KR101689856B1 - A method for manufacturing a cathode for a metal-air electrochemical cell - Google Patents

Abstract

The present invention relates to a method for producing a cathode material having a three-dimensional solid structure coated with a noble metal, the cathode material produced by the method, and a metal air cell including the cathode material.
The method of manufacturing a cathode material according to the present invention has advantages that a cathode material of a metal-air battery can be manufactured by a simple process using an electrolytic plating method and an electroless plating method at room temperature / normal pressure, The anode material can be manufactured. In addition, the cathode material produced by the method according to the present invention has a large specific surface area and can effectively reduce overvoltage upon charging when applied to a metal-air battery.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a cathode material for a cathode,

The present invention relates to a method for producing a cathode material having a three-dimensional solid structure coated with a noble metal, the cathode material produced by the method, and a metal air cell including the cathode material.

Lithium air cells have an electrochemical process in which lithium ions are reacted directly with oxygen outside, in a conventional lithium ion battery, away from the way in which lithium ions intercalate to the electrodes. The anode of the lithium air cell is reacted according to the following reaction 2Li ⁺ + O ₂ ↔ Li ₂ O ₂ A positive reaction occurs in which oxygen is supplied from the outside at the time of discharging to generate Li ₂ O ₂ discharge products by reacting with lithium ions, decomposition of Li ₂ O ₂ formed at the time of charging, and then oxygen is generated again and the reverse reaction Oxygen reductant / oxygen generating catalyst. Due to the accumulation of Li ₂ O ₂ products and side reaction products with poor electrical conductivity during the reversible reaction process, overpotential is required which is larger than theoretically necessary voltage, resulting in a problem of low energy efficiency. The carbon electrode, which is generally used as a lithium air electrode, induces the production of other side reaction products besides Li ₂ O ₂ due to electrolyte decomposition or decomposition of the electrode itself. In order to solve the above problem, it is necessary to reduce the overvoltage of the oxygen reduction and oxygen production reaction in the non-carbon type material, to have sufficient space to store the generated Li ₂ O ₂ , to maintain the original state after the decomposition of the product after charging An electrode material having a stable and porous structure is required.

In addition to carbon materials, there have been tried examples of porous electrode materials made of noble metals as lithium air electrodes. Ding Zhu et al., Chem. Comm. vol. 49, 9573-9575 (2013), nickel foam having a porous structure was purchased and galvanically substituted with a palladium precursor to uniformly platinum palladium on nickel and applied as a lithium air electrode. Palladium in noble metals is expected to show an effect of reducing overvoltage when used as an air electrode as a candidate for good oxygen reduction catalyst material, while being relatively inexpensive compared to other precious metals.

An example of testing a Pd / C electrode made by impregnating a porous carbon substrate with palladium metal by an atomic layer deposition method with a lithium-air cell is described in Yu Lei et al., Nano Letters, vol 13, 4182-4189 (2013)). The particle size of the deposited palladium metal has a diameter of about 5.5 nm and particle size can be controlled by growing the particles at the number of cycles of atomic layer deposition.

In another prior art document (Ji-Jing Xu et al., Nature communications, vol 4, article number 2438), a palladium metal particle is attached to a spherical silica sphere used as a template and a carbon shell (Pd) / hollow spherical carbon (Pd) / carbon (Pd / carbon) was applied to the lithium-air battery.

Among the prior art documents, Si Hyoung Oh et al., Nature. Chemistry, vol. 49, 1004-1010 (2012) discloses a process for preparing mesoporous lead-ruthenium pyrochlore by liquid-crystal templating, which is one of soft template methods, using ruthenium material among noble metals. lead ruthenium pyrochlore). The prepared lead-ruthenium pyrochlore has a mesoporous structure with a specific surface area of 155 m ² / g and a pore volume of 0.18 cm ³ / g and is applied as a cathode material of a lithium-air battery.

Accordingly, the present inventors have developed a three-dimensional porous metal structure electrode made by making a nano-sized three-dimensional porous metal structure by an electrochemical reduction method at room temperature and normal pressure using a simple electrochemical device and partially replacing a noble metal by a galvanic replacement method And thus the present invention has been completed.

