KR101561608B1 - The method for preparation of positive active material for lithium air battery and the positive active material thereby - Google Patents

Abstract

Provided is a preparation method of a positive electrode active material for a lithium air battery which may include the steps of: manufacturing a mixed solution having a pH of 0.05-1.0 by adding acids and mixing an aluminum precursor, a zinc precursor, and a ruthenium precursor to a solvent (Step 1); manufacturing a positive electrode active material precursor which includes ZnO:Al and RuO_2 by heating the mixed solution manufactured by the step 1 (Step 2); and thermal-treating the positive electrode active material precursor manufactured by the step 2 at 300-450°C (Step 3). The preparation method of a positive electrode active material for a lithium air battery can obtain a positive electrode active material having excellent functions without an additional catalyst process. In addition, by adjusting a mol ratio of the aluminum precursor, the zinc precursor, and the ruthenium precursor, a positive electrode active material having even more excellent functions can be obtained. By using microwaves, a positive electrode active material containing ZnO:Al and RuO_2 can be obtained simply and quickly.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive active material for a lithium ion battery,

The invention method of producing a lithium-air battery, the positive electrode active material and thus relates to a positive electrode active material produced in accordance with, specifically, the aluminum-doped zinc oxide (ZnO: Al) and lithium air battery positive electrode active material containing ruthenium oxide (RuO ₂₎ And a method for producing the same.

Recently, with the development of advanced electronic industry, it has become possible to reduce the size and weight of electronic equipment, and the use of portable electronic devices is increasing. Lithium air cells are being developed as an example of power sources for such portable electronic devices. The lithium air battery has a remarkably high energy density as compared with a lithium ion battery, and has advantages of miniaturization and light weight, by bringing lithium into contact with air. Therefore, when applied to an electric vehicle, it is possible to improve the mileage to 500 km or more, and a lithium ion battery having a mileage of only 160 km is being studied as a battery useful for electric vehicles.

Such a porous carbon material exhibiting excellent electrochemical performance is mainly used as a cathode material of lithium air cells. As a specific example, Korean Patent Laid-Open Publication No. 10-2014-0110572 discloses an anode for a lithium air battery, and more particularly, to a catalyst layer comprising a first conductive material supported on a binder and a catalyst supported on a second conductive material; And an anode for a lithium air battery including a current collector. At this time, the first conductive material and the second conductive material are carbon materials such as graphite, denka black, and ketjen black.

However, when a carbon material is used as a cathode material, lithium carbonate is generated as a reaction by-product between carbon and Li ₂ O ₂ , thereby deteriorating the performance of the battery. In order to solve this problem, a method of using a non-carbon material as a cathode material of a lithium air cell has been proposed.

At this time, in order to apply the non-carbon material as the cathode material, a material having a high electric conductivity should be used, no reactivity with the electrolyte, and a wide potential window is preferable. Of the various oxides satisfying these conditions, zinc oxide has advantages of easy synthesis and low cost.

The inventors of the present invention have been studying a method for producing a cathode active material for a lithium air battery in which when a cathode active material containing aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide is prepared, an aluminum precursor, a zinc precursor and a ruthenium The precursor is mixed with a solvent having a pH of from 0.05 to 1.0 and heat-treated at a temperature of from 300 to 450 ° C to develop a method for producing a cathode active material having an excellent performance as well as an additional catalyst introduction step, .

An object of the present invention is to provide a method for producing a cathode active material for a lithium air battery and a cathode active material produced thereby.

In order to achieve the above object,

Mixing the aluminum precursor, the zinc precursor and the ruthenium precursor in a solvent and adding an acid to prepare a mixed solution having a pH of 0.05 to 1.0 (Step 1);

(Step ₂ ) a cathode active material precursor including aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ) by heating the mixed solution prepared in step 1; And

And heat treating the cathode active material precursor prepared in step 2 at a temperature of 300 to 450 ° C (step 3).

In addition,

The present invention provides a cathode active material for a lithium air battery, which comprises aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ) and has a discharge capacity of 900 mAh / g or more.

Further,

There is provided a positive electrode for a lithium air battery including a positive electrode active material comprising aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ )

Further,

There is provided a lithium air battery including a positive electrode for a lithium air battery including a positive electrode active material including aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ).

