KR20090044307A - Method for preparation of co3o4 thin films having mesoporous structure by electrochemical deposition and co3o4 thin films prepared by the method - Google Patents

Abstract

The present invention relates to a method for producing a tricobalt tetraoxide thin film having an intermediate pore structure by an electrochemical vapor deposition method, and to a tricobalt tetraoxide thin film manufactured using the same, more specifically, after dissolving cobalt sulfate powder in distilled water, CTAB powder is added And mixing to prepare an electrolyte solution (step 1); Preparing a tricobalt tetraoxide thin film having an intermediate pore structure by immersing the substrate in the electrolyte solution prepared in step 1 and depositing the same by electrochemical method (step 2); And a method for producing a tricobalt tetraoxide thin film having a mesoporous structure comprising a step (step 3) of removing the CTAB from the thin film prepared in step 2 using a washing solution, and the tricobalt tetraoxide thin film manufactured using the same. . The tricobalt tetraoxide thin film according to the present invention can produce tricobalt tetraoxide having a uniform mesoporous structure even with a small amount of structure culture material without an additional deposition process, thereby increasing the specific surface area compared to tricobalt tetraoxide having no porosity. Since the performance can be significantly improved, it can be usefully used for electrode materials of catalysts, lithium secondary batteries and supercapacitors using the same.

Tricobalt tetraoxide (Co3O4), electrochemical deposition, mesoporous structure, CTAB,

Description

Method for preparing tricobalt tetraoxide thin film having an intermediate pore structure by electrochemical vapor deposition method and tri-cobalt tetraoxide thin film manufactured using the same {Method for preparation of CO3O4 thin films having mesoporous structure by electrochemical deposition and CO3O4 thin films prepared by the method}

The present invention relates to a method for producing a tri-cobalt tetraoxide thin film having a mesoporous structure by the electrochemical vapor deposition method and a tri-cobalt tetraoxide thin film manufactured using the same.

Plating usually refers to an operation of coating a thin layer of another metal or alloy on a metal surface. Plating began in the Roman era in the West and in the Chinese tradition in the East. In Korea, technology was transferred from China during the Three Kingdoms period, and many of the statues were used for plating. Ancient plating was limited to gold plating by painting amalgams, evaporating mercury, and fixing foils at high temperatures.

On the other hand, in general, plating is often referred to as electroplating. The purpose of such electroplating is sometimes combined with industrial applications such as decorative beautification, anticorrosion and abrasion resistance, improved contact resistance, carburizing and the like. Although there are some differences depending on the plating method and application, the general process of electroplating is the order of dehydration → polishing → degreasing → chemical dipping treatment → electroplating → post treatment → drying. When classified according to the purpose of improving the plating, it can be classified into a method, surface hardening, surface beautification, smoothing of the surface or improving the reflectance of light and the like. In order to compensate for the lack of corrosion resistance of raw materials, it is to apply metal that can endure in a certain environment, and surface hardening refers to attaching a thin layer of metal that is harder than the material to endure abrasion. In addition, the beautification of the surface is made by attaching a thin layer of precious metal or a beautiful metal alloy to the surface of the object to make it look beautiful. Smoothing the surface or improving the reflectance such as light has a high reflectivity or a very smooth and glossy metal. It means to put a thin layer. In such plating, electrochemical deposition refers to a method of producing a thin film by applying electrical energy to a precursor to cause chemical synthesis on the surface of a substrate.

Electrochemical vapor deposition is a method of preparing a precursor suitable for synthesis into a solution phase when synthesizing a thin film of a metal and a metal oxide, and then depositing on a substrate surface by applying electric energy from the outside.