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Ding Zhu et al., Chem. Commun., Vol. 49, 9573-9575 (2013) Si Hyoung Oh et al., Nature. Chemistry, vol. 49, 1004-1010 (2012) Yu Lei et al., Nano Letters, vol 13, 4182-4189 (2013) Ji-Jing Xu et al., Nature communications, vol 4, article number 2438 (2013)

It is an object of the present invention to provide a cathode material that can effectively reduce the overvoltage of a metal air cell by using a non-carbon material and a method of manufacturing the same. Other objects and advantages of the present invention will be understood by the following description. It is also to be easily understood that the objects and advantages of the present invention can be realized by the means or method described in the claims, and the combination thereof.

The present invention provides a method of manufacturing a cathode material for a metal air cell. The method comprises the steps of: (S10) forming a foam structure of a metal or metal oxide by an electrolytic plating method; And forming a noble metal reduction layer on the surface of the foam structure formed in the step (S10) (S20). Here, the foam structure is characterized by having a three-dimensional structure by hydrogen bubbles generated during electrolysis and / or deposition of metal or metal oxide in step (S10).

Here, the step (S10) may include preparing a conductive metal substrate (S11); And a step (S12) in which the metal or the metal oxide is electrodeposited in the form of a foam structure having a three-dimensional shape on the conductive metal substrate as the metal or the metal oxide is electrolyzed.

The step (S20) may include a step (S21) of preparing a precious metal-containing precursor aqueous solution; And (S22) dipping the foam structure of the step (S10) in the precursor aqueous solution and forming a noble metal reduction layer on the surface of the foam structure.

Here, the step (S22) may be performed by a galvanic displacement reaction.

Also, in the present invention, the foam-structure may be a porous structure, a dendrite structure, a needle-shaped structure, or a cone-shaped structure.

In the present invention, the noble metal may be one or more kinds selected from palladium (Pd), platinum (Pt), gold (Au), iridium (Ir), osmium (Os), silver (Ag) have.

The conductive metal substrate may be selected from the group consisting of stainless steel, platinum, silver, copper, titanium, nickel, ruthenium, carbon materials, and mixtures of two or more thereof.

The metal or metal oxide of (S20) may be at least one selected from the group consisting of nickel, copper, tin, lead, and oxides thereof. Here, the thickness of the noble metal reducing layer may be 20 nm to 100 nm. The present invention also provides a positive electrode for a metal air cell and a metal air cell comprising the positive electrode, wherein the positive electrode and the electrochemical device include a positive electrode material manufactured by the above-described method.

The method of manufacturing a cathode material according to the present invention has an advantage that a cathode material of a metal-air battery can be manufactured by a simple process using an electrolytic plating method and a non-electrolytic plating method at room temperature / normal pressure, The anode material can be manufactured. In addition, the cathode material produced by the method according to the present invention has a large specific surface area and can effectively reduce overvoltage upon charging when applied to a metal-air battery.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. On the other hand, the shape, size, scale or ratio of the elements in the drawings incorporated herein can be exaggerated to emphasize a clearer description.
1 is a process flow chart schematically showing a method of manufacturing a cathode material according to the present invention.
Figure 2 schematically shows a method of forming a metal foam structure.
3 schematically shows a method of forming a noble metal reduction layer on the surface of a metal structure.
4 is a SEM photograph of the surface of the nickel foam structure.
5 shows an SEM photograph of a nickel foam structure having a palladium reduction layer formed on its surface.
6 is a graph showing a charge / discharge profile of a lithium metal air cell using a nickel foam structure having a palladium reduction layer on its surface as a cathode material.
7 is a graph showing the cycle characteristics of a lithium metal air cell using a nickel foam structure having a palladium reduction layer on its surface as a cathode material.
8 is a SEM photograph of the surface of the copper foam structure.
9A to 9C are SEM photographs of a cathode material having a reduction layer of palladium, platinum and gold formed on the surface of the copper foam structure, respectively.
9D to 9F are SEM photographs of a cathode material having a reduction layer of palladium, platinum and gold formed on the surface of the nickel foam structure structure, respectively.
10 is a TEM photograph of the gold reducing layer formed on the surface of the copper foam structure.
11 shows the distribution of gold (red) and copper (green) in the cathode material by EDS mapping of the anode material of the gold reducing layer / copper foam structure.
12 shows a SEM photograph of a cathode material of a ruthenium / nickel foam structure.

In this specification, the terms or words used in the specification and claims are to be defined appropriately in order to explain the invention in its best mode, and such terms or words should be construed in accordance with the spirit of the invention . In addition, the embodiments described in this specification and the configurations shown in the drawings do not represent all the technical ideas of the present invention in a specific embodiment of the present invention. Accordingly, at the time of filing of the present invention, there may be various equivalents and modifications that may be substituted for within the scope of the present invention.