The method for preparing a cathode active material for a lithium-air battery according to the present invention comprises mixing an aluminum precursor, a zinc precursor and a ruthenium precursor in a solvent, adjusting the acidity to a specific range, and performing heat treatment at a temperature of 300 ° C to 450 ° C, It is possible to obtain a cathode active material having excellent performance without the catalyst introduction step. In addition, it is possible to obtain a cathode active material having a better performance by controlling the molar ratio of the aluminum precursor, the zinc precursor and the ruthenium precursor, and to easily and rapidly form the aluminum doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ) The cathode active material can be produced.

1 is a scanning electron microscope (SEM) photograph of the cathode active material prepared in Example 1 and Comparative Examples 2 to 5 according to the present invention;
FIG. 2 and FIG. 3 are graphs showing the charge and discharge at 15 mA / g current density of the cathode active material prepared in Example 1 and Comparative Examples 1 to 4 according to the present invention.

The present invention

Mixing the aluminum precursor, the zinc precursor and the ruthenium precursor in a solvent and adding an acid to prepare a mixed solution having a pH of 0.05 to 1.0 (Step 1);

(Step ₂ ) a cathode active material precursor including aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ) by heating the mixed solution prepared in step 1; And

And heat treating the cathode active material precursor prepared in step 2 at a temperature of 300 to 450 ° C (step 3).

Hereinafter, the method for producing the positive electrode active material for a lithium air battery according to the present invention will be described in detail for each step.

First, in the method for producing a cathode active material for a lithium air battery according to the present invention, step 1 is a step of preparing a mixed solution having a pH of 0.05 to 1.0 by mixing an aluminum precursor, a zinc precursor and a ruthenium precursor in a solvent and adding an acid .

When the cathode active material is produced using zinc oxide, which is a conductive oxide containing no carbon, generation of lithium carbonate can be suppressed as compared with carbon materials. The zinc oxide cathode active material has different specific surface area and pore volume depending on its size and shape, and its electrochemical characteristics are different. When the specific surface area is wide, it is possible to react with a wider surface area, It is advantageous.

Therefore, the performance of a lithium-air battery can be improved by preparing a zinc oxide cathode active material having a particle size of several hundred nanometers or less.

In addition, in step 1 of the present invention, a cathode active material is prepared by simultaneously adding an aluminum precursor and a zinc precursor together with a ruthenium precursor serving as a catalyst. Since the cathode active material is prepared by mixing the aluminum precursor, the zinc precursor, and the ruthenium precursor together in the step 1, no additional catalyst introduction step is required. Thus, the production step is reduced and the cathode active material is easily produced can do. Furthermore, the cathode active material can exhibit superior performance because a uniform and improved contact can be obtained as compared with a method of physically mixing aluminum-doped zinc oxide with ruthenium oxide through the above-described method.

At this time, in step 1, the pH of the acid is adjusted to a specific range. By adjusting the pH range to 0.05 to 1.0, the performance of the prepared cathode active material is improved. These conditions serve as important parameters for the morphogenesis of the particles of the zinc oxide cathode active material, and have the shape and size of specific particles according to the pH. The cathode active material prepared by adjusting to such a range can have significantly improved electrochemical characteristics and specific capacity.

The pH of step 1 is preferably 0.05 to 1.0, and more preferably 0.1 to 0.5. If the pH is less than or greater than the above range, the resulting cathode active material may have large particles of micron size. As a result, the electrochemical performance of the produced cathode active material may be deteriorated.

Further, the molar ratio of the aluminum precursor, the zinc precursor and the ruthenium precursor in the mixed solution of Step 1 is preferably 1: 9: 0.5 to 1: 9: 3.0, more preferably 1: 9: 1.0 to 2.0. If the molar ratio of the aluminum precursor, the zinc precursor and the ruthenium precursor in the mixed solution of the step 1 is out of the above range, the particle shape may be changed and the catalytic activity may be deteriorated.

The aluminum precursor of step 1 is selected from the group consisting of aluminum nitrate 9 hydrate (Al (NO ₃ ) ₃ .9H ₂ O), aluminum chloride (AlCl ₃ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) _{3) 3),} and ethyl aluminum _{(Al (CH 3 CO 2)} 3) , and the like, zinc precursor of step 1 is zinc nitrate and hexahydrate (Zn (NO _{3) 3} and 9H ₂ O), zinc chloride (ZnCl ₂ ), Zinc sulfate (ZnSO ₄ ), zinc hydroxide (Zn (OH) ₂ ) and zinc acetate (Zn (CH ₃ CO ₂ ) ₂ ) and the ruthenium precursor may be ruthenium chloride (RuCl ₃ ), ruthenium nitrate ₃ ) and ruthenium fluoride (RuF ₆ ), and the like, but it is not limited thereto.

