KR20180061985A - Forming method of porous coating layer using anatase sol - Google Patents

Forming method of porous coating layer using anatase sol Download PDF

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KR20180061985A
KR20180061985A KR1020160161772A KR20160161772A KR20180061985A KR 20180061985 A KR20180061985 A KR 20180061985A KR 1020160161772 A KR1020160161772 A KR 1020160161772A KR 20160161772 A KR20160161772 A KR 20160161772A KR 20180061985 A KR20180061985 A KR 20180061985A
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South Korea
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coating layer
reactor
anatase sol
tiocl
porous coating
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KR1020160161772A
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Korean (ko)
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KR101883076B1 (en
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장명철
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군산대학교산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention relates to a method for forming a porous coating layer using anatase sol, and specifically, to a method for forming a porous coating layer using anatase sol generated by adding ammonia water into a TiOCl_2 aqueous solution by reacting titanium tetrachloride (TiCl_4) with water. The method for forming a porous coating layer using anatase sol of the present invention is able to form an anatase porous coating layer with a simple process by using anatase sol relatively in an easy way compared to a conventional art. An electrode of a dye-sensitized solar cell including the porous coating layer formed by the method has a high current density such that energy efficiency of the dye-sensitized solar cell can be improved.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for forming a porous coating layer using an anatase sol,

The present invention relates to a method for forming a porous coating layer using an anatase sol, and more particularly, to a method for forming a porous coating layer using an anatase sol produced by reacting titanium tetrachloride (TiCl 4 ) with water to produce a TiOCl 2 aqueous solution and then adding ammonia water .

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.

Thus, the conventional method for producing anatase sol has problems such as complicated processes and long time. Also, in the case of the nanoporous titanium dioxide electrode material manufactured by the conventional 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 sensitive solar cell is lowered.

Japanese Patent Laid-Open No. 2008-188583 (published on Aug. 21, 2008)

An object of the present invention is to provide an anatase porous coating layer of a porous structure which is simple and easy to form. Another object of the present invention is to provide a method for forming a porous coating layer using an anatase sol having a high current density when the porous coating layer is used as an electrode of a dye-sensitized solar cell.

In order to achieve the above object, the porous coating layer of the present invention is titanium tetrachloride (TiCl 4) for generating a TiOCl 2 aqueous solution is reacted with water, by reacting ammonia water with the TiOCl 2 aqueous solution of titanium hydroxide (Ti (OH) 2) Generating an anatase sol in the first mixed solution by placing the first mixed solution and the water in the first mixed solution through an ion exchange membrane and then applying an electric current to the first mixed solution; , And coating the anatase sol on a substrate. The present invention also provides a method for forming a porous coating layer using an anatase sol.

The step of reacting the titanium tetrachloride (TiCl 4 ) with water to produce a TiOCl 2 aqueous solution may be carried out in a nitrogen gas atmosphere.

In the step of generating an anatase sol in the first mixed solution, a Ti electrode may be used for the first mixed solution and a Pt electrode may be used for the water.

In the step of producing the TiOCl 2 aqueous solution, titanium tetrachloride (TiCl 4 ) is supplied from a first vessel, the aqueous solution of TiOCl 2 is produced in a first reactor, the first vessel and the first reactor are connected by piping The titanium tetrachloride (TiCl 4 ) may be pressurized by the nitrogen gas supplied to the first vessel and supplied to the first reactor.

In the step of producing the aqueous TiOCl 2 solution, at least a part of the first reactor may be cooled by contacting with a refrigerant containing ice.

In another aspect of the present invention, there is provided an electrode for a solar cell comprising a porous coating layer, wherein the porous coating layer is an electrode for a solar cell manufactured using an anatase sol prepared by the method for forming a porous coating layer using the anatase sol Can be achieved.

The method for forming a porous coating layer using the anatase sol of the present invention can easily form an anatase porous coating layer by a simple process using an anatase sol as compared with the prior art, and the electrode of the dye-sensitized solar cell including the porous coating layer formed by this method It is possible to have a high current density and to increase the energy efficiency of the dye-sensitized solar cell.

1 is a flowchart showing a method of forming a porous coating layer using an anatase sol according to an embodiment of the present invention.
2 is a view showing an apparatus for producing anatase sol 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.