Cobalt oxides include cobalt oxide (II), cobalt oxide (III), cobalt oxide (IV), and tricobalt tetraoxide, among which tricobalt tetraoxide is a black powder of the formula Co ₃ O ₄ , having a specific gravity of 6.073. When it heats more than 950 degreeC, it becomes cobalt oxide (II). It is produced by heating cobalt hydroxide in air. Oxides based on tricobalt tetraoxide and various cobalt oxides have excellent catalytic and electrochemical activity due to their excellent oxygen generation and reduction ability, and therefore, electrochemical devices such as electrolysis catalysts, fuel cells, and secondary cells. Is important. In particular, tricobalt tetraoxide (Co ₃ O ₄ ) of the medium pore structure has a high specific surface area due to the porosity, the performance improvement of the active area of the catalyst, the improvement of the diffusion rate of ions, high electrical storage capacity is reported.

In the prior art of the method for producing a cobalt oxide thin film using an electrochemical vapor deposition method, 0.1 to 0.5 mol of aqueous solution of CoSO ₄ is heated to a temperature of 70 ° C. or higher, and a small amount of potassium hydroxide is added to control the pH of the solution. a method of using an electrode system, and in the external flow a constant current and voltage electric depositing a cobalt oxide thin film on a platinum substrate surface is known [Journal of Materials Research , 1998 , 13, 837-839].

The tricobalt tetraoxide has recently attracted attention as a representative electrode material of the supercapacitor. Supercapacitors focus on enhancing the performance of capacitors, in particular the capacity of capacitors, and are intended to be used for battery purposes. Capacitors used in electronic circuits electrically function like storage batteries. The basic purpose is to `` gather power and release it as needed '', and it is one of the necessary parts to operate electronic circuits stably. Used for the purpose. It is usually installed inside a device, and is used for safety devices that temporarily supply power to a setting memory or operate at a power failure.

As for the electrode material of such a supercapacitor, to improve the performance in the cobalt oxide it has, is a nano-fabrication techniques meet the sasanhwasam cobalt having a mesopore structure was recently invention, the manufacturing method using the hydrothermal method in [Journal of The Electrochemical society , 2005, 152, A871-A875], prepared by mixing 0.1 mole of sodium hydroxide and 30% hydrogen peroxide solution in 0.2 mole CoSO ₄ solution by adjusting pH and heating at 70 ° C. After filtering the precipitate is washed with ethanol and distilled water, it is a method of producing a tripobalt tetraoxide powder having a mesoporous structure synthesized by heat treatment at 160 to 350 ℃.

However, the method of manufacturing cobalt oxide having a mesoporous structure through the hydrothermal method requires a further process of depositing the prepared powder on a current collector such as conductive graphite again to be used as an electrode of a capacitor. Degradation of the material due to deposition occurs. In addition, the pores of the tricobalt tetraoxide particles are not evenly developed as a whole has the disadvantage of having an irregular mesoporous structure.

In addition, the Republic of Korea Patent No. 10-0346925-0000 has prepared a cobalt oxide based on the sol-gel method (cobalt oxide for supercapacitors having a large specific surface area and low internal resistance significantly improved performance and lifespan) A method for producing an electrode is disclosed.

The above patent has the advantage of obtaining cobalt oxide powder even with a simple manufacturing method, but an additional step of depositing the obtained cobalt oxide powder on a desired substrate is required, and because precipitation of cobalt oxide particles is obtained, There is a disadvantage that it is difficult to obtain cobalt oxide particles having pores smaller than nanometers.

Therefore, the present inventors use the advantages of the conventional electrodeposition method, and can be used as an electrode at the same time as the synthesis, so that no further process is required and the surfactant is formed by forming micelles on the surface of the substrate instead of the bulk micelles. To minimize the use, evenly distributed throughout the particles produced to find a method for producing a tricobalt tetraoxide thin film having a regular mesoporous structure, and completed the present invention.

An object of the present invention is to provide a method for producing a tricobalt tetraoxide thin film having an intermediate pore structure.

Another object of the present invention to provide a tricobalt tetraoxide thin film having an intermediate pore structure.