The solvent of step 1 may include distilled water, C ₁ to C ₃ alcohol, and the like. When the alcohol and distilled water are mixed, the volume ratio of alcohol to distilled water may be 1: 1 to 9: 1 . Here, the C ₁ to C ₃ alcohol may be methanol, ethanol, propanol, and isopropanol, but is not limited thereto.

If the volume ratio of the alcohol and the distilled water is out of the range, the particle size may increase or the shape may change, which may result in a decrease in specific surface area and pore volume of the cathode active material.

Next, in the method for producing a cathode active material for a lithium air battery according to the present invention, step 2 is a step of heating aluminum oxide-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ) Thereby producing a cathode active material precursor.

In the step 2, a precursor of the cathode active material containing aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ) can be obtained by heating the mixed solution prepared in the step 1 by the reaction of the precursors .

In the step 2, it is preferable to use microwave heating as the heating method of the mixed solution. In the microwave heating method, aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ). However, the method of heating is not limited thereto.

The heating in step 2 may be performed at a temperature of 130 ° C to 250 ° C for 10 minutes to 120 minutes, preferably at a temperature of 150 ° C to 200 ° C for 15 minutes to 200 ° C to increase specific surface area and pore volume. It can be heated for 30 minutes. If the heating condition of the step 2 is out of the above range, precipitation may not be generated, and the particle size may be increased or the shape may be changed to cause a decrease in specific surface area and pore volume.

Next, in the method for producing a cathode active material for a lithium air battery according to the present invention, step 3 is a step of heat treating the cathode active material precursor prepared in step 2 at a temperature of 300 ° C to 450 ° C.

In the step 3, the cathode active material precursor may be formed by heat-treating the precursor of the cathode active material prepared in the step 2, and the cathode active material may be heat-treated at a temperature of 300 ° C to 450 ° C.

Specifically, the heat treatment in step 3 is preferably performed at a temperature of 300 ° C to 450 ° C, more preferably at a temperature of 320 ° C to 380 ° C, and a time of 30 minutes to 300 minutes desirable. If the temperature is out of the above range, ruthenium oxide may not be formed or electrochemical performance may be deteriorated.

The heat treatment in step 3 is preferably performed in an oxidizing atmosphere.

As described above, the method of producing a cathode active material according to the present invention comprises mixing an aluminum precursor, a zinc precursor, and a ruthenium precursor in a solvent, adjusting the acidity to a specific range, , It is possible to obtain a cathode active material having excellent performance without further catalyst introduction steps.

In addition,

The present invention provides a cathode active material for a lithium air battery, which comprises aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ) and has a discharge capacity of 900 mAh / g or more.

The positive electrode active material according to the present invention as a cathode active material prepared by adjusting the heat treatment temperature, with also to adjust the pH of the mixed solution of a mixture of precursors of the respective metal, aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ).

The cathode active material according to the present invention can exhibit excellent performance by having a discharge capacity of 900 mAh / g or more.

The cathode active material according to the present invention preferably contains 8.75 wt% to 55 wt% of ruthenium oxide with respect to the total cathode active material. If the cathode active material contains less than 8.75 wt% of ruthenium oxide, the electrochemical performance such as discharge capacity tends to deteriorate. Even if the cathode active material contains more than 55 wt% of the ruthenium oxide, the electrochemical performance deteriorates have.

Further,

There is provided a positive electrode for a lithium air battery including a positive electrode active material comprising aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ).

The positive electrode active material according to the present invention as a cathode active material prepared by adjusting the heat treatment temperature, with also to adjust the pH of the mixed solution of a mixture of precursors of the respective metal, aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ).

The positive electrode active material according to the present invention exhibits excellent performance by having a discharge capacity of 900 mAh / g or more and can exhibit excellent performance when used as a positive electrode of a lithium air battery.

