KR101139326B1 - Method for manufacturing of nano-size manganese oxide catalyst for zinc-air battery and Method for manufacturing air electrode for zinc-air battery using the same - Google Patents

Abstract

The present invention relates to a method for producing a nano-sized manganese oxide (MnO ₂ ) catalyst for air-zinc batteries and a method for producing an air electrode using the same.

The present invention comprises the steps of dissolving the fibrous forming polymer material and manganese oxide precursor in a solvent to prepare a spinning solution; Spinning the spinning solution on a current collector plate to form a composite nanofiber web; And it provides a method for producing a nano-sized manganese oxide (MnO ₂ ) catalyst for air-zinc batteries comprising the step of heat-treating the composite nanofiber web to produce manganese oxide nanoparticles.

Electrospinning, manganese oxide, nanoparticles, air-zinc batteries, active materials

Description

Method for manufacturing of nano-size manganese oxide catalyst for zinc-air battery and Method for manufacturing air electrode for zinc-air battery using the same }

The present invention relates to a method for producing a manganese oxide catalyst for producing a manganese oxide used in the catalyst layer for an air-zinc battery to a nano size and a method for producing an air electrode having a catalyst layer using such a nano-size manganese oxide catalyst.

Air-zinc batteries have low self-discharge, and the electrode materials used are environmentally friendly and inexpensive. In addition, by using air for the anode and using a large amount of zinc powder for the electrode design, it is possible to design a smaller and ultra high capacity electrode.

Currently, air-zinc batteries are one of the fields where applications are being progressed as secondary batteries and fuel cells as well as for hearing aids.

An air-zinc battery is prepared by mixing and mixing a zinc (Zn) powder and a gelling agent in an aqueous alkali solution, which is an electrolyte, to prevent the flow of the electrolyte, making the zinc powder formable, and acting on the cathode. It consists of a silver catalyst layer and a hydrophobic membrane, and the catalyst layer is used by compressing nickel screen using activated carbon, conductive material, manganese oxide and binder.

An air-zinc battery has a theoretical capacity of 820 mAh / g, which is about 10 times larger than a lithium ion secondary battery, and has an advantage of miniaturization. In addition, since the oxygen of the cathode becomes hydroxide ions (OH ⁻ ) after the reaction, unlike the organic solvent for a lithium ion secondary battery, it is incombustible and can constitute a battery having high safety. In addition, the zinc (Zn) powder used for the cathode is rich and less than 1/100 of the price of lithium, so it is economical and provides flat voltage characteristics until all the zinc powder is oxidized to ZnO, and it is pollution-free due to low environmental load. High capacity batteries can be provided.

1 is a cross-sectional view showing the configuration of a general air-zinc battery.

Referring to FIG. 1, the air-zinc battery is a zinc gel 100 as a negative electrode, a PP (polypropylene) separator 200 having ion permeability to be separated from the negative electrode side, and reacts with oxygen in air. (1) a catalyst layer 400 containing carbon and manganese oxide (MnO ₂ ), which cause the anodic reaction, a metal mesh layer 500 having electron conduction, the separator 200 and the catalyst layer 400 The adhesive layer 300 to be bonded is composed of a PTFE (polytetraflouroethylene) hydrophobic film 600 configured to prevent the absorption of carbon dioxide (CO ₂ ) to extend the life of the battery.

The reaction formula of the air-zinc cell is shown in the following reaction formula (1), and when charged, the reverse reaction of this reaction occurs.

_{Cathode: O 2 + 2H 2 O +} 4e - ---> 4OH -

^{Cathode: 2Zn + 4OH - ---> 2ZnO} + 2H 2 O + 4e -

Total reaction: 2Zn + O ₂ ---> 2ZnO

However, when the amount of oxygen introduced into the anode is insufficient, the discharge voltage is lowered and the capacity of the battery is reduced. This phenomenon occurs due to the slow reduction of oxygen in the anode layer, and the reaction site of the catalyst should be increased by increasing the number of particles of manganese oxide (MnO ₂ ), which is an oxygen reduction catalyst of the anode layer.

