KR20140013130A - Method for manufacturing manganese rich composite transition metal hydroxide and the manganese rich composite transition metal hydroxide particle - Google Patents

Abstract

The present invention relates to a reaction chamber which is formed between the fixed cylinder and a rotary cylinder of a double cylindrical reactor having one or a plurality of inlets and a central cylinder of the same fixed cylinder and a rotary cylinder, A reaction solution containing an aqueous solution of manganese salt and a basic aqueous solution is introduced through one or a plurality of inlets and the pH of the reaction solution is kept at 9 to 13 and the reaction solution is periodically arranged along the central axis direction in the reaction space, Characterized in that the reaction liquid is mixed or agitated along the flow of annular vortex pairs rotating in the opposite direction to inhibit the formation of manganese oxides and to produce a complex transition metal hydroxide represented by the following formula ≪ / RTI > complex transition metal hydroxide particles.
Ni _a Mn _1-a (OH _1-x ) ₂ (1)
(a, x values are as defined in the specification).

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for preparing a composite transition metal hydroxide having a high manganese content and a manganese high content composite transition metal hydroxide particle produced therefrom,

The present invention relates to a method for producing a high manganese complex transition metal hydroxide by a coprecipitation reaction in which manganese is prevented from being oxidized by contact with external air, and a manganese high-content complex transition metal hydroxide particle produced therefrom.

As information technology (IT) technology has developed remarkably, various portable information and communication devices have been spreading, so that the 21st century is being developed into a "ubiquitous society" capable of providing high quality information services regardless of time and place.

As a development base for such a ubiquitous society, a lithium secondary battery occupies an important position.

Lithium secondary batteries have higher operating voltages and energy densities than other secondary batteries and can be used for a long time, thus meeting the complex requirements of diversification and combination of devices.

In recent years, efforts have been actively made worldwide to further expand the application fields of not only an environmentally friendly hydrogen system such as electric vehicles but also electric power storage by further developing the existing lithium secondary battery technology.

Among the components of the lithium secondary battery, the cathode material plays an important role in determining the capacity and performance of the battery in the battery.

Lithium cobalt oxide (LiCoO ₂ ) is a cathode material that has been commercialized for the first time, and is still used as a cathode material because of its relatively excellent structural stability and mass production ease compared to other lithium transition metal oxides. However, There is a problem that the price is expensive due to limitations.

Therefore, various studies have been made on a cathode material that can replace lithium cobalt oxide.

Lithium manganese oxide (LiMn ₂ O ₄ ) with a spinel structure has advantages such as relatively low cost and high power, but has a disadvantage in that the energy density is lower than that of lithium cobalt oxide.

In order to overcome the disadvantages described above, a technique of converting a part of manganese (Mn) into nickel (Ni) in LiMn ₂ O ₄ has been studied. Since the lithium manganese oxide having a spinel structure in which a part of manganese is substituted with nickel has a high operating potential of 4.7 V, it is very likely to be utilized as a cathode material for lithium secondary batteries for electric vehicles requiring high output characteristics .

Such lithium manganese oxide is generally produced by a solid phase method or a wet milling method. In recent years, attempts have been made to synthesize lithium manganese oxides in which a part of manganese is substituted with nickel as described above by coprecipitation in view of the mass productivity, but in the case of high manganese (Mn) content, Manganese oxides are formed due to the air, which makes it difficult to obtain uniform composite transition metal hydroxide particles.

In addition, although a continuous stirred tank reactor (CSTR) is mainly used in the conventional coprecipitation reaction, only a reducing gas for suppressing the oxidation of manganese in the CSTR reactor is added to solve the above problems .

DISCLOSURE Technical Problem Accordingly, the present invention has been made to solve the above-mentioned problems of the prior art and to provide a method for producing a high manganese complex transition metal hydroxide using a coprecipitation reaction and a manganese high- .