The present invention relates to a method of manufacturing a cathode material for a metal air cell, comprising the steps of: forming a metal or metal oxide foam structure by electrolytic plating; And forming a noble metal reduction layer on the surface of the foam structure.

Since the method of manufacturing the metal-air battery cathode material of the present invention is carried out under mild process conditions at room temperature and atmospheric pressure using the electrolytic plating method and the electroless plating method, the advantage of manufacturing the cathode material of the metal- . Also, it is possible to manufacture a large-area cathode material in the form of a film by the above method. In addition, the cathode material produced by the method according to the present invention has a large specific surface area and can effectively reduce the overvoltage upon charging when applied to a metal-air battery.

Hereinafter, the present invention will be described in detail with reference to the drawings.

1 is a process flow chart schematically showing a method of manufacturing a cathode material according to the present invention in accordance with a process sequence. As shown in FIG. 1, in the method of manufacturing a cathode material for a metal air battery according to the present invention, a metal foam structure is formed by an electrolytic plating method (S10). According to an embodiment of the present invention, the step (S10) includes the steps of preparing an electrochemical cell for electrolytic plating in detail (S11), and a step (S11) of electrolyzing the metal or metal oxide in the electrolyte to form a three- (S12) electrodeposited on the cathode surface of the electrochemical cell in the form of a foam structure.

According to a specific embodiment of the present invention, the electrochemical cell includes a working electrode, an opposite electrode, and an electrolytic solution, and may separately include a reference electrode. 2 schematically shows an electrochemical cell and a method of forming a foam structure using the same according to a specific embodiment of the present invention.

The working electrode is used as a substrate to which an electrolytic metal or metal oxide is electrodeposited. In one specific embodiment of the present invention, the working electrode may include a conductive metal such as stainless steel, platinum, silver, copper, gold, titanium, nickel, ruthenium and the like. Alternatively, a carbon material such as graphite, carbon nanotube, fullerene, carbon fiber, or the like may be used as the working electrode. According to a specific embodiment of the present invention, a flexible material such as silicon or polyimide film, glass, or the like may be used as the working electrode. In this case, an adhesive such as titanium or chrome may be additionally added Can be applied.

The electrolyte solution may be prepared in the form of a metal precursor aqueous solution by dissolving a metal that can be used as a cathode material of a metal air cell in an aqueous solution. The metal for the cathode material is not particularly limited and may be copper, nickel, ruthenium, manganese, cobalt, tin, lead, gold, palladium, platinum, silver or an alloy containing two or more of them.

When the electrochemical cell is prepared as described above, a constant current is applied to the electrochemical cell. Since the surface of the metal in the electrolytic solution is negatively charged, the colloid state can be maintained, and the hydrogen ion (H ⁺ ) in the aqueous solution surrounds the surface of the metal particle in the colloidal state to form an electric double layer. At this time, when the electrolytic solution is electrolyzed by applying power, metallic particles such as nickel or copper are electrodeposited on the working electrode by electrophoresis.

The metal electrodeposited on the working electrode has a three-dimensional solid shape in which pores are formed inside or on the surface of the metal particle due to hydrogen gas bubbles generated at the same time during electrolytic plating. The hydrogen bubbles are generated from the negative electrode reaction on the working electrode and continue to occur during the electrodeposition of the metal. Therefore, the metal ion is reduced along the region where the hydrogen bubble is not present, and the region where the metal electrodeposition is not caused by the hydrogen bubble remains as an empty space. Accordingly, the foam structure has porous properties in which pores exist in the surface and inside of the body. Also, the foam structure may be a porous dendrite structure, a porous needle-shaped structure, a porous protrusion-type structure, or a porous conical structure depending on the three-dimensional solid shape to be formed. The specific shape of the structure may vary depending on the metal component contained in the electrolytic solution.

Since the pores can be formed variously according to the type of the metal material contained in the electrolyte solution, the concentration of the metal material, and the like, the size of the pores can be from several tens nanometers to tens of microseconds. The diameter of the pores in the foam structure under the conditions according to the present invention is from about 1 탆 to 100 탆, preferably from about 10 탆 to 80 탆. Further, each particle of the metal forming the foam structure is spherical and has a diameter of 500 nm to 10 mm, preferably 1 mm to 3 mm.

The pores of the foam structure are determined according to the bubble size of the reduced hydrogen depending on the applied current, the concentration of the metal precursor in the electrolyte, the pH and / or current application time, the distance between the metal plate and the conductive substrate, It can be different.