To this end, the number of catalyst particles must be increased, but there is a limit to increasing the amount of high density manganese oxide (MnO ₂ ) in a limited space.

In addition, although the manganese oxide (MnO ₂ ) is being atomized through milling, etc., most of them do not reach the nano scale in a micro order of 1 µm or more, and manganese oxide (MnO ₂ ) The reality is that nanoparticles involve significant process costs.

Accordingly, an object of the present invention is to provide a method for preparing a manganese oxide catalyst capable of producing nano-sized manganese oxide used in a catalyst layer for an air-zinc battery through a simple method of electrospinning.

In addition, another object of the present invention to provide a method for producing a cathode that can produce a cathode using a nano-sized manganese oxide as a catalyst layer.

Furthermore, another object of the present invention is to prepare a manganese oxide catalyst of the nano-size to provide a method for producing a manganese oxide catalyst that can have a high energy density by using as a catalyst layer in the cathode for air-zinc batteries and a method for producing the cathode using the same do.

According to an aspect of the present invention for achieving the above object, the step of preparing a spinning solution by dissolving a fibrous forming polymer material and a manganese oxide precursor in a solvent; Spinning the spinning solution on a current collector plate to form a composite nanofiber web; And it provides a method for producing a nano-sized manganese oxide (MnO ₂ ) catalyst for air-zinc batteries comprising the step of heat-treating the composite nanofiber web to produce manganese oxide nanoparticles.

The fibrous forming polymer material may be polymethyl methacrylate (PMMA), polyvinylacetate (PVAc), polyvinylachol (PVA), polyvinylpyrrolidone (PVP), polyethyleneoxide (PEO), polyurethene (PU), polyvinylchloride (PVC), polyacrylic acid (PAA), PLA -At least one selected from derivatives.

The manganese oxide precursor is selected from manganese acetate, manganese acetate tetrahydrate, manganese acetate dihydrate, manganese acetylacetonate, manganese chloride It is characterized by any one or more.

The solvent is characterized in that a single or a plurality of mixed solutions in DMAc (N, N-dimethylaceticamide), DMF (Dimethylformamide), acetone (Acetone), alcohol (alcohol), THF (tetra hydro furan) water and the like.

The heat treatment may include performing a second heat treatment after pulverizing by cooling at room temperature after performing the first heat treatment.

The radiation is characterized in that at least one selected from electrospinning, electrospray, electrobrown spinning, centrifugal electrospinning, flash-electrospinning.

The content of the manganese oxide precursor includes 0.5 to 90 parts by weight based on 100 parts by weight of the fibrous forming polymer material.

In addition, according to another embodiment of the present invention, the step of preparing a slurry by mixing the resulting manganese oxide nanoparticles, activated carbon, conductive material, binder; After drying the prepared slurry, roll pressing on a metal mesh to form a catalyst layer; And arranging the formed catalyst layer on a hydrophobic film. The method provides a method of manufacturing an air electrode using a nano-sized manganese oxide (MnO ₂ ) catalyst for an air-zinc battery.

According to another aspect of the invention, the step of dissolving the carbon fiber precursor polymer material and manganese oxide precursor in a solvent to prepare a spinning solution; Spinning the spinning solution on a current collector plate to form a composite nanofiber web; Heat treating the composite nanofiber web to produce infusible nanofibers; And carbonizing the insoluble fiber to produce manganese oxide / carbon nanofibers. The method provides a method of preparing nano-sized manganese oxide (MnO ₂ ) catalyst for an air-zinc battery.

The carbon fiber precursor polymer material is polyacrylonitrile (PAN), cellulose (Cellulose), polybenzimidazole (PBI), pitch (polyimide), polyacetylene (polyacetylene), polyaniline (polyaniline), polypyrrole (polypyrrole), polythiol At least one selected from polythiophene and poly sulfur nitride.