In order to accomplish the above object, the present invention provides a method for preparing a high manganese complex transition metal hydroxide,

A reaction chamber in which one or a plurality of inlets and a central axis are formed of the same fixed cylinder and a rotating cylinder and which is formed between the fixed cylinder and the rotating cylinder of the double cylindrical reactor and in which the inflow of external air is blocked, And a basic aqueous solution are introduced through one or a plurality of inlets,

Maintaining the pH of the reaction solution at 9 to 13, more specifically at a pH of 10 to 12, along the flow of annular vortex pairs arranged periodically along the central axis direction in the reaction space and rotating in opposite directions And the reaction liquid is mixed or stirred to inhibit the formation of manganese oxide to produce a complex transition metal hydroxide represented by the following formula (1).

Ni _a Mn _1-a (OH _1-x ) ₂ (1)

Wherein 0.2? A? 0.25; 0 < x < 0.5.

In the conventional CSTR reactor, an air zone of 10 to 20 vol% is formed in the upper space of the reaction liquid, so that the inflow of air can not be completely blocked during the reaction as described above.

On the other hand, in the present invention, a coprecipitation reaction of a nickel salt and a manganese salt is performed in a state in which the reaction liquid is filled in a reaction space of a closed structure formed between the fixed cylinder and the rotating cylinder of the double cylindrical reactor.

At this time, the closed structure means a structure in which the inflow of air is minimized substantially in comparison with the conventional CSTR reactor, and does not mean that the inflow of air is necessarily blocked by 100%.

The only space in which the air can be introduced into the reaction space in the double cylindrical reactor is one or a plurality of inlets or outlets which are formed to have a relatively narrow width as compared with the CSTR reactor. Therefore, the present invention can effectively prevent the inflow of outside air during the reaction and suppress the formation of manganese oxide.

The inventors of the present application have found from the XRD results that manganese oxides are not produced in the complex transition metal hydroxides of high manganese content prepared according to the present invention, unlike the manganese high-content complex transition metal hydroxides prepared by the conventional CSTR reactor I could.

In one specific embodiment, the flow path width of the inlet may be 10 to 100% of the separation distance between the stationary cylinder and the rotary cylinder.

The inlet has a structure in which the width of the inlet communicated with the reaction space is the same as the width of the inlet communicated with the external space, or a taper width of the inlet becomes narrower from the inlet communicating with the external space to the inlet communicating with the reaction space. It may consist of a true structure.

In the structure in which a plurality of inlets are formed, part of the inlet and the outlet are communicated with each other from the inlet portion communicating with the outer space, And the width of the inlet is narrowed toward the inlet.

The double cylindrical reactor includes a fixed cylinder having the same central axis and a rotating cylinder; A motor for generating power for rotating the rotating cylinder; And one or a plurality of inlets and outlets for introducing and discharging the reaction fluid into and from the reaction space between the fixed cylinder and the rotating cylinder.

In one specific embodiment, the above-mentioned double cylindrical reactor has a structure in which the rotary cylinder is accommodated in the inner space of the fixed cylinder, the inlet and the outlet are formed on the outer peripheral surface of the fixed cylinder, and the hollow cylindrical fixed cylinder;

A rotating cylinder coaxial with the fixed cylinder and having an outer diameter smaller than an inner diameter of the fixed cylinder;

An electric motor for generating power for rotating the rotary cylinder;

A rotation reaction space in which annular vortex pairs periodically arranged along the rotation axis direction and rotating in opposite directions are generated as a spacing space between the fixed cylinder and the rotation cylinder; And

An inlet and an outlet for introducing and discharging the reaction fluid into the rotary reaction space;

As shown in FIG. At this time, it is very easy to additionally supply the reducing gas through the plurality of inlets in order to suppress oxidation of manganese.

In another embodiment, the ratio of the distance between the fixed cylinder and the rotary cylinder to the outer diameter radius of the rotary cylinder may be more than 0.05 to less than 0.4.

Due to this feature, the production process according to the invention can be carried out for a period of 1 to 6 hours, with the mixing or stirring process being carried out. Specifically, when a coprecipitation reaction is performed in a conventional CSTR reactor, a high residence time of 6 hours or more is required.

The inventors of the present application have confirmed that such a reduction in reaction time leads to an increase in the production amount per volume of about 1.5 to 10 times.

The above-mentioned effect can be expressed when the ratio of the distance between the fixed cylinder and the rotary cylinder to the outer diameter radius of the rotary cylinder is over 0.05.

