A temperature measuring unit 48 and a PH measuring unit 49 are provided for measuring the temperature and the hydrogen ion concentration in the spaces 42 and 43, respectively.

In the fourth embodiment, similar to the first embodiment, the precursor seeds synthesized in the synthesis space 42 are successively grown while sequentially moving to the next growth space 43. However, in the fourth embodiment, the precursor seed is transferred through the through hole 41a provided in the partition 41 without using any separate pipe or pump.

4, a precursor bore 41a is formed in the partition wall 41 in the production chamber 40 such that the height from the synthesis space 42 side to the final growth space 43 is gradually lowered. A heater 45 is installed in the spaces 42 and 43 between the partition 41 and the partition 41. The heater 45 is installed at a bottom portion so as to have a gap of a predetermined height.

Therefore, when the raw material solution, the sodium hydroxide solution, and the ammonia solution are put into the synthesis space 42 through the material input portion 44 and the stirrer 46 is operated at the predetermined temperature and the PH atmosphere, the precursor seeds are synthesized and precipitated. When the height of the reaction solution is increased by the height of the through hole 41a formed in the partition wall 41, the precipitate and the reaction solution are separated from each other by the precursor through the through hole 41a And proceeds to the growth space 43 of the next stage. At this time, the synthesized precursor seed precipitates and sinks to the bottom. There is a gap at the lower end of the heater 45, and the precipitated precursor seed rises along the partition wall 41 through the gap at the bottom of the heater 45 and the precursor passes through the through hole 41a And proceeds to the growth space 43 of the next stage.

The precursor seed that the precursor of the partition wall 41 has passed through the through hole 41a is grown in the PH atmosphere and the temperature of the growth space 43. The precursor seed continuously flows from the synthesis space 42 to the next growth space 43 When the reaction solution overflows and the height thereof increases, the precursor seed grown in the growth space 43 in the next stage is passed over and a continuous growth process is performed.

Since the height of the precursor bore 41a formed in the partition wall 41 is lowered step by step as the distance from the synthesis space 42 is increased, the precursor seed synthesized in the synthesis space 42 is separated from the growth space 42 at the next stage, The growth can be performed while sequentially passing through the growth space 42 of FIG. Finally, the precursor after the growth process is finally recovered in the last growth space 42, and the cathode active material for the secondary battery can be obtained by filtering, drying and firing.

Of course, as the synthesized precursor seed is moved to the growth space 42 of the next stage, the staying time is inevitably shortened. Therefore, the height of the precursor bore 41a and the number of the growth spaces 42 are appropriately designed in consideration of the entire growth time.

<Fifth Embodiment>

FIG. 5 is a view for explaining a precursor continuous mass production apparatus for a secondary battery using a coprecipitation reaction according to a fifth embodiment of the present invention (hereinafter referred to as a precursor continuous production apparatus).

The precursor continuous production apparatus according to the fifth embodiment has the same basic structure as the apparatus according to the fourth embodiment. A space inside the production chamber 40 is partitioned into a plurality of spaces 42 and 43 by barrier ribs 41 and material introducing portions 44 for forming a synthesis and growth atmosphere are formed in the spaces 42 and 43, A heater 45, a stirrer 46, a motor 47, a temperature measuring unit 48, and a PH measuring unit 49 are provided.

In the fifth embodiment, however, no separate precursor is formed in the partition wall 41, and the synthesized precursor seed is moved through the transfer pipe 50 and the pump 51. The transfer pipe 50 is connected to the bottom of the synthesis space 42 and the upper part of the growth space 43 at the next stage and a pump 51 is installed at one point on the transfer pipe 50. Similarly, a transfer pipe 50 and a pump 51 are installed between the growth spaces 43 and connected to each other.