The manganese oxide precursor is selected from manganese acetate, manganese acetate tetrahydrate, manganese acetate dihydrate, manganese acetate dihydrate, manganese acetylacetonate, manganese chloride It is characterized by one or more.

The solvent is characterized in that a single or a plurality of mixed solutions in DMAc (N, N-dimethylaceticamide), DMF (Dimethylformamide), acetone (Acetone), alcohol (alcohol), THF (tetra hydro furan) water and the like.

According to another aspect of the present invention, the step of preparing a slurry by mixing the resulting manganese oxide / carbon nanofibers, conductive material, binder; Drying the slurry thus prepared, followed by roll pressing on a metal mesh to form a catalyst layer; And arranging the formed catalyst layer on a hydrophobic film. The method provides a method of manufacturing an air electrode using a nano-sized manganese oxide (MnO ₂ ) catalyst for an air-zinc battery.

According to another embodiment of the present invention, the nano-size manganese oxide (MnO ₂₎ for air-zinc battery, characterized in that to form a cathode by forming a catalyst layer comprising the manganese oxide nanoparticles or manganese oxide / carbon nanofibers produced Provided is a method of manufacturing an air electrode using a catalyst.

Therefore, in the present invention, since the nano-sized manganese oxide is used as a catalyst, the air-zinc battery may have high capacity, high power, and high safety.

In addition, in the present invention, since the nano-sized manganese oxide is manufactured by a simple method through electrospinning, mass production at low cost is possible.

In addition, in the present invention, a carbon nanofiber layer in which nano-sized manganese oxides are uniformly formed is formed to have excellent electric conduction channels, thereby enabling high-speed charging and discharging.

The present invention is to prepare a manganese oxide catalyst for reducing the air, a cathode active material for air-zinc batteries in nano size and to prepare a manganese oxide nanoparticles or manganese oxide / carbon nanofibers through electrospinning to produce an air electrode using the manganese Used as an oxide catalyst.

First, in order to manufacture manganese oxide nanoparticles, a spinning solution is prepared by mixing a manganese oxide precursor material and a fibrous forming polymer material, and electrospinning them by an electrospinning method to form a composite nanofiber web, followed by heat treatment in an oxidizing atmosphere. Through the process, the fibrous forming polymer is decomposed to obtain manganese oxide nanoparticles.

In addition, in order to manufacture manganese oxide / carbon nanofibers, a spinning solution is prepared by mixing a manganese oxide precursor material and a carbon fiber precursor material, and electrospinning it by an electrospinning method to form a composite nanofiber web, and then the temperature is lower than 350 ° C. Infusible nanofibers are prepared by heat treatment in an oxidizing atmosphere. Carbonization of the infusible nanofibers in an inert atmosphere may form carbon nanofibers and form manganese oxide / carbon nanofibers in which manganese oxides of nanoparticles are uniformly distributed on the surface thereof.

The fibrous forming polymer material may be polymethyl methacrylate (PMMA), polyvinylacetate (PVAc), polyvinylachol (PVA), polyvinylpyrrolidone (PVP), polyethyleneoxide (PEO), polyurethene (PU), polyvinylchloride (PVC), polyacrylic acid (PAA), PLA Biodegradable polymers, such as derivatives, may be used alone or in combination, but are not limited to the above materials, and may be decomposed after heat treatment so that pyrolysates are not deposited on the metal oxide layer, and may form manganese oxide nanoparticles. no limits.

Carbon fiber precursor polymer materials include polyacrylonitrile (PAN), cellulose (Cellulose), polybenzimidazole (PBI), pitch (polyimide), polyacetylene (polyacetylene), polyaniline (polyaniline), polypyrrole (polypyrrole), polythiophene (polythiophene), poly sulfur nitride (poly sulfur nitride) and the like can be used alone or in combination, but is not limited to the above materials, and if the material that can form a carbon fiber or carbon layer after heat treatment is special no limits.