Further,

There is provided a lithium air battery including a positive electrode for a lithium air battery including a positive electrode active material comprising aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ )

The positive electrode active material according to the present invention as a cathode active material prepared by adjusting the heat treatment temperature, with also to adjust the pH of the mixed solution of a mixture of precursors of the respective metal, aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ).

The cathode active material according to the present invention exhibits excellent performance by having a discharge capacity of 900 mAh / g or more, so that the lithium air battery manufactured using the anode as the anode of the lithium air battery can exhibit excellent performance.

Hereinafter, the present invention will be described in detail with reference to the following examples and experimental examples.

It should be noted, however, that the following examples and experimental examples are illustrative of the present invention, but the scope of the invention is not limited by the examples and the experimental examples.

≪ Example 1 > Preparation of cathode active material 1

Step 1: 0.3755 g of aluminum nitrate 9 hydrate (Al (NO ₃ ) ₃ .9H ₂ O), zinc nitrate hexahydrate (Zn (NO ₃ ) ₃ .9H ₂ O) were added so that the aluminum precursor, zinc precursor and ruthenium precursor had a molar ratio of 1: _{3) 3} · 9H ₂ O) 2.6799 g, ruthenium chloride (RuCl _{3) the} mixed solution was stirred, hydrochloric acid was placed to 0.2302 g of a mixed solution of isopropanol 16 ml) and distilled water (4 ml was added to a pH of 0.1 was prepared .

Step 2: The mixed solution prepared in Step 1 was placed in a microwave heater, reacted at 170 ° C for 20 minutes, washed with distilled water and ethanol to remove residual solvent, and dried at 90 ° C to obtain a cathode active material precursor .

Step 3: The cathode active material precursor prepared in the step 2 was reacted at 350 DEG C for 1 hour in an oxidizing atmosphere to prepare a cathode active material containing aluminum-doped zinc oxide and ruthenium oxide.

≪ Comparative Example 1 &

Step 1: 0.3755 g of aluminum nitrate 9 hydrate (Al (NO ₃ ) ₃ .9H ₂ O) and zinc nitrate hexahydrate (Zn (NO ₃ ) ₃ .9H ₂ O) (2.6799 g) was mixed with 16 ml of isopropanol and 4 ml of distilled water, and hydrochloric acid was added thereto at a pH of 0.1, followed by stirring.

Step 2: The mixed solution prepared in step 1 was placed in a microwave heater, reacted at a temperature of 170 ° C for 20 minutes, washed with distilled water and ethanol to remove residual solvent, and then dried at 90 ° C to obtain a zinc oxide precursor .

Step 3: A zinc oxide cathode active material was prepared by reacting the zinc oxide precursor prepared in the above step 2 at 600 DEG C for 2 hours in an oxidizing atmosphere.

Step 4: 0.09 g of zinc oxide cathode active material and 0.01 g of ruthenium chloride were dissolved in 20 ml of ethylene glycol so that the mass ratio of zinc oxide cathode active material and ruthenium precursor produced in step 2 was 9: 1, To 13, and the mixture was heated with stirring at a temperature of 160 DEG C under a nitrogen atmosphere for 3 hours. After heating, the pH was adjusted to 5 with a 0.1 M hydrochloric acid solution and then stirred for 12 hours or longer to prepare a zinc oxide cathode active material containing ruthenium.

At this time, Comparative Example 1 and Example 1 contained the same amount (20 wt%) of noble metal catalyst.

≪ Comparative Example 2 &

The cathode active material was prepared in the same manner as in Example 1, except that the heat treatment was carried out at a temperature of 500 ° C in the step 3 of Example 1.

≪ Comparative Example 3 &

The cathode active material was prepared in the same manner as in Example 1 except that the heat treatment was performed at a temperature of 600 ° C in the step 3 of Example 1.

≪ Comparative Example 4 &

The cathode active material was prepared in the same manner as in Comparative Example 3 except that the aluminum precursor, the zinc precursor and the ruthenium precursor were mixed in a molar ratio of 1: 9: 0.4 in the step 1 of Comparative Example 3.

≪ Comparative Example 5 &

The cathode active material was prepared in the same manner as in Comparative Example 3, except that the aluminum precursor, the zinc precursor, and the ruthenium precursor were mixed in a molar ratio of 1: 9: 0.33 in the step 1 of Comparative Example 3.

