WO2011136466A2

WO2011136466A2 - Method for manufacturing lithium manganese oxide

Info

Publication number: WO2011136466A2
Application number: PCT/KR2011/001080
Authority: WO
Inventors: 김건일; 김천중; 박연정; 장동규; 양우영
Original assignee: 삼성정밀화학(주)
Priority date: 2010-04-30
Filing date: 2011-02-18
Publication date: 2011-11-03
Also published as: WO2011136466A3; KR101825914B1; KR20110121273A

Abstract

Disclosed is a method of manufacturing lithium manganese oxide. The disclosed method for manufacturing lithium manganese oxide comprises the steps of: injecting reaction materials containing lithium and manganese into a reactor, and mixing the raw materials at the molecular level in the reactor; and allowing the reaction materials to chemically react in the reactor so as to cause nucleation.

Description

Method of producing lithium manganese oxide

A method for producing lithium manganese oxide is disclosed. More specifically, lithium comprising the step of injecting a reaction raw material including lithium and manganese into the reactor, mixing at the molecular level and chemical reaction (nucleating) A method for producing manganese oxide is disclosed.

Lithium manganese oxide (LiMn ₂ O ₄ , hereinafter referred to as LMO) is a material that is expected to be used as a positive electrode active material of a lithium secondary battery.

As a method for producing such LMO, for example, there are a solid phase method, a coprecipitation method and a Pechini method.

The solid phase method is a method of producing a LMO by mixing and heat treating a reaction material of a solid phase, it is difficult to produce uniform nanoparticles due to the high heat treatment temperature, the fine particles of several hundred nanometers or less for the production of uniform nanoparticles Since the reaction raw material must be used, there is a problem that the price competitiveness is lowered due to the increased dependency on the reaction raw material. In addition, the share of manganese raw material prices is gradually increasing.

The coprecipitation method is a method of coprecipitating manganese salts through an acidic reaction, mixing them with lithium salts, and drying and sintering to prepare LMOs. It is difficult.

The pechini method is a method of producing LMO by esterifying ethylene glycol and citric acid and then drying and sintering lithium salt and manganese salt.

One embodiment of the present invention comprises the step of injecting a reaction raw material containing lithium and manganese into the reactor to mix at the molecular level (nucleating) by mixing (chemical reaction) at the molecular level (chemical reaction) It provides a method for producing lithium manganese oxide.

One aspect of the invention,

Injecting a reaction raw material including lithium and manganese into a reactor and mixing at the molecular level in the reactor; And

It provides a method for producing lithium manganese oxide comprising the step of chemical reaction of the reaction raw material in the reactor (nucleating).

The chemical reaction may be an acid group reaction.

The reaction raw material may be injected into the reactor in the form of at least one of a solution form and a suspension form.

The reaction raw material may include an acid raw material and a basic raw material, the acid raw material may be injected into the reactor through a first raw material injection line, and the basic raw material may be injected into the reactor through a second raw material injection line.

The acidic raw material may include lithium and manganese, and the basic raw material may include a metal hydroxide.

The acidic raw material may include manganese, and the basic raw material may include lithium.

The acidic raw material may include lithium, and the basic raw material may include manganese.

The basic raw material may include lithium and manganese, and the acidic raw material may include at least one of an inorganic acid and an organic acid.

The time (T _M ) required for mixing at the molecular level may be shorter than the time (T _N ) required for nucleation.

The T _M may be 10 to 100 μs, and the T _N may be 1 μm or less.

The molar ratio (Mn / Li) of manganese to lithium in the reaction raw material may be 1.8 to 2.2.

The reactor includes a chamber defining an internal space, a rotatable permeable packed bed disposed in the chamber and filled with a porous filler, and at least one raw material for injecting the reaction material into the permeable packed layer. It may be a high gravity rotating packed bed reactor having an injection line and a slurry outlet for discharging the slurry from the inner space.

Centrifugal acceleration of the permeable packed layer may be maintained at 10 ~ 100,000 m / s ² .

The lithium manganese oxide may have a spinel type crystal structure.