FIG. 1 is a flowchart showing a method of forming a porous coating layer using an anatase sol according to an embodiment of the present invention, and FIG. 2 is a view showing an apparatus for producing an anatase sol according to an embodiment of the present invention.

As shown in FIG. 1, in order to prepare an anatase sol according to an embodiment of the present invention, TiOCl 2 aqueous solution is produced by reacting titanium tetrachloride (TiCl 4 ) in a liquid state with water (S 100). In this case, if the reaction occurs quickly, the hydrolysis process will generate heat and explosion may occur. To prevent such an explosive reaction, an anatase sol production apparatus as shown in Fig. 2 can be used.

The anatase sol manufacturing apparatus may include a first vessel 100 containing liquid titanium tetrachloride (TiCl 4 ) and a first reactor 200 for reacting with water. The first vessel 100 and the first reactor 200 are sealed and filled with nitrogen (N 2 ) in a gaseous state. When nitrogen is charged doemeuro result can prevent the water and titanium tetrachloride (TiCl 4) in the air react in the first container 100, the titanium tetrachloride (TiCl 4) and the water react in the first reactor (200) So that the reaction can be performed stably. A first supply pipe 410 is installed in the first vessel 100 and a third supply pipe 430 is installed in the first reactor 200 in order to inject nitrogen gas therein.

The first vessel 100 is connected to a first supply pipe 410 through which nitrogen gas flows and a first pipe 510 through which liquid titanium tetrachloride (TiCl 4 ) is transferred to the first reactor. The inside of the first supply pipe 410 and the first pipe 510 is also set to a nitrogen gas atmosphere. The first supply pipe 410 is installed such that one end of the first supply pipe 410 is located above the first container 100. The first supply pipe 410 may be provided with a valve therein for injecting nitrogen gas. The first pipe (510) is installed such that one end thereof is located at the lower part of the first container (100). One end of the first pipe 510 is in a titanium tetrachloride (TiCl 4 ) solution. The liquid titanium tetrachloride (TiCl 4 ) contained in the first vessel 100 moves through the first pipe 510 by flowing nitrogen gas through the first supply pipe 410.

The hydrolysis reaction of titanium tetrachloride (TiCl 4 ) with water generates a large amount of heat due to an exothermic reaction. Therefore, when titanium tetrachloride (TiCl 4 ) moves to the first reactor 200 at a high speed, an exothermic reaction occurs rapidly in the first reactor 200, and there is a risk of explosion. Accordingly, the injection rate of the nitrogen gas is controlled so as to slow the reaction in the first reactor 200. The rate of movement of titanium tetrachloride (TiCl 4 ) can be controlled by adjusting the rate of the nitrogen gas introduced into the first supply pipe 410. The rate can be controlled more slowly when the reaction heat is generated by observing the hydrolysis process of titanium tetrachloride (TiCl 4 ) with TiOCl 2 . And may include a first cooling unit 610 to prevent an explosive reaction from occurring in the first reactor 200. The first cooling unit 610 may have a concave shape to accommodate the first reactor 200 and may be formed of a metal such as copper having a high thermal conductivity. The first cooling portion 610 accommodates the refrigerant. The refrigerant transfers the reaction heat of the first reactor 200 to the first cooling unit 610 to lower the temperature of the first reactor 200, thereby stably causing the hydrolysis reaction of titanium tetrachloride (TiCl 4 ). The stirrer (not shown) and the first cooling unit 610 reduce the heat generated during the hydrolysis process to prevent an explosive reaction. The first cooling portion 610 may be filled with ice.

In order to produce a TiOCl 2 aqueous solution by reacting titanium tetrachloride (TiCl 4 ) in a liquid state with water using an anatase sol production apparatus according to this embodiment, nitrogen gas is injected into the first vessel 100. When nitrogen gas is injected, liquid titanium tetrachloride (TiCl 4 ) contained in the first vessel 100 is moved to the first reactor 200 through the first pipe 510 by the pressure. Accordingly, the rate at which the titanium tetrachloride (TiCl 4 ) moves to the first reactor 200 can be controlled by controlling the injection rate of the nitrogen gas. In this case, when titanium tetrachloride (TiCl 4 ) moves to the first reactor 200 at a high speed, an exothermic reaction occurs rapidly in the first reactor 200 and there is a risk of explosion. Therefore, nitrogen gas is slowly injected into the first reactor 200 It is preferable that the reaction occurs slowly.

