KR20180061984A - Manufacturing method of anatase multi-channel porous structure - Google Patents

Abstract

The purpose of the present invention is to provide a method for producing an anatase multi-channel porous structure, which has a simple forming process, wherein the structure is porous while maximizing a contact area of an anatase per unit volume through a three-dimensional multi-channel, and can have high current density when used as an electrode of a dye-sensitized solar cell. The present invention can easily form a first porous body by using polystyrene granules, can easily form a multi-channel by forming a second porous body in a first pore part of the first porous body, and can have high current density when used as an electrode of a dye-sensitized solar cell by increasing an electrolyte contactable area of an anatase per unit volume compared to the related art. Thus, it is possible to improve energy efficiency of a dye-sensitized solar cell.

Description

TECHNICAL FIELD [0001] The present invention relates to an anatase multi-channel porous structure,

More particularly, the present invention relates to a method for manufacturing an anatase multi-channel porous structure, and more particularly, to a method for manufacturing an anatase multi-channel porous structure by mixing granules containing polystyrene monosphere with a slurry containing anatase powder and then firing to remove polystyrene to form a first porous article To a method for manufacturing an anatase multi-channel porous structure in which a second porous body is formed in pores in a first porous body.

Dye-sensitized solar cell is composed of redox electrolyte, and the dye molecules chemically adsorbed on the surface absorb the sunlight to generate electrons and generate electricity. In a dye-sensitized solar cell, when nanoparticle semiconductor oxide electrodes chemically adsorbed dye molecules on the surface are absorbed by the sunlight, the dye molecules emit electrons, which are transferred to the transparent conductive substrate through various paths, . Dye-sensitized solar cells use nano-sized dye molecules and generally use titanium dioxide (TiO ₂ ).

In order to increase the energy efficiency of the dye-sensitized solar cell, the electrode must be formed in a structure capable of increasing the current density. In general, the electrode is formed into a porous structure. Conventionally, a powdered nanoporous titanium dioxide was formed by using a sol-gel method to form an electrode as a porous structure, and the electrode material was made into a paste state. For example, Korean Patent Laid-Open Publication No. 2011-0093153 discloses a method comprising the steps of dissolving titanium isopropoxide in 2-propanol and adding carbon black, and adding ammonium hydroxide (NH 3) ₄ OH) aqueous solution is added and stirred to form a sol state, followed by drying to form a gel state; a step of forming a powdered nanoporous TiO ₂ powder after sintering in a sintering furnace; There is disclosed a method of manufacturing a nanoporous titanium dioxide electrode material through a step of producing nanoporous TiO ₂ powder as an electrode material in a paste state.

However, in the case of the nanoporous titanium dioxide electrode material manufactured by this method, the manufacturing process is complicated, and the structure of the formed pores is not constant, so that the current density of the electrode is not high. When the current density of the electrode is low, the energy efficiency of the dye-sensitized solar cell is lowered.

Korean Registered Patent No. 1634620 (registered on June 23, 2016) Korean Registered Patent No. 1663593 (registered on Feb. 20, 2014)

An object of the present invention is to provide a dye-sensitized solar cell which has a simple structure and is structured to maximize an accessible area of anatase per unit volume through a three-dimensional multi-channel structure, And a method for manufacturing an anatase multi-channel porous structure.

In order to accomplish the above object, the present invention provides a method for producing a polystyrene granule, which comprises mixing polystyrene monosphere with a binder to form a polystyrene paste, passing the long polystyrene paste through a tubular body to form polystyrene granules, Anatase mixture to form a first porous body formed by removing the polystyrene granules by first heating the polystyrene-anatase mixture to form a first porous body; And an anatase dispersed material is added to the first stage of the anatase dispersion, and the second porous material having the anatase dispersed material is heated to form a second porous material.

The size of the polystyrene monosphere may range from 300 to 500 nm in average diameter.

The step of forming the polystyrene granules may be performed such that the average size of the polystyrene granules is 0.1 to 100 탆.

The step of forming the polystyrene granules may be performed such that the average size of the polystyrene granules is 0.1 to 10 탆.

The step of forming the polystyrene granules may be performed such that the average size of the polystyrene granules is 10 to 100 탆.

The step of passing the elongated tubular body to form polystyrene granules may be performed using an injection needle.

The average size of the anatase particles contained in the polystyrene-anatase mixture may include monodisperse particles of 4 to 10 nm.

The form of the anatase dispersion may be at least one selected from among slurry, sol, and gel.