In addition, the size of each particle of the metal forming the foam structure may vary depending on the kind of metal, pH, and / or current application time.

2 schematically shows a method of forming a foam structure according to a specific embodiment of the present invention. A method for forming a nickel foam structure will be described in detail with reference to FIG. First, an aqueous nickel precursor solution is prepared from an electrolyte. Next, a stainless steel mesh was used as a working electrode as a working electrode, and a nickel metal metal plate used as a counter electrode was installed on both sides of the stainless steel mesh so as to be electrically Prepare a chemical cell. When a reducing current is applied to a stainless steel mesh connected to the electrochemical cell by connecting a potentiostat to the electrochemical cell, nickel cations are reduced together with the generation of hydrogen gas, and nickel is formed on the surface of the working electrode in the form of a foam structure And electrodeposited.

FIG. 4 is an SEM image of a nickel foam structure formed according to one embodiment of the present invention, and FIG. 8 is an SEM image of a copper foam structure, and it is confirmed that the SEM image is formed into a three-dimensional shape having a pore structure.

Next, a noble metal reduction layer is formed on the surface of the foam structure formed in the above-described step (S20). According to a specific embodiment of the present invention, the step (S20) comprises a step (S21) of preparing a precious metal-containing precursor aqueous solution and a step of immersing the foam structure formed in the step (S10) And forming a noble metal reduction layer on the surface of the structure (S22). According to a specific embodiment of the present invention, the step (S22) may be performed by a galvanic substitution reaction.

In the present invention, the noble metal is not particularly limited, but palladium, platinum, gold, iridium, silver, osmium, ruthenium and the like are used.

 FIG. 3 schematically shows a galvanic substitution reaction using a noble metal reduction layer palladium metal. The aqueous solution of the noble metal-containing precursor may be prepared by dissolving a chloride of a noble metal in an acid solution. For example, when a reducing layer of palladium is formed, palladium chloride is dissolved in a hydrochloric acid solution to prepare an anionic palladium tetrachloride, which is a palladium precursor having anions.

Next, the metal foam structure formed in the above-described step is immersed in the precursor aqueous solution to induce a galvanic substitution reaction. In the foam structure immersed in the precursor aqueous solution, the metal on the surface is oxidized to a cation, and a noble metal anion in the aqueous solution of the precursor, for example, a palladium anion, is reduced by receiving electrons liberated by oxidation and deposited on the surface of the metal foam structure. Oxidation of the surface of the metal foam structure and reduction of the noble metal proceed simultaneously by the galvanic substitution reaction, whereby the metal foam structure is used as a template, and the noble metal is reduced and deposited on the surface thereof to form a noble metal reduction layer. For example, when the nickel foam structure is immersed in the precursor solution under normal temperature conditions, the palladium cations are reduced and the nickel is oxidized to the nickel cations simultaneously, and partial substitution occurs. The immersion time is preferably 30 minutes or more, but is not limited thereto. According to a specific embodiment of the present invention, the thickness of the noble metal reducing layer is about 20 nm to about 100 nm. However, the thickness of the noble metal reducing layer is not particularly limited to the above range. The immersion time and / or the thickness of the noble metal reducing layer can be appropriately adjusted according to the desired catalytic activity.

9A to 9C are SEM images of a cathode material having a noble metal reduction layer of palladium (a), platinum (b) and gold (c) formed on the surface of a copper foam structure, (d), platinum (e) and gold (f) noble metal reduction layers are formed on the surface of the foam structure.

The method for manufacturing a cathode material for a metal air battery according to the present invention uses an electrolytic plating and a non-electrolytic plating method performed at normal temperature / atmospheric pressure, so that the manufacturing method is simple and the amount of metal used is minimized, . In addition, since the shape of the foam structure and the size of the pores can be appropriately controlled, various porous electrodes can be manufactured.

The present invention also provides a cathode material for a metal air cell produced by the above-described manufacturing method and a metal air cell including the cathode material.

The cathode material for a metal air cell manufactured using the above-described method has a sufficient porous space for storing Li ₂ O ₂ produced during the operation of the battery and has a stable porous structure capable of maintaining the original state even after decomposition of the product after charging.