According to one embodiment of the present invention, a reaction raw material containing lithium and manganese in the form of inexpensive chloride and / or hydrate is injected into a reactor, mixed at the molecular level, and chemically determined. By including nucleating, a method for producing lithium manganese oxide having a particle size of several hundred nanometers or less and having a uniform particle size distribution and high-purity LMO can be mass produced at low cost.

1 is a cross-sectional view schematically showing a high gravity rotary packed bed reactor used in the method for producing lithium manganese oxide according to one embodiment of the present invention.

2, 4, 6 and 8 are TEM photographs of lithium manganese oxide nanoparticles prepared in Examples 1 to 4 of the present invention, respectively.

3, 5, 7 and 9 are XRD diffraction patterns of the lithium manganese oxide nanoparticles prepared in Examples 1 to 4 of the present invention, respectively.

Next, a method of manufacturing lithium manganese oxide according to one embodiment of the present invention will be described in detail.

Method for producing a lithium manganese oxide according to an embodiment of the present invention is a step of injecting a reaction raw material containing lithium and manganese into the reactor mixing at the molecular level (mixing at the molecular level) in the reactor, and in the reactor And chemically reacting the reaction raw materials with each other to generate crystal nuclei and to grow them to nanoscale. Thereafter, the slurry discharged from the reaction may be filtered, washed, dried and / or heat treated to obtain a uniform nano-sized lithium manganese oxide (LMO).

In the present specification, 'lithium' means a lithium compound, a lithium atom and / or a lithium ion in some cases, and 'manganese' means a manganese compound, a manganese atom and / or a manganese ion in some cases.

In addition, in the present specification, the "molecular level of mixing" means the level of mixing at which each molecule is mixed. In general, 'mixing' can be divided into 'macro-mixing' and 'micro-mixing', where macro mixing means mixing at the vessel scale, Micro mixing is synonymous with mixing at the molecular level described above.

In addition, the reaction raw material may include an acid raw material and a basic raw material. In this case, the acidic raw material may be injected into the reactor through a first raw material injection line, and the basic raw material may be injected into the reactor through a second raw material injection line. Specifically, the acidic raw material and the basic raw material are injected into the reactor through the first raw material injection line and the second raw material injection line, respectively, mixed at the molecular level in the reactor, and then subjected to a chemical reaction such as an acid group reaction. LMO nanoparticles are formed.

The acidic raw material may include lithium and manganese. Specifically, the acidic raw material may include lithium chloride and manganese chloride. The acidic raw material may be, for example, a mixed aqueous solution of LiCl / MnCl ₂ or a mixed aqueous suspension. In this case, the basic raw material may include a metal hydroxide such as NaOH.

In addition, the acidic raw material may include manganese, and the basic raw material may include lithium. Specifically, the acidic raw material may include manganese chloride such as MnCl _2, and the basic raw material may include lithium hydroxide such as LiOH.

In addition, the acidic raw material may include lithium, and the basic raw material may include manganese. Specifically, the acidic raw material may include lithium chloride such as LiCl, and the basic raw material may include manganese hydroxide such as Mn (OH) ₂ .

In addition, the basic raw material may include lithium and manganese. Specifically, the basic raw material may include lithium hydroxide and manganese hydroxide. The basic raw material may be, for example, a mixed aqueous solution of LiOH / Mn (OH) ₂ or a mixed aqueous suspension. In this case, the acidic raw material may include an inorganic acid and / or an organic acid such as HCl or acetic acid.

Such lithium chloride, manganese chloride, lithium hydroxide and manganese hydroxide is low in cost can reduce the manufacturing cost of lithium manganese oxide nanoparticles.

The chemical reaction may be an acid group reaction in which the acid and the base in the reaction raw material react by one equivalent, thereby losing the properties of the acid and the base.

In the present specification, 'T _M ' refers to the time taken from the start of mixing until the composition of the mixture becomes spatially uniform, and 'T _N ' means that the seed formation rate is in equilibrium from the point where the seed starts to form. It means the time it takes to reach and produce seed at a constant rate.