Specifically, when the ratio of the distance between the fixed cylinder and the rotary cylinder to the outer diameter radius of the rotary cylinder is 0.05 or less, the distance between the fixed cylinder and the rotary cylinder is too small to manufacture. Also, even if manufacture is possible, the effective volume of the rotating reaction space in which the vortex pairs are generated is reduced, and the residence time is reduced, which is not preferable because the production amount is greatly reduced.

On the other hand, since one vortex pair substantially plays the role of one fine CSTR, the vortex pairs periodically arranged along the rotation axis act as if the fine CSTRs are connected, and as the number of the vortex pairs increases The flow characteristics are enhanced.

However, since the size of the one vortex pair is substantially similar to the interval between the fixed cylinder and the rotating cylinder, the larger the ratio of the distance between the fixed cylinder and the rotating cylinder to the outer diameter radius of the rotating cylinder, The number of vortex pairs (&apos; CSTR number &apos;) in the reactor gradually decreases.

Therefore, when the ratio of the distance between the fixed cylinder and the rotary cylinder to the outer diameter radius of the rotary cylinder is 0.4 or more, when the ratio of the distance between the fixed cylinder and the rotary cylinder to the outer diameter radius of the rotary cylinder is less than 0.4 The flow characteristics of the vortex pairs are lowered and it is difficult to produce uniform precursor particles having a small particle diameter distribution and a small average particle diameter.

When the ratio of the distance between the fixed cylinder and the rotary cylinder with respect to the radius of the outer diameter of the rotary cylinder is 0.4 or more, (Vortices of 'laminar flow'), wave vortices, modulated vortex vortices and turbulent vortices do not appear, and the transition from turbulent flow areas of the laminar flow to turbulent flow areas occurs immediately , It is difficult to produce uniform precursor particles having a small average particle diameter and a small particle diameter distribution due to a decrease in flow characteristics of the vortex pairs.

That is, the complex transition metal hydroxide prepared using the reactor of the present invention can be produced as uniform precursor particles having a small particle size distribution and a small average particle diameter as compared with the complex transition metal hydroxide prepared using the CSTR, The distribution and the control of the average particle diameter can be expressed when the ratio of the distance between the fixed cylinder and the rotating cylinder to the outer diameter radius of the rotating cylinder is less than 0.4.

The reactor is a precursor of a lithium complex transition metal oxide for a lithium secondary battery and is optimally designed for the production of a complex transition metal hydroxide. The mixing or stirring rate of a reaction solution having a kinetic viscosity of 0.4 to 400 cP in the reactor is preferably in the range of The power consumption may be 0.05 to 100 W / kg. The power consumption per unit mass can be defined as the stirring speed of the rotating cylinder.

The number of critical Reynolds in which the vortex pairs occur is about 300, the vortex pairs have a Reynolds number of 300 , The fluid flowing between the stationary cylinder having the same center and the rotating cylinder is formed over the entire surface of the rotating reaction space by becoming unstable due to the tendency to move toward the fixed cylinder by the centrifugal force.

The reactor of the present invention can produce uniform precursor particles having a smaller particle size than the CSTR reactor using the above-mentioned annular vortex pairs.

The complex transition metal hydroxide particles represented by Formula 1 can be obtained through the outlet of the double cylindrical reactor.

The composite transition metal hydroxide particles prepared by the conventional coprecipitation method have a minimum average particle diameter of 6 to 10 탆, whereas the composite transition metal hydroxide particles of the present invention may have a minimum average particle diameter of 1 to 5 탆, The standard deviation of the particle size distribution is 1 to 5, which shows a monodispersed particle size distribution compared to the conventional composite transition metal hydroxide particles.

Therefore, since the precursor particles of the present invention have a monodispersed small particle size as compared with the conventional precursor particles, the moving distance of lithium is small during charging and discharging, and the rate characteristic is improved. In addition, the improvement in the low-temperature rate characteristic is larger than that in the low-temperature rate characteristic, and the electrode packing density is increased when the large particles are added.