In order to achieve the above object, the present invention provides a method for producing a tri-cobalt tetraoxide thin film having a mesoporous structure and a tri-cobalt tetraoxide thin film manufactured using the same.

The tricobalt tetraoxide thin film according to the present invention does not need to perform an additional deposition process that is essentially required in the conventional manufacturing method, thereby simplifying the processing process and reducing costs. In addition, even a small amount of the structural culture material can be produced in the triad cobalt tetraoxide with a uniform mesoporous structure, this can increase the specific surface area compared to the conventional tripobalt tetraoxide without porosity, thereby significantly improving the performance of the catalyst, It can be usefully used for electrode materials of lithium secondary batteries and supercapacitors.

The present invention comprises the steps of dissolving cobalt sulfate (CoSO ₄ ) powder in distilled water, and then adding and mixing the cetyltrimethylammonium bromide (hereinafter referred to as "CTAB") powder to prepare an electrolyte solution (step 1);

Preparing a tricobalt tetraoxide thin film having an intermediate pore structure by immersing the substrate in the electrolyte solution prepared in step 1 and depositing the same by electrochemical method (step 2); And

It provides a method for producing a tricobalt tetraoxide thin film having an intermediate pore structure comprising the step (step 3) of removing the CTAB from the thin film prepared in step 2 using a washing solution.

Hereinafter, the present invention will be described in more detail step by step.

Step 1 according to the present invention is a step of preparing an electrolyte solution by dissolving cobalt sulfate (CoSO ₄ ) powder in distilled water, and then adding and mixing the CTAB powder.

The cobalt sulfate may be used in a concentration of 0.01 to 2 M. At this time, when the addition amount of the cobalt sulfate powder is less than 0.01 M tricobalt tetraoxide thin film is difficult to synthesize during the electrochemical deposition, while when the addition amount of the cobalt sulfate powder exceeds 2 M, the synthesis rate of the thin film is no longer increased compared to the addition amount. Do not.

On the other hand, the CTAB is a kind of surfactant, by interacting with cobalt sulfate to form a micelle on the surface of the substrate during the electrodeposition of the structure to form a tripobal tetraoxide of the mesoporous structure in which the pores are evenly developed as a whole Used as a substance.

CTAB in step 1 may be added 1 to 10% by weight. In this case, when the amount of CTAB to be used is less than 1% by weight, micelles are difficult to form. On the other hand, when the amount of CTAB to be added is more than 10% by weight, the formation of micelles is no longer increased compared to the amount of addition. There is a problem that it is difficult to manufacture tricobalt tetraoxide in a regular mesoporous structure.

Step 2 according to the present invention is a step of preparing a tricobalt tetraoxide thin film having an intermediate pore structure by immersing the substrate in the electrolyte solution prepared in step 1, and deposited by an electrochemical method.

In order to deposit tricobalt tetraoxide having a mesoporous structure from the electrolyte of step 2, thermal energy is required together with electrical energy. The electrolyte solution can be used while maintaining a constant temperature of 10 to 90 ℃ during deposition. In this case, when the temperature of the electrolyte solution is less than 10 ℃, it is difficult to expect sufficient deposition of cobalt oxide, as well as difficult to dissolve CTAB, which serves as a structural culture material. On the other hand, when the temperature of the electrolyte solution exceeds 90 ℃ it is difficult to form a uniform mesoporous structure due to the rapid evaporation rate of distilled water.

In addition, the voltage during the electrochemical deposition of step 2 may be added in the range 0.1 to 5V. In this case, when the voltage is less than 0.1 V, it is difficult to expect the deposition of a sufficient mesoporous structure, and when the voltage exceeds 5 V, no increase in the amount of deposition more than the applied voltage occurs.