The manganese oxide precursor material includes manganese acetate, manganese acetate tetrahydrate, manganese acetate dihydrate, manganese acetylacetonate, manganese chloride, and the like. It may be used alone or in combination, but is not limited to the above material, and there is no particular limitation as long as it can form manganese oxide particles after heat treatment.

The radiation method is characterized in that at least one selected from electrospinning, electrospray, electrobrown spinning, centrifugal electrospinning, flash-electrospinning and the like. .

Hereinafter, each step will be described in detail.

A. Step of preparing spinning solution containing metal oxide precursor

After the manganese oxide precursor and the fibrous forming polymer material or the manganese oxide precursor and the carbon fiber precursor polymer material are mixed, the spinning solution is prepared by stirring and dissolving to a spinning concentration using a compatible solvent.

The amount of manganese oxide precursor in preparing the spinning solution is 0.5 to 90 parts by weight based on 100 parts by weight of the fibrous forming polymer material. If the amount is less than 0.5 parts by weight, there is no economic efficiency, and if it exceeds 90 parts by weight, it is impossible to uniformly disperse the manganese oxide precursor because the content of the polymer is low and the spinning is impossible.

In addition, the solvent is not particularly limited, but a single or a plurality of mixed solutions may be used in DMAc (N, N-dimethylaceticamide), DMF (Dimethylformamide), acetone, alcohol (alcohol), and THF (tetra hydrofuran) water. have. The solvent should be included in the range of 3 to 60% by weight based on the total weight of the spinning solution to facilitate the formation of the fibrous structure and to control the morphology of the fiber.

B. Formation of Composite Nanofiber Web

Each spinning solution prepared above is transferred to a spin pack using a metering pump, and a high voltage regulator is used to apply a voltage to the spinning pack to perform electrospinning.

At this time, the voltage used can be adjusted to 0.5kV ~ 100kV, the current collector can be grounded or charged to the (-) pole. The current collector plate is composed of an electrically conductive metal plate, a release paper, and the like. In the case of the current collector plate, it is preferable to attach and use a suction collector to smoothly focus the fibers during electrospinning.

In addition, the distance between the spin pack and the collector plate is preferably adjusted to 5 to 50 cm. In the case of electrospinning, the discharge amount is discharged by discharging at 0.01 ~ 5cc / holemin per hole using a metering pump, and spinning is conducted in the environment of 10-90% relative humidity in a chamber where temperature and humidity can be controlled. Prepare less than composite nanofiber webs.

Hereinafter, the composite nanofiber web formed of the manganese oxide precursor and the fibrous forming polymer material is called a fibrous forming polymer material composite nanofiber web, and the composite nanofiber web formed of the manganese oxide precursor and the carbon fiber precursor polymer material is carbon fiber. Called the precursor composite nanofiber web.

C-a. Manganese Oxide Nanoparticle Formation Step

When the fibrous forming polymer composite nanofiber web prepared above is heat-treated, the fibrous forming polymer is pyrolyzed and oxygen is deposited on the manganese (Mn) nanoparticles to form manganese oxide nanoparticles. At this time, the heat treatment is preferably carried out in an oxidizing atmosphere or air, such conditions are to form manganese oxide by depositing oxygen on the manganese nanoparticles.

The heat treatment may be carried out in a multi-stage heat treatment, it is preferable to perform a second heat treatment after the first heat treatment through a process such as grinding, classification. In the case of the first heat treatment, it is carried out at around 300 ~ 500 ℃ to prevent entanglement between nanoparticles, and pulverized and classified using a method such as a ball mill, an attention mill, or a jet mill, and then secondary at 500 ~ 1000 ℃. Heat treatment is performed to prepare manganese oxide nanoparticles for air-zinc batteries.

The manganese oxide nanoparticles which have been pulverized and classified in the above have a length of less than 1 μm in terms of electrode slurry production.

The metal oxide is grown while the heat treatment is performed. According to the manufacturing method of the present invention, since the metal oxide is covered by the fibrous forming polymer during the first heat treatment, it cannot grow and quickly forms crystals. The heat treatment is preferably performed when the fibrous forming polymer remains or the crystals of the metal oxide do not grow, and the temperature is preferably set in a temperature range in which the metal oxide is not grown or coalesced.