In one specific embodiment, the average particle size of the precursor particles is from 1 to 5 占 퐉, where the standard deviation can be from 1 to 5. In addition, the coefficient of variation may be 0.2 to 0.7. The coefficient of variation is a value obtained by dividing the standard deviation by the average particle diameter (D50).

The complex transition metal hydroxide particles exhibit higher crystallinity than conventional precursors. Specifically, the degree of crystallinity can be judged from the content of impurities derived from the transition metal salt for producing a complex transition metal hydroxide.

The nickel salt and the manganese salt preferably have an anion which is easily decomposed and easily volatilized during firing, and may be a sulfate or a nitrate.

For example, one or more selected from the group consisting of nickel sulfate, manganese sulfate, nickel nitrate, manganese nitrate, and the like, but is not limited thereto.

The inventors of the present application have found that the composite transition metal hydroxide particles contain an impurity derived from a transition metal salt for preparing a complex transition metal hydroxide in an amount of 0.4% by weight or less based on the total weight of the composite transition metal hydroxide particles. The impurity may be sulfate ion (SO ₄ ) -containing salt ion.

The impurity may be sulfate ion (SO ₄ ) -containing salt ion. The transition metal salt from which the sulfate ion (SO ₄ ) -containing salt ion is derived may be a sulfate, and examples of the sulfate include nickel sulfate and manganese sulfate. These sulfate salts may be used alone or in combination of two or more. .

In some cases, the sulfate ion (SO ₄ ) -containing salt ion may further contain nitrate ions (NO ₃ ), which may be derived from nickel nitrate, manganese nitrate, etc. as transition metal salts .

More preferably, the content of the sulfate ion (SO ₄ ) -containing salt ion may be 0.3 to 0.4% by weight based on the total weight of the composite transition metal hydroxide particles.

The method of measuring the content of salt ions in the precursor particles may be various, and preferably a detection method by an ion chromatograph method defined below can be used.

The basic aqueous solution may be an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, or an aqueous solution of lithium hydroxide, preferably an aqueous solution of sodium hydroxide, but is not limited thereto.

Meanwhile, an additive capable of forming a complex with the transition metal and / or alkali carbonate may be further added to the aqueous solution of the raw materials. As the additive, for example, an ammonium ion source, an ethylene diamine compound, a citric acid compound, or the like can be used. Examples of the ammonium ion supplier include ammonia water, ammonium sulfate aqueous solution, ammonium nitrate aqueous solution and the like. The alkali carbonate may be selected from the group consisting of ammonium carbonate, sodium carbonate, potassium carbonate and lithium carbonate. In some cases, these may be used by mixing two or more thereof.

The addition amount of the additive and alkali carbonate can be appropriately determined in consideration of the amount of transition metal-containing salt, pH, and the like.

The inventors of the present application have confirmed that when the complex transition metal hydroxide is produced according to the production method of the present invention, the amount of the complex formation additive, for example, the aqueous ammonia solution can be reduced.

In a specific embodiment of the present invention, the aqueous ammonia solution is based on the total amount of nickel salts and manganese salts 5 to 90 mol%.

This is because the complex transition metal hydroxide is prepared with about 60% of the additive compared to the case where the complex transition metal hydroxide is prepared by using CSTR. The process according to the present invention can provide a relatively inexpensive lithium complex transition metal oxide .

The present invention also provides a lithium complex transition metal oxide represented by the following Chemical Formula 2, which is produced by subjecting the precursor particles to a calcination reaction with a lithium precursor.

Li _{1 + b} Ni _y Mn _2-y O _{4 -z} (2)

Wherein 0? B? 0.1; 0.2? Y? 0.5; 0? Z? 0.1; to be.

The lithium precursor is not particularly limited and includes, for example, lithium hydroxide, lithium carbonate, lithium oxide and the like, preferably lithium carbonate (Li ₂ CO ₃ ) and / or lithium hydroxide (LiOH).

The present invention also provides a lithium secondary battery comprising the lithium composite transition metal oxide as a cathode active material.

The secondary battery according to the present invention can be used not only in a battery cell used as a power source for a small device but also as a unit cell in a middle or large battery module including a plurality of battery cells.