Furthermore, the deposition time during electrochemical deposition can be selected in the range of 1 second to 60 minutes to adjust the thickness of the synthetic thin film. In this case, when the deposition time is less than 1 second, the particles do not grow sufficiently and are difficult to visually identify. When the deposition time exceeds 60 minutes, the thickness of the thin film is greatly increased so that the substrate adhesion of the thin film does not overcome gravity. There is a problem falling.

Meanwhile, the electrochemical deposition may use a three-way electrode system. In this case, the reference electrode may be an Ag / AgCl electrode or an SCE electrode, the counter electrode may be a platinum electrode, and the working electrode may be a substrate to be deposited.

The substrate of step 2 is not particularly limited, but preferably ITO glass, stainless steel, graphite, platinum plate, or the like may be used, and the method may further include washing to use the substrate to be deposited. As a solution used for washing, a mixed solution of C ₁ to C ₄ alcohol and acetone may be used. Preferably, a solution in which isopropanol and acetone is mixed in a 1: 1 ratio may be used.

Step 3 according to the present invention is a step of removing CTAB using a washing solution from the thin film prepared in step 2.

When the cobalt oxide particles are deposited on the substrate surface, there are a firing method and an extraction method for removing the structural culture material deposited on the substrate. In general, both methods are used, and in the method for producing a tricobalt tetraoxide thin film having an intermediate pore structure by the electrochemical vapor deposition according to the present invention, there is no particular limitation on the method of removing the structural culture material. However, in the case of the calcination method, particles are agglomerated with each other due to thermal energy, and there is a risk of breaking the synthesized mesoporous structure. Therefore, the extraction method is preferably used in the present invention.

The CTAB is a structural culture material for constructing micelles for forming the mesoporous structure, and may be removed from the thin film by the washing solution of step 3.

As the washing solution, distilled water, C ₁ to C ₃ alcohol, a mixed solution thereof, and the like may be used. Preferably, a mixed solution of distilled water and C ₁ to C ₃ alcohol may be used, and more preferably distilled water and ethanol. 1: 1 mixed solution can be used.

After dipping the thin film prepared in Step 2 in the washing solution, fixing the thin film prepared, the CTAB may be removed by stirring the solution for 1 hour.

In addition, the substrate washed by the mixed solution may further comprise the step of drying. The drying method is not particularly limited but is preferably dried in an air atmosphere at room temperature for 24 hours.

In another aspect, the present invention provides a tri-cobalt tetraoxide thin film having a mesoporous structure prepared by the manufacturing method.

The tricobalt tetraoxide thin film of the mesoporous structure manufactured by the method may have a pore size of 1 to 5 nm and a particle thickness of 1 to 5 nm. The mesoporous structure having a uniform pore size and particle thickness increases the specific surface area of the thin film to be deposited, and at the same time, the performance of the thin film can be improved by improving the diffusion rate of ions due to the development of uniform pores.

Hereinafter, the present invention will be described in more detail with reference to Examples and drawings. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

< Example  1> of mesoporous structure Samcobalt tetraoxide  Manufacture of thin film

Step 1: CoSO ₄ Powder and CTAB  Preparation of Electrolyte Solution Using Powder

An electrolyte solution was prepared as follows for the synthesis of the tricobalt tetraoxide thin film of the mesoporous structure of the present invention.

2.83 g of cobalt sulfate (CoSO ₄ ) powder was quantitatively placed in a 50 ml beaker, distilled water was filled to 50 ml of total solution, and stirred for 5 minutes to completely dissolve the solute. 0.5 g of CTAB was quantified into the prepared solution, reacted for about 5 minutes to completely dissolve, and a small amount of sulfuric acid (H ₂ SO ₄ ) was added thereto to titrate to pH 2.

Step 2: Through Electrochemical Deposition Samcobalt tetraoxide  Manufacture of thin film

To heat the solution prepared in step 1, the beaker containing the solution of step 1 was immersed in a container containing silicone oil, and heated by adjusting the temperature of the solution to be kept at 70 ° C. using a heater. . At this time, the top of the beaker was sealed using a silicone lid to minimize evaporation of distilled water.