The polystyrene-anatase particles in the step of forming the anatase mixture is then by the titanium tetrachloride (TiCl ₄₎ in a liquid phase reaction with water generates a TiOCl ₂ aqueous solution, to the TiOCl ₂ aqueous solution ion-exchange membrane as the boundary of water and The anatase titanium dioxide nanopowder produced in the aqueous solution of TiOCl ₂ may be used.

The present invention can easily form the first porous body by using polystyrene granules. By forming the second porous body in the pores of the first porous body, it is possible to easily form multi-channels, The contact area of the anatase becomes large, so that it can have a high current density when used as an electrode of a dye-sensitized solar cell, thereby enhancing the energy efficiency of the dye-sensitized solar cell.

1 is a conceptual view illustrating a method of manufacturing an anatase multi-channel porous structure according to an embodiment of the present invention.
FIG. 2 is a conceptual view of a hydrolysis apparatus according to an embodiment of the present invention. FIG.
3 is a view conceptually showing an ion exchange apparatus according to an embodiment of the present invention.
4 is a view conceptually showing a granule manufacturing apparatus according to an embodiment of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are included to provide a further understanding of the technical concept of the present invention, are incorporated in and constitute a part of the specification, and are not intended to limit the scope of the present invention. For the same reason, some of the components in the drawings are exaggerated, omitted, or schematically illustrated.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a conceptual view illustrating a method for manufacturing an anatase multi-channel porous structure.

As shown in FIG. 1A, a polystyrene granule 102 is first formed to form an anatase multi-channel porous structure 1000 according to an embodiment of the present invention. The polystyrene granules 102 are granules comprised of polystyrene mono-spheres 101 particles.

The mean size of the polystyrene monosphere 101 particles was about 300 to 500 nm in particle diameter. The average size of the polystyrene single spheres 101 is determined in consideration of a range in which the granule size in the subsequent process can be easily controlled and the pore size of the first porous body formed later. The polystyrene monosphere 101 and the binder are mixed to form a polystyrene paste.

4 is a view conceptually showing a polystyrene granule manufacturing apparatus 4000 according to an embodiment of the present invention. The apparatus for manufacturing polystyrene granules 4000 includes a long elongated body 4100. The polystyrene paste 103 produced in the above process is pressurized by using the pressing portion 4200 included in the polystyrene granule manufacturing apparatus 4000 and is passed through the long body 4100 to be discharged intermittently, ≪ / RTI > The shape of the pressing portion 4200 and the pressing method are not particularly limited, and any method can be used as long as the granules can be easily formed. In the present invention, granules were formed using a syringe and a needle. The size of the granules may vary depending on the diameter of the elongated tube 4100, and the interval between discharges during intermittent discharging is also a factor determining the size of the granules. The discharged granular polystyrene paste is dried to form the polystyrene granules 102. The average size of polystyrene granules can be varied to suit applications ranging from 0.1 to several hundred microns. In the case of a thin film-like porous body, the electrode is suitably in the range of 0.1 to 10 mu m. In the case of the photocatalyst for hydrogen production, the structure is larger than the thin film, and preferably 10 to 100 mu m in the manufacturing process. When the polystyrene granules were formed using a long elongated tubular body, it was difficult to form an average size smaller than 0.1 탆. When the average size of the granules was larger than several hundred 탆, the primary pores of the first porous body were too large, It is difficult to expect the function of one channel.

As shown in FIG. 1 (b), the polystyrene granules 102 and the anatase slurry 210 are mixed to form a polystyrene-anatase mixture. The method of mixing the polystyrene granules 102 and the anatase slurry 210 to form the polystyrene-anatase mixture is not particularly limited. However, in order to easily form multi-channels, the container 300 is filled with the polystyrene granules 102 It is preferable to inject the postanatase slurry 210 to form a uniform first pore 221 in the first porous article 220 in a subsequent step. Here, the uniformity means that the variation of the volume of the pores per unit volume is not large, which is not mathematically equivalent. The polystyrene granules 102 and the anatase slurry 210 are mixed to form a polystyrene-anatase mixture, followed by drying. As the moisture contained in the anatase slurry 210 is evaporated through drying, the anatase particles are positioned in a weakly bonded state between the particles in the space between the polystyrene granules 102.

After the drying step, the primary heating step is performed as shown in Fig. 1 (c). In the present invention, the primary heating is carried out at a temperature of 600 to 700 ° C. The primary purpose of the primary heating is to dissolve the polystyrene granules 102 at a high temperature to form the first apertures 221 and the other purpose is to maintain the first apertures 221 in a stable state, The first porous body 220 is formed.