Also, the present invention provides a battery pack including the battery module as a power source of a middle- or large-sized device, wherein the middle- or large-sized device is an electric vehicle (EV), a hybrid electric vehicle (HEV) An electric vehicle including a plug-in hybrid electric vehicle (PHEV), a power storage device, and the like, but the present invention is not limited thereto.

Lithium complex transition metal oxide, lithium secondary battery, battery pack, etc., reaction conditions, constituent elements, etc. are well known in the art and will not be described in detail below.

The present invention relates to a process for producing a manganese oxide which suppresses the formation of manganese oxides by carrying out a coprecipitation reaction in a closed reaction space in which contact with external air is blocked and mixes the reaction solution using the above- It is advantageous to produce complex transition metal hydroxide particles having a high manganese content.

1 is a side schematic view of a reactor according to one embodiment of the present invention;
Figure 2 schematically illustrates the flow patterns of annular vortex pairs and reaction fluids occurring in the rotating reaction space of the reactor of Figure 1;
3 is a graph comparing the power consumption per unit mass of the CSTR and the reactor according to the present invention.

Hereinafter, the present invention will be described in further detail with reference to examples and drawings, but the scope of the present invention is not limited thereto.

FIG. 1 is a schematic side view of a reactor according to an embodiment of the present invention, and FIG. 2 is a schematic view of a flow pattern of annular vortex pairs and a reaction fluid occurring in a rotating reaction space of the reactor of FIG. 1 .

Referring to FIG. 1, a reactor 100 for producing a lithium complex transition metal oxide precursor for a lithium secondary battery according to the present invention includes a fixed cylinder 110 in a hollow cylindrical fixed cylinder 110, (2 x r2) smaller than the inner diameter (2 x r1) of the stationary cylinder is provided between the stationary cylinder 110 and the rotary cylinder 120. The rotary cylinder 120 has an outer diameter A plurality of inlets 140, 141 and 142 for introducing the reaction fluid into the reaction space and an outlet 151 for discharging the reaction fluid are provided on the fixed cylinder 110, 110 is provided at one side thereof with an electric motor 130 for generating power for rotating the rotary cylinder 120.

The effective volume of the reaction space is determined by the ratio (d / r2) of the distance d between the fixed cylinder 110 and the rotary cylinder 120 to the outer diameter radius r2 of the rotary cylinder 120. [

Referring to FIGS. 1 and 2 together, when the rotating cylinder 120 rotates and reaches the critical Reynolds number by the power generated from the motor 130, the nickel (Ni) charged into the rotating reaction space through the inlets 140, 141, The reaction liquid such as an aqueous solution of a salt and a manganese salt, an aqueous ammonia solution and an aqueous solution of sodium hydroxide becomes unstable due to centrifugal force in the direction of the fixed cylinder 110 from the rotary cylinder 120 and as a result, Shaped vortex pairs 160 are periodically arranged in the reaction space.

The length of the annular vortex pairs 160 in the gravitational direction is substantially equal to the distance d between the fixed cylinder 110 and the rotary cylinder 120.

The outer circumference of the rotary shaft 120 may be sealed by using a sealing means such as an O-ring in order to block the air sucked into the gap between the rotary shaft and the bearing when the rotary cylinder 120 rotates.

The reaction liquid may be introduced into the reaction space through the inlet 140 and the reducing gas may be introduced into the reaction space through the inlet 141 or the inlet 142.

3 is a graph comparing the power consumption per unit mass of the CSTR and the reactor according to the present invention. In the case of a 4L CSTR, a rotational force of 1200 to 1500 rpm is consumed to form a desired particle size when the precursor is synthesized, and is converted to about 13 to 27 W / kg in terms of stirring power per unit mass. On the other hand, the 0.5 L reactor according to the present invention can synthesize a precursor having a desired particle size in the range of 600 to 1400 rpm, which is 1 to 8 W / kg in terms of stirring power per unit mass.

That is, the reactor of the present invention is capable of synthesizing a precursor having a desired particle size with stirring power per unit mass, which is smaller than that of CSTR. This indicates that the reactor of the present invention has better stirring efficiency than CSTR.