The existing carbonaceous electrode has a problem that the side reaction product other than Li ₂ O ₂ is generated due to the decomposition of the electrolyte or the electrode itself, and the energy efficiency is deteriorated due to the increase of the resistance and the formation of the overvoltage. However, since the cathode material manufactured according to the present invention does not use a carbon material, problems caused by the conventional carbon electrode can be prevented.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the above-described embodiments. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Example 1: Formation of a copper foam structure

An electrochemical cell for electroplating was prepared. In the electrochemical cell, a stainless steel mesh was used as a working electrode, and a copper plate as an opposite electrode was provided on both sides of the stainless steel mesh. A potentiostat was connected to the electrode. 0.1 M CuSO ₄ + 1.5 MH ₂ SO ₄ aqueous solution was used as the electrolyte. A current of 0.375 A / cm < ² > was flown through the electrochemical cell for 45 seconds to form a copper foam structure. 8 is a SEM photograph of the copper foam structure. According to the SEM image, the copper foam structure represents a dendritic structure of spiral-shaped dendritic leaves. Each dendritic structure composed of copper particles having an average size of 500 nm has a size of about 10 to 50 μm.

Example 2: Formation of nickel foam structure

An electrochemical cell for electroplating was prepared. In the electrochemical cell, a stainless steel mesh was used as a working electrode, and a nickel plate as an opposite electrode was provided on both sides of the stainless steel mesh. A potentiostat was connected to the electrode. A 0.1M NiCl ₂ + 2M NH ₄ Cl aqueous solution was used as the electrolyte. A constant reduction current (0.75 A / cm ² ) was applied to the electrochemical cell for 300 seconds to generate hydrogen bubbles and the nickel cations in the electrolyte were reduced on a stainless steel mesh, thereby forming a nickel foam structure.

FIG. 4 shows an image of the nickel foam structure formed in the second embodiment. The pores of the resulting foam had a diameter of about 10 to 80 탆 and the precipitated nickel particles were spherical and had a diameter of about 2 to 6 탆.

Example 3: Formation of noble metal reduction layer and production of cathode material

The nickel foam structure and the copper foam structure prepared in Examples 1 and 2 were immersed in a precursor aqueous solution of each noble metal and allowed to stand for a predetermined time to perform a noble metal cation reduction reaction (galvanic substitution reaction). The raw materials and the reaction conditions used in the respective Examples are shown in Table 1 below.

Example Used metal Total spherical concentration Reaction time The metal component after substitution (EDS) Example 3-1 Copper 1mM Na ₂ PdCl ₄ 30min Copper 89.66 wt%
Palladium 3.2wt% Example 3-2 Copper 1 mM K ₂ PtCl ₆ 60min Copper 81.19 wt%
Platinum 3.94 wt% Example 3-3 Copper 1 mM KAuCN ₂ 10 min Copper 83.09wt%
Gold 1.32wt% Example 3-4 nickel 1mM Na ₂ PdCl ₄ 30min Nickel 88.18wt%
Palladium 6.68 wt% Example 3-5 nickel 5 mM K ₂ PtCl ₆ 60min Nickel 90.82 wt%
Platinum 0.94 wt% Examples 3-6 nickel 1 mM HAuCl ₄ 30min Nickel 88.90wt%
Gold 3.62wt% Examples 3-7 nickel 5mM Na ₂ PdCl ₄ > 10hr Nickel 18.69 wt%
Palladium 75.06 wt% Examples 3-8 nickel 5 mM RuCl ₃ in H ₂ O + ethanol (v / v = 2: 1) > 10hr Nickel 73.24 wt%
Ruthenium 8.78 wt%

Experimental Example 1: Determination of the surface of a cathode material having a noble metal reduction layer

5 is an SEM image of the surface of the cathode material prepared in Examples 3-7. According to this, most of the reduced palladium metal has a dendrite shape, and a part of the palladium metal is aggregated and aggregated. It was confirmed that the shape of the original nickel foam structure was not largely changed even by palladium reduction by the galvanic substitution reaction. The finally fabricated electrode can be divided into three layers: a nickel foam structure on the bottom layer, an alloy layer on the surface of the nickel structure plated with palladium catalyst particles, and an outer surface layer rich in agglomerated palladium particles.