C-b-1. Composite Nanofiber Infusible Nanofiber Forming Step

The carbon fiber precursor composite nanofiber web prepared above is heated by 1 to 3 ° C. per minute in air and heat-treated at a temperature in the range of 240 to 350 ° C. to obtain an oxidative stabilized fiber, that is, an incompatible fiber.

The oxidative stabilization process is a process of introducing oxygen into the thermoplastic polymer to convert it into a thermosetting material. The final temperature is preferably adjusted and set according to the precursor material to be used.

C-b-2. Manganese Oxide / Carbon Nanofiber Forming Step

The insoluble fiber prepared in Cb-1 is carbonized at an inert atmosphere (N ₂ , Ar or He) at a temperature in the range of 600 to 1500 ° C. to form manganese oxide / carbon nanofibers. The manganese oxide / carbon nanofibers formed are those in which manganese oxide nanoparticles are present on the surface of the carbon nanofibers.

The carbon fiber precursor polymer, which has undergone infusion, is composed of only carbon elements while releasing heterogeneous elements other than carbon out of the system, and as the heat treatment temperature increases, the conductivity increases due to the formation of graphite crystals, but the process cost increases when the heat treatment temperature increases. It is preferable to carry out by setting the temperature range which the crystal | crystallization of a manganese oxide does not destroy suitably.

In addition, by supplying an inert gas and water vapor at the same time during the carbonization process to form fine pores on the surface of the carbon fiber it can significantly improve the specific surface area. At this time, the activation temperature is suitable 700 ~ 1000 ℃, at the temperature of more than 1000 ℃ pore blockage due to the growth of the activated carbon crystals, the yield is reduced, it is difficult to expect economic activation. In addition, at a temperature of less than 700 ° C., water vapor hardly forms pores on the surface of the carbon fiber, which makes it difficult to improve the specific surface area. Therefore, it is preferable to use the activation adjusted appropriately according to the physical properties of the final product.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples, and the following examples are appropriately changed by those skilled in the art within the scope of the present invention. Can be.

(Example 1)

18 parts by weight of polyvinylacetate (PVAc) was dissolved in a solvent in which DMAc (N, N-dimethylaceticamide) and THF (tetrahydrofuran) were mixed at a weight ratio of 70:30 (% by weight), and then polyvinylacetate (PVAc) Manganese acetylacetonate (Manganese acetylacetonate) was mixed to 20 parts by weight to prepare a spinning solution.

The spinning solution thus prepared was subjected to electrospinning at room temperature and normal pressure at an applied voltage of 30 kV, a distance of 15 cm between the spinneret and the current collector, and a discharge amount of 0.05 cc / g (cc / h). 2 shows a scanning electron micrograph of the composite nanofiber web spun at this time.

The spun web was heated at 5 ° C. per minute in air, heat-treated at 400 ° C. for 2 hours, and then cooled to room temperature. The cooled sample was pulverized through a ball mill for 4 hours, classified into 50-200 nm, and then heated up to 700 ° C. in air, followed by heat treatment for 1 hour. Thus, manganese oxide nanoparticles were prepared.

Figure 3 shows a scanning electron micrograph of the prepared manganese oxide nanoparticles. As shown in Figure 3, the nanoparticle diameter of the prepared manganese oxide showed a distribution of about 50 ~ 300nm, an average of 200nm was prepared.

(Example 2)

In the same ratio as in Example 1, PAN (polyacrylonitrle) and manganese acetylacetonate were mixed, dissolved in DMF (N, N-dimethylformamide) solvent to prepare a spinning solution.

The spinning solution thus prepared was spun in the same manner as in Example 1 to prepare a composite nanofiber web.

The composite nanofiber web thus prepared was heated to 1 ° C. per minute using a hot air circulation furnace and heat-treated at 240 ° C. for 1 hour to obtain dark-brown infusible fibers.