&Lt; Example 1 >

Nickel sulfate and manganese sulfate were mixed at a ratio (molar ratio) of 0.25: 0.75 to prepare a 1.5 M concentration transition metal aqueous solution, and a 3M aqueous sodium hydroxide solution was prepared. The ammonia solution prepared an aqueous solution in which 25 wt% of ammonium ions were dissolved.

The prepared transition metal aqueous solution was introduced into the reactor using a metering pump so that the residence time was 1 hour. The sodium hydroxide aqueous solution was variably added using a metering pump so that pH was maintained at 11.0. The aqueous ammonia solution was continuously supplied at a concentration of 30 mol% based on the aqueous solution of the transition metal.

Nitrogen gas was fed at a rate of 0.06 L / h while the reaction was continued.

Manganese complex transition metal precursor prepared by reacting continuously for 20 hours after reaching a steady state with an average residence time of 1 hour was washed several times with distilled water and dried in a constant temperature drier at 120 ° C. for 24 hours to obtain a nickel- Transition metal precursors were prepared.

&Lt; Comparative Example 1 &

The same procedure as in Example 1 was repeated except that a CSTR (Continuous Stirred Tank Reactor) having a size of 5 L was used and an ammonia aqueous solution was supplied at a concentration of 50 mol% based on the aqueous solution of the transition metal and the amount of nitrogen gas was changed to 1 L / h. - manganese complex transition metal precursor.

Manufacture of Coin Cell

The nickel-manganese complex transition metal precursors prepared in Example 1 and Comparative Example 1 were mixed with Li ₂ CO _{3 at} a ratio (molar ratio) of 1: 1, heated at a heating rate of 5 ° C / min, And then fired for 10 hours to prepare a cathode active material powder of Li [Ni _0.25 Mn _0.75 ] ₂ O ₄ .

Denka Black as a conductive material and KF1100 as a binder were mixed in a weight ratio of 95: 2.5: 2.5 to the cathode active material powder thus prepared to prepare a slurry and uniformly coated on an aluminum foil having a thickness of 20 占 퐉 Respectively. This was dried to 130 ℃ to prepare a positive electrode for a lithium secondary battery.

A lithium secondary battery positive electrode prepared above, a lithium metal foil as a counter electrode (cathode), a polyethylene film (Celgard, thickness: 20 μm) as a separator, and ethylene carbonate, dimethylene carbonate, diethyl carbonate were 1: 2 : A 2016 coin battery was manufactured using a liquid electrolyte in which LiPF ₆ was dissolved in 1 M in a solvent mixed with 1.

<Experimental Example 1> The initial charge-discharge characteristics

Coin batteries prepared in Example 1 and Comparative Example 1 were charged and discharged once at a voltage range of 3.5 to 4.9 V at a current of 0.1 C to evaluate charge and discharge characteristics. The results are shown in Table 1 below.

Initial charge capacity
(mAh / g) Initial discharge capacity
(mAh / g) Initial charge and discharge efficiency
(%) Example 1 148.1 143.8 97.1 Comparative Example 1 147.2 141.8 96.3

<Experimental Example 2>

Life characteristics

Coin batteries prepared in Example 1 and Comparative Example 1 were charged and discharged 50 times at a current of 1.0 C to evaluate the life characteristics. The results are shown in Table 2 below.

Life characteristics
50 ^th / 1 ^st discharge capacity (%) Example 1 98.1 Comparative Example 1 97.2

As a result of the electrochemical characterization, it was confirmed that the precursor having a high manganese content was effectively synthesized and exhibited its performance despite a small amount of the reducing gas.