In order to remove impurities of the ITO glass used as the substrate, the ITO glass was immersed in a washing solution (isopropanol: acetone = 1: 1 mixed solution) and washed with an ultrasonic cleaner for 20 minutes. The washed ITO glass was rinsed in distilled water and dried using an air gun. In order to electro-deposit the ITO glass, a three-electrode system was prepared using an Ag / AgCl electrode, a counter electrode of platinum, and a working electrode of the washed ITO glass.

Each electrode was placed in a reactor in the electrolyte solution at 70 ° C. prepared in Step 1, and a voltage difference of 1.5 V was applied to the reactor for 10 minutes based on the reference electrode to prepare tricobalt tetraoxide thin film on an ITO glass plate.

Step 3: through solution washing CTAB Extraction and drying

The ITO glass substrate on which tricobalt tetraoxide prepared in step 2 was deposited was immersed in a washing solution (distilled water: ethanol = 1: 1 mixed solution), and stirred for 1 hour to wash the thin film. The washed tricobalt tetraoxide thin film was dried in an air atmosphere at room temperature for 24 hours.

< Comparative example  1> without mesoporous structure Samcobalt tetraoxide  Manufacture of thin film

A tricobalt tetraoxide thin film was prepared in the same manner as in Example 1, except that CTAB was added in Step 1 of Example 1.

< Comparative example  2> As structure culture material SDS ( sodium dodecyl sulfate Of mesoporous structure using Samcobalt tetraoxide  Manufacture of thin film

In step 1 of Example 1, instead of CTAB, which is a cationic surfactant, as the structure culture material, a tricobalt tetraoxide thin film having an intermediate pore structure was prepared in the same manner as in Example 1 above.

< Experimental Example  1> Samcobalt tetraoxide  Electron Microscope Observation

In order to observe the microporous structure and the particle shape of the surface of the tri-cobalt tetraoxide thin film prepared in Example 1 was observed through a transmission electron microscope and a scanning electron microscope.

In order to observe the microporous structure and the particle shape of the surface of the tri-cobalt tetraoxide thin film prepared by Example 1 and Comparative Example 1 and observed the tri-cobalt tetraoxide thin film prepared by transmission electron microscope and scanning electron microscope, this is shown in Figs . 2 is shown.

Referring to FIG. 1 , in the transmission electron micrograph (Philps, CM200) of the tricobalt tetraoxide thin film manufactured by Example 1, the contrast between the particles (dark region) and the pores (bright region) appears to appear. It was found that a porous particle structure having a uniform mesoporous structure was formed.

In addition, referring to Figure 2 , (a) is a scanning electron micrograph of the tri-cobalt tetraoxide thin film prepared by Comparative Example 1 shows the surface particle shape (leaf shape) of the general tri-cobalt tetraoxide synthesized by the electrochemical vapor deposition method, Scanning electron micrograph (b) of the tricobalt tetraoxide thin film prepared in Example 1 shows the surface particle shape (sphere shape) modified by the influence of the added CTAB (Hitach, S-4200).

< Experimental Example  2> X-ray Diffraction analysis

In order to analyze the microporous structure characteristics of the tricobalt tetraoxide thin film prepared in Example 1, the tricobalt tetraoxide thin film was used in an incineration region (2θ = 1 to 10 ^o) using an incineration X-ray diffractometer (Rigaku, Mini flex). analysis and the results are shown in Fig.

Referring to FIG. 3 , an incidence X-ray diffraction data having a 2θ value of 1.40 represents an array pattern of particles and pores in a nano-area, and measures an entire thin film sample, and thus, an entire microstructure of the intermediate pore structure is synthesized therefrom. It can be seen that the uniform production. In addition, X-ray diffraction analysis before and after washing the synthesized thin film using the cleaning solution, it can be seen that the tripobal tetraoxide thin film synthesized in the present invention has a very stable microporous structure.