FIG. 1 (d) shows the step of injecting the anatase dispersion 310 into the first porous body 220 including the first base 221. The anatase dispersion may be an anatase slurry used in the step of forming the polystyrene-anatase mixture, and an anatase sol and an anatase gel may be used. The anatase sol may be added to the first stage of the first stage 221 to form the second porous article 320 having an anatase in the first stage 221 of the first porous article, It is most preferable to consider it from the aspect. The interatomic bond strength of the anatase dispersion 310 is increased through the secondary heating step after the anatase dispersing body 310 is introduced into the first stage of the first stage 221 and the second porous body 310 320 are formed. The secondary heating temperature is possible if the temperature range is such that the required structural strength can be obtained for the application to be subsequently applied. In the present invention, the secondary heating was performed in the range of 400 to 650 ° C. If the second heating temperature is lower than 400 ° C, the inter-particle bonding of the second porous body 320 is weakened and the bonding with the first porous body is not properly performed. On the other hand, when the second heating temperature is 650 ° C or higher, Phase mixture is increased to cause deterioration of optical characteristics, and there is a problem that the inter-particle sintering proceeds and the channel in the porous body is rapidly reduced.

FIG. 1 (e) shows an anatase multi-channel porous structure 1000 formed through the above-described manufacturing steps. The second porous body 320 is formed within the first porous body 220 of the anatase first porous body 220. At least a part of the first porous body adjacent to the first porous body 220 is spatially connected to form a first channel And the second porous body 320 in the first porous body is loosely coupled between the anatase particles in the second porous body and includes the second channel. Due to such a structure, the specific surface area of the first porous body 220 and the specific surface area of the second porous body are combined, so that the porous structure 1000 of the present invention includes multi-channels, and the specific surface area of the anatase is increased .

The anatase particles contained in the anatase slurry in the present invention were in the form of monodisperse particles having an average size of 4 to 10 nm. The smaller the size of the particles, the larger the specific surface area of the particles, which facilitates the coagulation between the particles. Thus, it is difficult to obtain nano-sized anatase monodisperse particles. In the present invention, monodisperse particles having a nano size range are easily manufactured using an electrolytic process using an ion exchange membrane.

In order to prepare the anatase titanium nano powder according to the embodiment of the present invention, TiOCl ₂ aqueous solution is first produced by reacting titanium tetrachloride (TiCl ₄ ) in liquid state with water. In this case, if the reaction occurs quickly, the hydrolysis process will generate heat and explosion may occur. To prevent this explosive reaction, a hydrolysis apparatus 2000 as shown in Fig. 2 may be used.

The hydrolysis apparatus 2000 may include a first container 2100 containing liquid titanium tetrachloride (TiCl ₄ ) and a second container 2200 containing water. The first container 2100 and the second container 2200 are sealed and filled with nitrogen (N ₂ ) in a gaseous state. The sealed state in the present invention means that the remaining portion except for each pipe for supplying and discharging connected to each container is not easily exchanged with the outside air in the container so that the gas atmosphere contained in the container can be maintained constantly . When nitrogen is charged doemeuro result can prevent the water and titanium tetrachloride (TiCl ₄₎ in the air, the reaction in the first vessel 2100, the titanium tetrachloride (TiCl ₄₎ and water reaction in the second vessel 2200 So that the reaction can be performed stably. A first supply pipe 2110 is installed in the first container 2100 and a second supply pipe 2210 is installed in the second container 2200 in order to inject nitrogen gas therein.

The first container 2100 and the second container 2200 are connected to each other through the first pipe 2300. One end of the first pipe 2300 is located close to the inner bottom surface of the first container 2100 and the other end is located inside the second container 2200. Titanium tetrachloride (TiCl ₄ ) contained in the first vessel is supplied to the second vessel 2200 through the connection pipe 2300.

A stirrer 2220 may be installed inside the second container 2200 and a cooling unit 2230 may be provided outside the second container 2200. The stirrer 2220 and the cooling unit 2230 reduce the heat generated during the hydrolysis process to prevent excessive explosive reaction. The cooling portion 2230 may be filled with ice.

Nitrogen gas is injected into the first container 2100 in order to react the water with titanium tetrachloride (TiCl ₄ ) in liquid state using the hydrolysis apparatus 2000 according to the present embodiment to produce a TiOCl ₂ aqueous solution. When nitrogen gas is injected, titanium tetrachloride (TiCl ₄ ) in a liquid state contained in the first container 2100 is moved to the second container 2200 through the connection pipe 2300 by the pressure. Accordingly, the rate at which titanium tetrachloride (TiCl ₄ ) moves to the second vessel 2200 can be controlled by controlling the injection rate of the nitrogen gas. In this case, when titanium tetrachloride (TiCl ₄ ) moves to the second container 2200 at a high speed, an exothermic reaction occurs rapidly in the second container 2200 and there is a risk of explosion. Therefore, nitrogen gas is slowly injected into the second container 2200 It is preferable that the reaction occurs slowly.