Claims (23)

A reaction space formed between the fixed cylinder and the rotary cylinder of the double cylindrical reactor in which one or a plurality of inlets and a central axis are the same fixed cylinder and a rotary cylinder,
A reaction solution containing an aqueous solution of a nickel salt and a manganese salt and a basic aqueous solution is introduced through one or more inlets and the pH of the reaction solution is maintained at 9 to 13,
The reaction liquid is mixed or agitated along the flow of annular vortex pairs periodically arranged along the central axis direction in the reaction space and rotating in opposite directions,
A process for producing a complex transition metal hydroxide represented by the following formula (1), wherein the production of manganese oxide is inhibited:
Ni _a Mn _1-a (OH _1-x ) ₂ (1)
Wherein 0.2? A? 0.25; 0 <x <0.5. 2. The dual cylinder reactor according to claim 1,
A fixed cylinder and a rotating cylinder having the same central axis;
A motor for generating power for rotating the rotating cylinder; And
And one or a plurality of inlets and outlets for introducing and discharging the reaction fluid into and from the reaction space between the fixed cylinder and the rotating cylinder. The manufacturing method according to claim 2, wherein the rotating cylinder is accommodated in the inner space of the fixed cylinder, and the inlet and the outlet are formed on the outer circumferential surface of the fixed cylinder. 4. The method according to claim 3, wherein the ratio of the distance between the fixed cylinder and the rotating cylinder to the outer diameter radius of the rotating cylinder is in the range of more than 0.05 to less than 0.4. The manufacturing method according to claim 2, wherein the flow path width of the inlet is 10 to 100% of a separation distance between the fixed cylinder and the rotating cylinder. 3. The method according to claim 2, wherein the inlet has a structure in which the width of the inlet communicated with the reaction space is the same as the width of the inlet communicated with the external space. The manufacturing method according to claim 2, wherein the inlet has a tapered structure in which the width of the inlet is narrower from the inlet communicating with the external space to the inlet communicating with the reaction space. 3. The apparatus according to claim 2, wherein some of the plurality of inlets have a structure in which the width of the inlet communicated with the reaction space is the same as the width of the inlet communicated with the outer space, Wherein the inlet port has a tapered structure in which the width of the inlet port becomes narrower toward the communicating inlet port. The method according to claim 1, wherein the mixing or stirring is performed at a stirring speed of 0.05 to 100 W / kg as a power consumption per unit mass. 2. The method of claim 1, wherein the vortex pairs have a critical Reynolds number of 300 or greater. The production method according to claim 1, further comprising introducing a reducing gas through a plurality of inlets so as to suppress the production of manganese oxide which is additionally produced. The method of claim 1, wherein the mixing or stirring step is performed for 1 to 6 hours. The process according to claim 1, wherein the reaction liquid further comprises an aqueous solution of a complex forming additive in a range of 5 to 90 mol% based on the total amount of the nickel salt and the manganese salt. 14. The method according to claim 13, wherein the aqueous solution of the complex formation additive is an aqueous ammonia solution. 1. A composite transition metal hydroxide particle represented by a composition represented by the following formula (1) and having an average particle diameter within a range of 1 to 10 占 퐉, a monodispersed particle diameter distribution, and a standard deviation of 1 to 5:
Ni _a Mn _1-a (OH _1-x ) ₂ (1)
Wherein 0.2? A? 0.25; 0 <x <0.5. The composite transition metal hydroxide particles of claim 1, wherein the average particle size is in the range of 1 to 5 占 퐉. The composite transition metal hydroxide particles according to claim 15, wherein the coefficient of variation of the composite transition metal hydroxide particles is 0.2 to 0.7. The method of claim 15, wherein the composite transition metal hydroxide particles contain impurities derived from a transition metal salt for producing a composite transition metal hydroxide, the impurities are 0.4% by weight or less based on the total weight of the composite transition metal hydroxide particles. Composite transition metal hydroxide particles. The composite transition metal hydroxide particles according to claim 18, wherein the impurities are 0.3 to 0.4 wt% based on the total weight of the composite transition metal hydroxide particles. A lithium composite transition metal oxide having a composition represented by the following Chemical Formula 2 prepared by calcining the composite transition metal hydroxide particles according to claim 15 with a lithium precursor.
Li _{1 + b} Ni _y Mn _2-y O _{4 -z} (2)
Wherein 0? B? 0.1; 0.2? Y? 0.5; 0 ≦ z ≦ 0.1; to be. A lithium secondary battery comprising the lithium composite transition metal oxide according to claim 20 as a positive electrode active material. A battery pack comprising a lithium secondary battery according to claim 21. An electric vehicle using the battery pack according to claim 22 as a power source.

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