As such, by controlling T _M to be shorter than T _N , when the maximum mixing between molecules is achieved before the start of nucleation in the reactor, LMO particles having a uniform particle size distribution can be prepared.

The T _M may be 10 to 100 μs, and the T _N may be 1 μm or less. If the T _M is less than 10 GPa, it is not preferable from the economical point of view. In addition, when the T _N exceeds 1 kPa, an appropriate level of reaction does not occur and thus yield is not preferable.

In the production of the LMO nanoparticles, the internal temperature of the reactor may be maintained at 0 ~ 90 ℃, for example, 20 ~ 80 ℃. If the temperature is less than 0 ° C., an appropriate level of yield cannot be secured, which is not preferable. If the temperature is higher than 90 ° C., T _N is difficult to control, which is not preferable.

In addition, the molar ratio (Mn / Li) of manganese to lithium in the reaction raw material, that is, the reaction raw material injected into the reactor may be 1.8 to 2.2. If the molar ratio (Mn / Li) is less than 1.8, a LiMnO ₂ phase is formed, which is not preferable. If it exceeds 2.2, Mn ₂ O ₃ is precipitated, which is not preferable.

The residence time of the reaction raw material in the reactor may be 1㎳ ~ 10s, for example, 10㎳ ~ 5s. When the residence time of the reaction raw material is less than 1 ms, an appropriate level of reaction does not occur, which is not preferable. When the reaction time exceeds 10 s, it is difficult to control the particle size of the LMO, and it is not preferable because the economy is poor.

FIG. 1 is a schematic cross-sectional view of a high gravity rotating packed bed reactor used in a method of manufacturing lithium manganese oxide according to one embodiment of the present invention.

This high gravity rotary packed reactor 10 is a chamber 11 defining an interior space, a rotatable permeable packed bed disposed in the chamber 11 and filled with a porous filler 12a ( 12) at least one raw material injection line 14-1, 14-2 for injecting the reaction raw material into the transparent filling layer 12; And a slurry outlet 15 for discharging the slurry from the inner space.

The raw material injection lines 14-1 and 14-2 are disposed to extend through the reactor 10 to the center of the rotating shaft of the permeable packed layer 12, and a plurality of injection holes (not shown) are formed at each end of the reactor. The reaction raw material injected into (10) is sprayed into the transparent packed layer 12.

In addition, the reactor 10 may further include a gas outlet 16 for discharging gas from the internal space.

Porous filler 12a may contain titanium which is highly corrosion resistant. Specifically, the porous filler 12a may be titanium foam.

The permeable filler layer 12 is filled with a porous filler 12a therein and transmits the reaction raw material injected into the reactor 10 in the form of a solution or a suspension, and may be rotated by the drive shaft 13. The centrifugal acceleration of the permeable filler 12 can be maintained at 10 ~ 100,000 m / s ² . If the centrifugal acceleration of the permeable packed layer 12 is less than 10 m / s ^{2, the} reaction may not proceed to an appropriate level. On the other hand, it is not easy in the reactor design technology that the centrifugal acceleration of the permeable packed layer 12 exceeds 100,000 m / s ² .

Although the reactor 10 having the above configuration is operated under atmospheric pressure, the reaction raw materials can be mixed at a molecular level by a large centrifugal force by controlling the rotational speed of the permeable packed bed 12, so that the reaction proceeds smoothly even at low temperatures. You can. That is, uniformly mixing LMO nanoparticles at low temperature can be obtained by mixing fine droplets of reaction raw materials well before the growth of LMO particles. Since the reactor 10 is a continuous reactor, LMO can be produced in large quantities.

The LMO prepared by the method for preparing a lithium manganese oxide according to an embodiment of the present invention may have a spinel crystal structure, and an average particle diameter thereof may be 0.01 to 10 μm, for example, 0.05 to 0.8 μm. Therefore, the prepared lithium manganese oxide may be used as a cathode active material of a lithium secondary battery.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

EXAMPLE

Example 1

(1) 6.0 mol / L aqueous NaOH solution was prepared and used as the basic raw material.