<Experimental Example 1> Microstructure of AZO / RuO ₂ cathode active material

In order to confirm the microstructure of the cathode active material prepared by the production method according to the present invention, the cathode active materials prepared in Example 1 and Comparative Examples 2 to 5 were observed under a scanning electron microscope (SEM, Tescan Mira 3 LMU FEG, , Coater was observed with Quorum Q150T ES / 10 mA, 120 s Pt coating). The results are shown in Fig.

As shown in FIG. 1, in the case of Example 1, which is a cathode active material subjected to heat treatment at a temperature of 350 ° C., which is a heat treatment temperature range of the present invention, a nonuniform short rod shape of 100 nm or less and a nonuniform shape It can be confirmed that the particles are mixed.

On the other hand, in the case of Comparative Examples 2 to 5, which were the cathode active materials subjected to the heat treatment at a temperature of 500 ° C and a temperature of 600 ° C outside the heat treatment temperature range of the present invention, it was confirmed that the particles had a heterogeneous shape with a size of several tens of nanometers

Accordingly, the microstructure of the cathode active material prepared by controlling the heat treatment temperature according to the present invention provides a structure in which uneven short rod shapes of 100 nm or less and heterogeneous particles of several tens of nanometers are mixed, It was confirmed that the shape of the particles varies according to the range. On the other hand, it was confirmed that the shape of the particles did not change greatly depending on the molar ratio of the starting materials (aluminum precursor, zinc precursor and ruthenium precursor).

<Experimental Example 2> Electrochemical Characterization of Cathode Active Materials

In order to confirm the electrochemical characteristics of the cathode active material prepared by the production method according to the present invention, the following experiment was conducted using the cathode active material prepared in Example 1 and Comparative Examples 1 to 5.

The electrodes were fabricated using the cathode active materials prepared in Example 1 and Comparative Examples 1 to 5 to form half cells. The manufacturing process of the electrode is as follows. The PTFE (Polytetrafluoroethylene) used as a binder is dissolved in a mixture of distilled water and isopropanol in a volume ratio of 1: 1, and then mixed with the cathode active material. At this time, the weight ratio of the cathode active material and the binder was 8: 2. The slurry thus prepared was coated on a SUS (Steel Use Stainless) net having a circular shape and then dried in an oven controlled at a temperature of 120 ° C for 15 minutes. The half-cell was fabricated using a 2032-type coin cell with a bipolar half-cell. Lithium metal foil was used for the cathode, and glass fiber was used for the separation membrane. The electrolyte used was N, N-dimethylacetamide (DMAc) in which 1.0 M of LiNO ₃ was dissolved. Half cells were fabricated in a dry box in an inert argon (Ar) atmosphere.

Charging and discharging tests were carried out at 25 ° C using a constant current (CC) and a constant current of 15 mA / g was applied. At this time, the discharge cut-off voltage was fixed to 2.0 V (vs. Li / Li ⁺ ) and the charge cut-off voltage was fixed to 4.2 V (vs. Li / Li ⁺ ). The results are shown in the following Tables 1, 2 and 3

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Cathode active material
Discharge capacity (mAh / g) 920 880 830 292 12 12 Cathode active material
Overvoltage (V) 0.9 1.1 1.1 1.3 1.7 1.7

As shown in Table 1, FIG. 2 and FIG. 3, in Comparative Example 1 in which aluminum-doped zinc oxide cathode active material was prepared and ruthenium was introduced as a catalyst, a discharge capacity of 880 mAh / And the overvoltage was confirmed. On the other hand, Example 1, which is a cathode active material produced by using both aluminum precursor, zinc precursor and ruthenium precursor, showed excellent discharge capacity of 920 mAh / g and excellent electrochemical performance of 0.9 V.

In addition, it was confirmed that the electrochemical characteristics of the cathode active material differ greatly according to the heat treatment temperature after microwave heating. Example 1, which was heat-treated in an oxidizing atmosphere at a temperature range of 350 ° C. according to the present invention, exhibited a high capacity of 920 mAh / g and a relatively low overvoltage of 0.9 V, but was heat-treated in an oxidizing atmosphere at a temperature of 500 ° C. It was confirmed that the electrochemical performance of Comparative Example 2 was lower than that of Example 1 at a capacity of 830 mAh / g and an overvoltage of 1.1 V. Also, in the case of Comparative Example 3 which was heat-treated in an oxidizing atmosphere at a temperature of 600 ° C, the electrochemical performance was greatly reduced with a capacity of 292 mAh / g and a high overvoltage of 1.3 V.