Therefore, when the precursor seed is synthesized by stirring the raw material solution, the sodium hydroxide solution and the ammonia solution after the synthesis space 42 is maintained in the predetermined temperature atmosphere, the control means (not shown) The precursor seeds synthesized in the space 42 are transferred to the growth space 43 at the next stage. Thereafter, the temperature and the PH atmosphere are maintained by the operation of the heater 45 and the introduction of the ammonia solution in the growth space 43, and the sodium hydroxide solution is introduced to grow the precursor seed for a predetermined time, The precursor is transported to the growth space 43 at the next stage.

Through the continuous precursor continuous production apparatus according to the fifth embodiment, the synthesis and growth of the precursor seeds can be continuously performed, and a homogeneous precursor can be mass-produced.

FIG. 6 is a view for explaining the concept of a device for continuously producing precursors by combining a plurality of production chambers shown in FIG. 4 and FIG.

In other words, the side surfaces of the production chambers 40, which are connected in a line, of the synthesis space 42 and the growth space 43 are stacked to face each other, and the tips of the growth spaces 43 are connected to each other so that the precursor seeds can move . In this case, the space in which the raw material is first injected becomes the synthesis space 42, and all subsequent spaces become the growth space 43.

The raw material solution, the sodium hydroxide solution and the ammonia solution are introduced through the material inlet 44 of the synthetic space 42 on the lower left side in FIG. 6 and the stirrer 46 is operated to synthesize the precursor seeds, The precursor seed synthesized in the next growth space 43 is transferred through the transfer pipe 50, and the precursor seed is grown while repeating the transfer.

The number of the growth spaces 43 and the number of the production chambers 40 to be stacked are designed in consideration of the total growth time. Although the agitator 46 and the motor 47 are shown in the respective growth spaces 43 in the drawing, in the growth process other than the synthesis process, precursor seeds can be grown by adjusting only the temperature and the PH atmosphere without the stirring process Environment can be created. Therefore, the agitator 46 and the motor 47 may not be installed in the entire growth space 43, and the agitator 46 may be installed at a constant interval.

As described in detail above, the synthesis chamber 10 and the growth chamber 20 are continuously connected to each other or a space in the production chamber 40 is divided into a plurality of spaces so that the precursors are synthesized in the first synthesis spaces 12 and 42 , The synthesized precursor can be grown homogeneously while sequentially moving in the subsequent growth spaces 22 and 43, thereby enabling continuous mass production.

The foregoing description of the preferred embodiments of the present invention has been presented for the purpose of illustration and it will be apparent to those skilled in the art that various modifications, additions and substitutions are possible within the spirit and scope of the invention, And additions should be considered as falling within the scope of the claims of the present invention.

10: synthesis chamber
20: Growth chamber
40: Production chamber
11, 21, 44:
41:
41a: Precursor
12,42: Composite space
22,43: Growth space
13, 23, 45:
14, 24,
15, 25,
16, 26,
17, 27, 49: PH measuring unit
18,28: full water outlet
30,50: Feed pipe
31, 51: Pump
32: Valve

Claims (8)

delete delete delete delete delete A production chamber having a space inside;
A partition wall dividing a space inside the production chamber into a composite space in which a precursor is synthesized and a plurality of growth spaces in which the synthesized precursor is grown;
An agitator which stirs the raw material, sodium hydroxide, and ammonia, which are installed in at least one of the synthesis space and the plurality of growth spaces, into the synthesis space, or agitates the precursor introduced into the growth space; And
And a heater installed in at least one of the synthetic space and the plurality of growth spaces to adjust the temperature,
Wherein the precursor synthesized in the synthesis space is grown by sequentially moving the plurality of growth spaces.
The method according to claim 6,
Wherein the precursors synthesized in the synthesis space are sequentially transported to the neighboring growth spaces when the precursors rise to the hole height, thereby growing the precursors. Continuous mass production device for precursor for secondary cell.
The method according to claim 6,
Wherein the synthetic space and the growth spaces are connected to each other by a pump and a transfer pipe so that the synthesized and grown precursor can move to the next space through the operation of the pump. Production equipment.

Images