When a TiOCl ₂ aqueous solution is formed, the resulting TiOCl ₂ aqueous solution is placed in one region bounded by the ion exchange membrane and water is placed in the opposite region of the ion exchange membrane. Thereafter it was added the aqueous solution of TiOCl ₂ and the current in the water to produce the anatase titanium dioxide nano-powder in the aqueous solution of TiOCl _2. In this case, the ion exchange apparatus 3000 as shown in FIG. 3 may be used.

The ion exchange apparatus 3000 is provided with an ion exchange membrane 3200 for supplying a current to a solution contained in a first reaction vessel 3100 and a first reaction vessel 3100 which are divided into a first region 3100a and a second region 3100b, And electrodes 3300a and 3300b for applying an electric field. A first region (3100a) of the storage container 3100 is put into the aqueous solution of TiOCl ₂ second area (3100b) is inserted into the water. In this embodiment, the ion exchange membrane (3200) is an anion exchange membrane, and it is possible to use an ion exchange membrane in which Cl ^- ions can pass and Ti ^{2 +} ions can not pass through.

Ti-Pt electrodes 3300a and 3300b may be used as an electrode for applying a current. That is, a negative (-) voltage is applied to the TiOCl ₂ aqueous solution of the first region 3100a using the Ti electrode 3300a and a positive (+) voltage is applied to the water of the second region 3100b using the Pt electrode 3300b. . When an electric current is applied, Cl ^- ions move from the TiOCl ₂ aqueous solution of the first region 3100a through the ion exchange membrane 3200 to the water in the second region 3100b. Therefore, the second water zone (3100b) is increasing more and the concentration of HCl, this is the anatase nano-powder of a white TiOCl ₂ in the aqueous solution of the first region (3100a) is generated.

In such a porous titanium dioxide structure, the size of the first perforations in the first porous body is uniform and the specific surface area is greatly increased by the second porous body in the first perforation. Therefore, when the porous structure manufactured by the method of manufacturing an anatase multi-channel porous structure is used as an electrode of a dye-sensitized solar cell, high current density can be obtained and energy efficiency of the dye-sensitized solar cell can be enhanced.

 While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes and modifications may be made without departing from the scope of the present invention. Accordingly, the true scope of protection of the present invention should be determined only by the appended claims.

Claims (9)

Mixing the polystyrene monosphere with a binder to form a polystyrene paste;
Passing the elongated tube through the tubular body using the polystyrene paste to form polystyrene granules;
Mixing the polystyrene granule with an anatase slurry containing anatase particles to form a polystyrene-anatase mixture;
Forming a first porous body including a first porous layer formed by removing polystyrene granules by first heating the polystyrene-anatase mixture;
Introducing an anatase dispersion into a first pore of the first porous body;
Forming a second porous body by second heating the first porous body into which the anatase dispersed body is charged; Lt; RTI ID = 0.0 > a < / RTI > multi-channel porous structure. The method of claim 1,
Wherein the size of the polystyrene mono-spheres ranges from 300 to 500 nm in average diameter. The method of claim 1,
Wherein the forming of the polystyrene granules is performed such that the average size of the polystyrene granules is 0.1 to 100 μm. 4. The method of claim 3,
Wherein the forming of the polystyrene granules is performed such that the average size of the polystyrene granules is 0.1 to 10 μm. 4. The method of claim 3,
Wherein the forming of the polystyrene granules is performed such that the average size of the polystyrene granules is 10 to 100 μm. 4. The method of claim 3,
Wherein the step of forming the polystyrene granules through the elongated tubular body is performed using an injection needle. The method of claim 1,
Wherein the anatase particles contained in the polystyrene-anatase mixture include monodisperse particles having an average size of 4 to 10 nm. The method of claim 1,
Wherein the shape of the anatase dispersion is at least one selected from the group consisting of slurry, sol, and gel. The method of claim 1,
The polystyrene-anatase particles in the step of forming the anatase mixture is then by the titanium tetrachloride (TiCl ₄₎ in a liquid phase reaction with water generates a TiOCl ₂ aqueous solution, to the TiOCl ₂ aqueous solution ion-exchange membrane as the boundary of water and And an anatase titanium dioxide nanopowder formed in the TiOCl ₂ aqueous solution is used by applying an electric current to the anatase titanium dioxide nanopowder.

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