FIGS. 9A to 9C are graphs showing the results of measurement of the surface roughness of the positive electrode material having the noble metal reducing layer of palladium (Example 3-1), platinum (Example 3-2), and gold (Example 3-3) formed on the surface of the copper foam structure, 9D to 9F are graphs showing the results of the SEM image of the noble metal reduced layer of palladium (Example 3-4), platinum (Example 3-5), and gold (Example 3-6) formed on the surface of the nickel foam structure, respectively SEM image of the anode material. Referring to FIGS. 9A and 9B, palladium and platinum electrodeposited on the copper foam structure are electrodeposited on the copper foam structure in a nonuniform size of 20 to 100 nm, and tend to aggregate between palladium metal and platinum. On the other hand, in the case of FIG. 9C, it was confirmed that the gold particles were uniformly formed in a size of about 30 nm on the surface of the spiral-shaped copper foaming structure originally formed. On the other hand, as shown in FIGS. 9D to 9F, the cathode material manufactured using the nickel foam structure exhibited a similar appearance regardless of the kind of the noble metal.

FIG. 10 and FIG. 11 show the distribution of gold particles on the copper particles of the cathode material prepared in Example 3-3 by TEM EDS mapping, confirming that gold particles were substituted on the surface of the particles. 12 is a SEM photograph of the electrode prepared in Example 3-8 in which ruthenium is substituted on the nickel foam structure. Unlike the other embodiments in which the size of the plated noble metal particles can be distinguished, it is difficult to confirm the size of the ruthenium particles in this magnification photograph, and the nickel surface is oxidized by the ruthenium precursor to show a rough surface like a crater shape, Which is different from the shape of the electrode.

Experimental Example 2: Preparation of metal air cell and measurement of charge / discharge profile

A metal air cell was manufactured and its cycle characteristics were confirmed. The palladium / nickel film prepared in Example 3-4 was used as a cathode material, a lithium foil was used as an anode material, a 1M LiCoO ₂ concentration was used as an electrolyte, and a glass fiber was used as a separator A coin-shaped lithium air cell was assembled. The assembly process of the entire cell was carried out in a glove box filled with argon gas. The lithium air cell prepared above was charged and discharged at a current density of 40 mA / g in a voltage range of 2 to 4.2 V under an oxygen pressure of 1.5 bar, and its profile is shown in FIG. At discharge, stable voltage was observed at about 2.7V, about 3.55V at charging, and the fully discharged capacity was about 2250mAh / g.

Experimental Example 3: Determination of cycle characteristics of metal air cell

The cycle characteristics were confirmed using the battery prepared in Experimental Example 2. [ The cycle characteristics were tested by limiting the capacity to about 10% of the discharge capacity, and the results were plotted and shown in FIG. According to the results shown in FIG. 7, the overvoltage was increased but the capacity was kept constant up to 15 cycles.

Claims (10)

(S10) forming a metal or metal oxide foam structure by electrolytic plating; And
(S20) forming a noble metal reduction layer on the surface of the foam structure formed in step (S10), wherein the foam structure is formed by electrolysis and / or electrolysis of metal or metal oxide in step (S10) Dimensional structure due to hydrogen bubbles generated at the time of deposition,
Here, the step (S10) includes the steps of: (S11) preparing a conductive metal substrate; (S12) depositing a metal or a metal oxide on the conductive metal substrate in the form of a foam having a three-dimensional shape as the metal or the metal oxide is electrolyzed; Lt; / RTI >
The step (S20) includes the steps of: (S21) preparing an aqueous solution of a noble metal-containing precursor; And (S22) dipping the foam structure of the step (S10) in the precursor aqueous solution to form a noble metal reduction layer on the surface of the foam structure,
The metal or metal oxide of (S20) is copper or copper oxide,
The step (S22) is performed by a galvanic displacement reaction,
Wherein the foam structure has a pore diameter of 10 to 80 占 퐉.
delete delete The method according to claim 1,
Wherein the foam-structure is a porous structure, a dendrite structure, a needle-shaped structure, or a cone-shaped structure.
The method according to claim 1,
Wherein the noble metal is at least one selected from palladium (Pd), platinum (Pt), gold (Au), iridium (Ir), osmium (Os), silver (Ag), and ruthenium A method of manufacturing a cathode material for a battery.
The method according to claim 1,
Wherein the conductive metal substrate is selected from the group consisting of stainless steel, platinum, silver, copper, nickel, ruthenium, manganese, cobalt, tin, lead, gold, palladium, carbon materials and mixtures of two or more thereof. A method of manufacturing a cathode material for a battery.
delete The method according to claim 1,
Wherein the noble metal reducing layer has a thickness of 20 nm to 100 nm.
An anode for a metal air battery comprising a cathode material produced by the method according to any one of claims 1, 4, 5, 6 and 8.
11. A metal air cell comprising a positive electrode according to claim 9.

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