Thus prepared infusible fibers were heated by 5 ℃ per minute using a tube-type carbonization furnace in a nitrogen gas atmosphere and carbonized at 700 ℃ for 1 hour to prepare a manganese oxide / carbon nanofibers.

Figure 4 shows a scanning electron micrograph of the prepared manganese oxide / carbon nanofibers, the diameter of the carbon nanofibers was confirmed to have a distribution of approximately 100 ~ 500nm. The manganese oxide / carbon nanofiber shown in FIG. 4 is carbonized with PAN fibers by heat treatment, and the manganese oxide precursor is formed from manganese oxide nanoparticles shown in FIG. 2 on the surface of carbon nanofibers. It can be expected that the oxide nanoparticles are uniformly distributed.

(Example 3)

The manganese oxide nanoparticles prepared by the method of Example 1 were prepared using an activated carbon having a specific surface area of 800 m 2 / g to prepare a cathode of an air-zinc battery.

The cathode was mixed with 10 parts by weight of manganese oxide of nanoparticles, 55 parts by weight of activated carbon, 5 parts by weight of conductive carbon black, and 30 parts by weight of a PTFE suspension solution as a binder in distilled water and stirred.

The mixed slurry was dried at 100 ° C. oven and then kneaded with 400 cc of IPA (isopropyl alcohol). After kneading with a roll press to make a thickness of 800㎛ and then pressed to a nickel mesh (Ni-mesh) to produce an electrode of 400㎛ and heat-treated to 150 ℃ through a thermocompressor to remove moisture And pores, which are inflow paths of oxygen, were formed.

The negative electrode was mixed with 0.5 parts by weight of PAA with a gelling agent (gelling agent) to prevent evaporation of the electrolyte in an aqueous solution of 8.5M KOH, stirred for 3 hours and kneaded so that the zinc powder is 74 parts by weight to prepare a zinc gel.

The battery is filled with 1.3 g of zinc gel in a 1.4 × 1.4 × 0.2 rectangular silicon rubber, placed on a hydrophilized PP separator (celgard 3501), a PTFE non-woven fabric, a carbon layer, and the like, and then an oxygen intake hole is formed. The battery was assembled and evaluated by covering the top cap.

(Example 4)

A battery was manufactured in the same manner as in Example 3, except that manganese oxide / carbon nanofibers prepared by the method of Example 2 were used, and activated carbon was not added during slurry preparation.

Performance evaluation of the batteries prepared by Examples 3 and 4 was a constant current discharge and pulse discharge at a current density of 50 ~ 500 ㎃ / ㎠ to compare the capacity and energy average discharge voltage of the battery.

In order to perform comparative experiments according to the manganese oxide particle size, the electrode was manufactured and evaluated using a particle size of 10 μm and 1 μm of manganese oxide under the same composition as the above conditions.

From the results of Examples 3 and 4, there was no significant change in the performance according to the particle size of manganese oxide in the low current discharge, but in the case of high current discharge of 100 mA / cm 2 or more, the smaller the particle size of the manganese oxide was, the battery performance was improved. Was found to improve dramatically.

Especially in the case of pulse discharge, the smaller the particle size of the manganese oxide, the better the battery performance was confirmed.

According to the present invention, it is possible to produce a nano-particle or nano-fiber metal oxide in a desired nano-size using a metal precursor can be applied as an electrode composition to a variety of batteries.

1 is a cross-sectional view showing the configuration of a general air-zinc battery,

2 is a scanning electron micrograph of the spun composite nanofiber web,

3 is a scanning electron micrograph of the prepared manganese oxide nanoparticles,

Figure 4 is a scanning electron micrograph of the prepared manganese oxide / carbon nanofibers.