(2) A 2.0 mol / L LiCl aqueous solution and a 2.0 mol / L MnCl ₂ aqueous solution were prepared, respectively, and the two aqueous solutions were mixed with each other in a volume ratio of 1: 2 to use the mixed solution as an acidic raw material. At this time, the molar ratio (Mn / Li) of Mn to Li in the LiCl / MnCl ₂ mixed solution was 2.

(3) A reactor 10 similar to the reactor of FIG. 1 was manufactured by itself. The specifications of the manufactured reactor 10 were as follows.

Permeable filling layer (12): stainless steel, inner diameter 10 cm, outer diameter 30 cm, thickness 10 cm cylindrical

Porous filler (12a): 4 pieces of titanium foam (approximately 400 pores per meter, outer diameter 30cm, inner diameter 10.5cm, axial thickness 2.5cm)

(4) In order to manufacture the LMO nanoparticles, the drive shaft 13 of the reactor 10 is rotated to rotate the permeable packed bed 12 at a speed of 1440 rpm (centrifugal acceleration: 60,000 m / s ² ). ) Was maintained at 80 ° C.

(5) The acidic raw material prepared in the above (2) and the basic raw material prepared in the above (1) are respectively passed through the first raw material injection line 14-1 and the second raw material injection line 14-2. 10) was continuously injected at a flow rate of 40 L / min to obtain LMO nanoparticles.

(6) The slurry containing the prepared LMO nanoparticles was discharged to the slurry outlet 15.

(7) The slurry was filtered with a filter, washed with water, and then dried at a temperature of 120 ° C. in a dryer to obtain LMO nanoparticles.

Example 2

(1) A 4.0 mol / L aqueous MnCl ₂ solution was prepared.

(2) A 2.0 mol / L LiOH aqueous solution and a 2.0 mol / L (NH ₄ ) OH aqueous solution were prepared, respectively, and the two aqueous solutions were mixed with each other in a volume ratio of 1: 1.

The LiOH / (NH ₄ ) OH mixed solution prepared in the above (2) and the MnCl ₂ aqueous solution prepared in the above (1) were respectively injected into the first raw material injection line 14-1 and the second raw material injection line 14-2. LMO nanoparticles were prepared in the same manner as in Example 1, except that each of the reactors 10 was continuously injected at a flow rate of 40 L / min through filtration, washing, and drying to obtain LMO nanoparticles. . In this embodiment, the ratio of the reaction raw material components injected into the reactor 10, that is, the molar ratio of Mn to Li (Mn / Li) was 2.

Example 3

(1) After preparing 2.0 mol / L LiCl aqueous solution and 2.0 mol / L HCl aqueous solution, respectively, the two aqueous solutions were mixed with each other in a volume ratio of 1: 1.

(2) 4.0 mol / L of Mn (OH) ₂ aqueous solution was prepared.

The internal temperature of the reactor was maintained at 70 ° C., and the LiCl / HCl mixed solution prepared in (1) and the Mn (OH) ₂ aqueous solution prepared in (2) were respectively prepared in the first raw material injection line 14-1. And LMO nanoparticles were prepared in the same manner as in Example 1, except that the second raw material injection line 14-2 was continuously injected into the reactor 10 at a flow rate of 40 L / min, respectively. Filtration, washing and drying yielded LMO nanoparticles. In this embodiment, the ratio of the reaction raw material components injected into the reactor 10, that is, the molar ratio of Mn to Li (Mn / Li) was 2.

Example 4

After preparing 2.0 mol / L HCl aqueous solution, 2.0 mol / L LiOH aqueous solution and 4.0 mol / L Mn (OH) ₂ aqueous solution, respectively, the LiOH aqueous solution and Mn (OH) ₂ aqueous solution were 1: 1 in volume ratio. Mixing, maintaining the internal temperature of the reactor at 80 ° C., and mixing the HCl aqueous solution and the LiOH / Mn (OH) ₂ mixed solution with the first raw material injection line 14-1 and the second raw material injection line 14-, respectively. LMO nanoparticles were prepared in the same manner as in Example 1, except that the reactor 10 was continuously injected at a flow rate of 100 L / min and 40 L / min, respectively, through filtration, washing, and drying. To obtain LMO nanoparticles. In this embodiment, the ratio of the reaction raw material components injected into the reactor 10, that is, the molar ratio of Mn to Li (Mn / Li) was 2.