On the contrary, referring to FIG. 4 , the tri-cobalt tetraoxide thin film of the mesoporous structure synthesized using SDS as a structural culture material was greatly degraded in structural stability, and it was observed that the mesoporous structure formed during the washing process collapsed.

< Experimental Example  3> Samcobalt tetraoxide  Analysis of Components of Thin Films

In order to determine the components of the tricobalt tetraoxide thin film prepared in Example 1, the following experiment was conducted.

In order to determine the constituents of the tricobalt tetraoxide thin film prepared in Example 1, the photoelectron spectrometer (X-ray photoelectron spectroscopy, SPECS, EA200) was analyzed. The results are shown in Fig.

Referring to FIG. 5 , the peak position of the binding energy of the thin film of Example 1 according to the present invention indicates Co 2 p 1/2 (795.5) and Co 2 p 3/2 (780.6) from the left, so that the chemical bonding state of the thin film is tricobalt tetraoxide. It can be seen that. This is consistent with the results of photoelectron spectroscopy analysis of tricobalt tetraoxide in the literature [ J. Phys . Chem . B , 2006, 110, 6871-6880.].

< Experimental Example  4> Cyclic voltammetry  Electrochemical behavior through

In order to compare and analyze the performance of the tricobalt tetraoxide thin film prepared in Example 1 as an electrode catalyst, the tri-cobalt tetraoxide thin film and the non-porous tricobalt tetraoxide thin film of the non-porous structure prepared by Comparative Examples 1 and 2 and Using the tri-cobalt tetraoxide thin film of the mesoporous structure prepared in Example 1 was carried out the following experiment.

In order to determine the electrochemical characteristics of the tricobalt tetraoxide thin films prepared by Examples 1, Comparative Example 1 and Comparative Example 2 using a potentstate (Potentiostat, Princeton Applied Research, VSP) circulating voltage in 1 mol of NaOH electrolyte Analyzes were made by amphoteric analysis. The results are shown in Fig.

Referring to FIG. 6 , the thin film of Example 1 of the present invention exhibits a very high current density per unit area when compared to Comparative Examples 1 and 2, and thus, when used as an electrode material of an electrochemical device such as a supercapacitor, It was found that it has higher electric storage capacity and faster charge / discharge rate compared to the pore structure of tricobalt tetraoxide. In addition, in the case of Comparative Example 2 using SDS as a structural culture material, although the synthesized mesoporous structure was not stable and collapsed, due to the partially present pores, the current density was higher than that of the non-porous tricobalt tetraoxide of Comparative Example 1. Sloth. Therefore, it was found that tricobalt tetraoxide of the mesoporous structure manufactured in the present invention has superior performance as the electrode material of the electrochemical device.

< Experimental Example  5> discharge curve ( Discharge curve ) Capacitance evaluation through analysis

In order to evaluate the capacitance of the tri-cobalt tetraoxide thin film prepared in Example 1 as a supercapacitor, the tri-cobalt tetraoxide thin film and non-porous tricobalt tetraoxide thin film prepared in Comparative Example 1 and Comparative Example 2 and Using the tri-cobalt tetraoxide thin film of the mesoporous structure prepared in Example 1 was carried out the following experiment.

In order to evaluate the capacitance of the tricobalt tetraoxide thin films prepared in Example 1, Comparative Example 1 and Comparative Example 2, the discharge characteristics were analyzed in a 1 mole NaOH electrolyte solution using a potentiometer. Discharge capacity was measured by applying a constant current of 1 A / g, and the results are shown in FIG. 7 .

Referring to FIG. 7 , it was confirmed that the tricobalt tetraoxide thin film having an intermediate pore structure of Example 1 had an electric capacity of about 488 F / g and about twice higher than that of 255 F / g of Comparative Example 1. The capacitance was calculated using the formula C = (I · Δt) / (m · ΔV), where I is the discharge current, Δt is the discharge time, m is the weight of the material, and ΔV is the potential difference. it means.