The above difference according to the heat treatment temperature seems to be due to the crystallinity of ruthenium oxide. As the crystallinity of the ruthenium oxide is lowered, the amorphous ruthenium oxide exhibits superior catalytic activity, and thus the amorphous ruthenium oxide has better catalytic activity than the crystalline ruthenium oxide, and thus the amorphous ruthenium-doped cathode active material has excellent electrochemical performance such as high capacity and low overvoltage . In addition, the electrochemical characteristics are different according to the molar ratio of aluminum, zinc and ruthenium in the synthesis of the cathode active material including aluminum-doped zinc oxide and ruthenium oxide. When the molar ratio of aluminum, zinc and ruthenium is 1: 9: 1.11 Comparative Example 5 in which the molar ratio of aluminum, zinc and ruthenium was 1: 9: 0.40 and the molar ratio of aluminum, zinc and ruthenium was 1: 9: 0.33 as compared with the discharge capacity of 292 mAh / g in Comparative Example 3 It was confirmed that the discharge capacity of 12 mAh / g and the overvoltage of 1.7 V were exhibited.

Therefore, when the molar ratio of aluminum, zinc and ruthenium is mixed at 1: 9: 0.5 to 3.0, especially 1: 9: 1.11 and the heat treatment temperature is controlled at 300 to 450 캜, particularly 350 캜, Lt; RTI ID = 0.0 &gt; electrochemical &lt; / RTI &gt;

Claims (10)

Mixing the aluminum precursor, the zinc precursor and the ruthenium precursor in a solvent and adding an acid to prepare a mixed solution having a pH of 0.05 to 1.0 (Step 1);
(Step ₂ ) a cathode active material precursor including aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ) by heating the mixed solution prepared in step 1; And
And heat treating the cathode active material precursor prepared in the step 2 at a temperature of 300 ° C to 450 ° C (step 3).
The method according to claim 1,
Wherein the molar ratio of the aluminum precursor, zinc precursor and ruthenium precursor in the mixed solution of step 1 is 1: 9: 0.5 to 1: 9: 3.0.
The method according to claim 1,
The aluminum precursor of step 1 is selected from the group consisting of aluminum nitrate 9 hydrate (Al (NO ₃ ) ₃ .9H ₂ O), aluminum chloride (AlCl ₃ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) ) ₃ ) and aluminum acetate (Al (CH ₃ CO ₂ ) ₃ ), and the zinc precursor is at least one selected from zinc nitrate hexahydrate (Zn (NO ₃ ) ₃ .9H ₂ O), zinc chloride (ZnCl ₂ ), zinc sulfate (ZnSO ₄ ), zinc hydroxide (Zn (OH) ₂ ) and zinc acetate (Zn (CH ₃ CO ₂ ) ₂ ), and the ruthenium precursor is at least one selected from the group consisting of ruthenium chloride Wherein the positive electrode active material is at least one selected from the group consisting of RuCl ₃ , ruthenium nitrate (RuNO ₃ ), and ruthenium fluoride (RuF ₆ ).
The method according to claim 1,
Wherein the acid of step 1 is hydrochloric acid.
The method according to claim 1,
Wherein the solvent of step 1 comprises at least one selected from the group consisting of distilled water and C ₁ to C ₃ alcohols, and the volume ratio of the alcohol to the distilled water is 1: 1 to 9: 1. A method for producing an active material.
The method according to claim 1,
Wherein the heating of step 2 is performed at a temperature of 130 ° C to 250 ° C for 10 minutes to 120 minutes.
The method according to claim 1,
Wherein the heat treatment in step 3 is performed at a temperature of 320 ° C to 380 ° C for 30 minutes to 300 minutes.
A cathode active material for a lithium air battery, comprising aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ), and having a discharge capacity of 900 mAh / g or more manufactured by the manufacturing method of claim 1.
An anode for a lithium air battery comprising a cathode active material comprising aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ), and produced by the manufacturing method of claim 1.
A lithium air battery comprising a cathode for a lithium air battery comprising a cathode active material comprising aluminum-doped zinc oxide (ZnO: Al) and ruthenium oxide (RuO ₂ ) and produced by the manufacturing method of claim 1.

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