Analysis example

TEM images and XRD diffraction patterns of the lithium manganese oxide nanoparticles prepared in Examples 1 to 4 were analyzed and shown in FIGS. 2 to 9, respectively. The specifications and analysis conditions of the TEM and XRD used are shown in Table 1 below.

Table 1

		TEM	XRD
Specification	manufacturer	JEOL	Rikagu
Specification	model name	2100F	D / Max-2500VK / PC
Analysis condition		200 kV	CuKa radiation, speed 4 ° min ^-1

Referring to Figures 2 to 9, it can be seen that even though a low-cost reaction raw material is used, LMO particles having a relatively uniform particle size distribution and nano-sized particles can be obtained. Specifically, it can be seen from FIGS. 2, 4, 6, and 8 that the particles prepared in Examples 1 to 4 have a nano size and that the particle size distribution of each particle is uniform, and FIGS. 3, 5, and 7 From 9 and it can be seen that each particle produced is LMO (LiMn ₂ O ₄ ). Each numerical value (e.g., 100 nm in Fig. 2) shown in Figs. 2, 4, 6 and 8 means the length of the thick bar shown in each figure, and each numerical value indicated in Figs. For example, (111) of FIG. 3 means a crystal plane index.

Although preferred embodiments of the present invention have been described above with reference to the drawings and embodiments, these are merely exemplary, and various modifications and equivalent other embodiments are possible to those skilled in the art. You will understand. Therefore, the protection scope of the present invention should be defined by the appended claims.

Claims

Injecting a reaction raw material including lithium and manganese into a reactor and mixing at the molecular level in the reactor; And

A method for producing lithium manganese oxide comprising the step of chemical reaction (nucleating) the reaction raw material in the reactor (nucleating).
The method of claim 1,

The chemical reaction is an acid group reaction method for producing lithium manganese oxide.
The method of claim 1,

Wherein the reaction raw material is injected into the reactor in the form of at least one of a solution form and a suspension form.
The method of claim 3,

The reaction raw material includes an acidic raw material and a basic raw material, the acidic raw material is injected into the reactor through a first raw material injection line, the basic raw material of the lithium manganese oxide injected into the reactor through a second raw material injection line Manufacturing method.
The method of claim 4, wherein

The acidic raw material includes lithium and manganese, and the basic raw material is a method of producing a lithium manganese oxide containing a metal hydroxide.
The method of claim 4, wherein

The acidic raw material includes manganese, and the basic raw material comprises a lithium manganese oxide.
The method of claim 4, wherein

The acid raw material comprises lithium, and the basic raw material manufacturing method of lithium manganese oxide containing manganese.
The method of claim 4, wherein

The basic raw material includes lithium and manganese, and the acidic raw material comprises at least one of an inorganic acid and an organic acid.
The method of claim 1,

The time (T M ) required for the mixing of the molecular level is shorter than the time (T N ) for the production of nuclei.
The method of claim 9,

The T M is 10 ~ 100 ㎲, T N is 1 ㎳ or less manufacturing method of lithium manganese oxide.
The method of claim 1,

A molar ratio (Mn / Li) of manganese to lithium in the reaction raw material is a method of producing lithium manganese oxide of 1.8 ~ 2.2.
The method of claim 1,

The reactor,

A chamber defining an interior space;

A rotatable permeable packed bed disposed in said chamber and filled with a porous filler;

At least one raw material injection line for injecting the reaction raw material into the transparent packing layer; And

A method for producing lithium manganese oxide, which is a high gravity rotating packed bed reactor having a slurry outlet for discharging a slurry from the internal space.
The method of claim 12,

Centrifugal acceleration of the permeable packed layer is a manufacturing method of lithium manganese oxide is maintained at 10 ~ 100,000 m / s 2 .
The method of claim 1,

The lithium manganese oxide is a manufacturing method of lithium manganese oxide having a spinel type crystal structure (spinel type crystal structure).