1 is a transmission electron micrograph showing the tricobalt tetraoxide of the mesoporous structure deposited on ITO glass prepared according to an embodiment of the present invention (magnification of (a): 41000X, (b): 30000X),

FIG. 2 is a scanning electron micrograph of a thin film deposited on ITO glass to compare a tri-cobalt tetraoxide thin film (a) having no pore structure and a tri-cobalt tetraoxide thin film (b) having an intermediate pore structure prepared according to an embodiment of the present invention. ego,

3 is a graph showing the results of incineration X-ray diffraction analysis of the tricobalt tetraoxide thin film having an intermediate pore structure prepared according to an embodiment of the present invention,

4 is a graph showing the results of incineration X-ray diffraction analysis of the tricobalt tetraoxide thin film prepared using SDS according to Comparative Example 2 of the present invention,

Figure 5 is a graph showing the results of the optoelectronic analyzer of the tri-cobalt tetraoxide thin film of the mesoporous structure prepared according to an embodiment of the present invention,

6 is a circulating voltage of tri-cobalt tetraoxide thin film of the mesoporous structure prepared by using CTAB and the collapsed pore structure and non-porous structure of the thin porous film synthesized by Comparative Example 1 and Comparative Example 2 according to an embodiment of the present invention This graph shows the current analysis results.

Figure 7 is a graph showing the analysis results of the capacitance of the tri-cobalt tetraoxide thin film of the intermediate pore structure prepared by using the CTAB according to an embodiment of the present invention and the tricobalt tetraoxide thin film synthesized by Comparative Examples 1 and 2.

Claims (11)

Dissolving cobalt sulfate (CoSO ₄ ) powder in distilled water, and then adding and mixing cetyltrimethylammonium bromide (CTAB) powder to prepare an electrolyte solution (step 1); Preparing a tricobalt tetraoxide thin film having an intermediate pore structure by immersing the substrate in the electrolyte solution prepared in step 1 and depositing the same by electrochemical method (step 2); And Method for producing a tricobalt tetraoxide thin film having an intermediate pore structure comprising the step (step 3) of removing the CTAB from the thin film prepared in step 2 using a washing solution. The method of claim 1, wherein the cobalt sulfate powder of Step 1 is dissolved in an electrolyte solution so as to have a concentration of 0.01 to 2 M. The method according to claim 1, wherein the CTAB of step 1 is a method for producing a tricobalt tetraoxide thin film having an intermediate pore structure, characterized in that added in the range of 1 to 10% by weight. The method of claim 1, wherein the electrolyte solution of Step 2 is maintained in a temperature range of 10 to 90 ℃ constant method for producing a tricobalt tetraoxide thin film having an intermediate pore structure. The method of claim 1, wherein the electrochemical deposition of step 2 is performed by applying a voltage in the range of 0.1 to 5 V. The method of claim 1, wherein the electrochemical deposition of Step 2 is performed for 1 second to 60 minutes. The method of claim 1, wherein the electrochemical deposition of step 2 is performed using a three-way electrode system. The tricobalt tetraoxide having an intermediate pore structure according to claim 7, wherein the ternary electrode system comprises a reference electrode as an Ag / AgCl electrode or an SCE electrode, a counter electrode as a platinum electrode, and a working electrode as a substrate. Method for producing a thin film. The method of claim 1, wherein the substrate of step 2 is selected from the group consisting of ITO glass, stainless steel, graphite, and platinum plates. A tricobalt tetraoxide thin film having a mesoporous structure manufactured by the method according to any one of claims 1 to 9. The tricobalt tetraoxide thin film according to claim 10, wherein the tricobalt tetraoxide thin film having a mesoporous structure has pores of 1 to 5 nm and particle thickness of 1 to 5 nm.

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