Claims (13)

Preparing a spinning solution by dissolving a fibrous forming polymer material and a manganese oxide precursor in a solvent; Spinning the spinning solution on a current collector plate to form a composite nanofiber web; And heat treating the composite nanofiber web to produce manganese oxide nanoparticles, The manganese oxide precursor is selected from manganese acetate, manganese acetate tetrahydrate, manganese acetate dihydrate, manganese acetate dihydrate, manganese acetylacetonate and manganese chloride. One or more, The heat treatment is a method for producing a nano-sized manganese oxide (MnO ₂ ) catalyst for an air-zinc battery comprising the step of performing a second heat treatment after cooling and grinding at room temperature after the first heat treatment. According to claim 1, wherein the fibrous forming polymer material is polymethyl methacrylate (PMMA), polyvinylacetate (PVAc), polyvinylachol (PVA), polyvinylpyrrolidone (PVP), polyethyleneoxide (PEO), polyurethene (PU), polyvinylchloride (PVC), PAA (polyacrylic acid), a method for producing a nano-sized manganese oxide (MnO ₂ ) catalyst for an air-zinc battery, characterized in that any one or more selected from PLA- derivatives. delete The method of claim 1 wherein the solvent is DMAc (N, N-dimethylaceticamide) and THF (tetrahydrofuran) air, characterized in that a mixture of a zinc cell of nanoscale manganese oxide (MnO ₂₎ process for producing a catalyst. delete The method of claim 1, wherein the radiation is at least one selected from electrospinning, electrospray, electrobrown spinning, centrifugal electrospinning, and flash-electrospinning. Method for producing a nano-sized manganese oxide (MnO2) catalyst for an air-zinc battery, characterized in that. The method of claim 1, wherein the content of the manganese oxide precursor is 0.5 to 90 parts by weight based on 100 parts by weight of the fibrous forming polymer material. Preparing a spinning solution by dissolving a carbon fiber precursor polymer material and a manganese oxide precursor in a solvent; Spinning the spinning solution on a current collector plate to form a composite nanofiber web; Heat treating the composite nanofiber web to produce infusible nanofibers; And carbonizing the incompatible fiber to produce manganese oxide / carbon nanofibers, The manganese oxide precursor is selected from manganese acetate, manganese acetate tetrahydrate, manganese acetate dihydrate, manganese acetate dihydrate, manganese acetylacetonate, manganese chloride One or more, The heat treatment is a method for producing a nano-sized manganese oxide (MnO ₂ ) catalyst for an air-zinc battery comprising the step of performing a second heat treatment after cooling and grinding at room temperature after the first heat treatment. The method of claim 8, wherein the carbon fiber precursor polymer material is polyacrylonitrile (PAN), cellulose (Cellulose), polybenzimidazole (PBI), pitch (polyimide), polyacetylene (polyacetylene), polyaniline (polyaniline), polypyrrole (Polypyrrole), polythiophene (polythiophene) and poly sulfur nitride (poly sulfur nitride) any one or more selected from the method of producing a nano-sized manganese oxide (MnO ₂ ) catalyst for an air-zinc battery. delete Preparing a slurry by mixing the manganese oxide nanoparticles, the activated carbon, the conductive material, and the binder produced by claim 1; Drying the slurry thus prepared, followed by roll pressing on a metal mesh to form a catalyst layer; And A method of manufacturing an air electrode using a nano-sized manganese oxide (MnO ₂ ) catalyst for an air-zinc battery, comprising the step of disposing the formed catalyst layer on a hydrophobic film. Preparing a slurry by mixing manganese oxide / carbon nanofibers, a conductive material, and a binder produced by claim 8; Drying the slurry thus prepared, followed by roll pressing on a metal mesh to form a catalyst layer; And A method of manufacturing an air electrode using a nano-sized manganese oxide (MnO ₂ ) catalyst for an air-zinc battery, comprising the step of disposing the formed catalyst layer on a hydrophobic film. The nano-sized manganese oxide (MnO ₂ ) for air-zinc batteries, characterized in that to form a cathode by forming a catalyst layer containing manganese oxide nanoparticles or manganese oxide / carbon nanofibers produced by claim 1 or claim 10 Method for producing an air electrode using a catalyst.

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