When titanium tetrachloride (TiCl 4 ) flows into the first reactor (200), heat due to the reaction is cooled by the stirrer and the first cooling unit (610). Therefore, it is possible to prevent an explosive reaction from occurring. In another embodiment, water and ice may be mixed in the first reactor 200 to cool the reaction.

When a TiOCl 2 aqueous solution is produced by reacting titanium tetrachloride (TiCl 4 ) with water in the first reactor 200, ammonia water (NH 4 OH aqueous solution) is supplied to the first reactor 200 through the fourth supply tube 440. The resulting TiOCl 2 aqueous solution is combined with ammonia water (NH 4 OH aqueous solution) to produce titanium hydroxide (Ti (OH) 2 ) and ammonium chloride (NH 4 Cl) (S200). As the reaction proceeds, an aqueous solution containing TiOCl 2 , Ti (OH) 2 , ammonium chloride (NH 4 Cl) and hydrochloric acid (HCl) is mixed in the first reactor 200. In the present invention, A solution containing at least one of TiOCl 2 , titanium hydroxide (Ti (OH) 2 ), ammonium chloride (NH 4 Cl) and hydrochloric acid (HCl) produced through the reaction in the first reactor 200, 1 mixed solution.

The reaction solution in the first reactor 200 is transferred to the first region 310 of the second reactor 300 through the second pipe 520. The second pipe 520 is installed such that one end thereof is located above the first region 310 of the second reactor 300 and the other end thereof is located below the first reactor 200. One end of the second pipe 520 is in the first mixed solution. The first mixed solution contained in the first reactor 200 moves through the second pipe 520 by flowing nitrogen gas through the third supply pipe 430.

The second reactor 300 includes a first region 310, a second region 320 and an ion exchange membrane 350. The second region 310 includes a first region 310, 2 region section 320. In this case, Water is contained in the interior of the second reactor 300 before the start of the reaction. The first region 310 includes a Ti electrode 370. The second region 320 includes a Pt electrode 380. In the second reactor 300, a first mixed solution is included in the first region 310, and water is contained in the second region 320 with the ion exchange membrane 350 as a boundary. Thereafter, an anatase sol is generated in the first region 310 by applying an electric current to the first mixed solution and the water (S300).

When the first mixed solution is contained in the first region 310, an electric current is applied to perform ion exchange. A Ti electrode 370 is provided in the first region 310 and a Pt electrode 380 is provided in the second region 320 to apply a current. (-) voltage is applied to the reaction solution of the first region 310 using the Ti electrode 370 and a positive voltage is applied to the water of the second region 320 using the Pt electrode 380 I will do it.

The second region 320 of the second reactor 300 may include a fifth supply pipe 450 for supplying water and a first discharge pipe 530 for discharging an aqueous hydrochloric acid solution. When the reaction was started claim 2 Cl in the reactor 300, the ion exchange membrane first area 310 through 350 of the-ion will be taken to the second area 320, this second region 320, according (HCl) is generated and the concentration of hydrochloric acid is increased. As the concentration of hydrochloric acid increases, the movement of chlorine ions through the ion exchange membrane 350 is slowed down. Therefore, water is supplied through the fifth supply pipe 450 to dilute the hydrochloric acid concentration in the second region 320, When the aqueous solution is discharged through the first discharge pipe 530, the movement speed of the chlorine ions is maintained, thereby shortening the time for producing the anatase sol of the apparatus.

The first mixed solution in the first region 310 forms an anatase sol of white as ion exchange proceeds. The resulting anatase sol is coated on the substrate to form a coating layer (400). The anatase coating layer thus obtained maintains porosity even after complete drying and firing due to a loose binding structure in a sol state. Such a porous structure is very useful as an electrode of a dye-sensitized solar cell.

The anatase sol prepared by this method is formed by binding spherical particles having an average size of 10 nm or less and the porous structure has a uniform shape as compared with the porous article formed by the sol produced by the conventional production method, Type solar cell can have a high current density and can increase the energy efficiency of the dye-sensitized solar cell.

 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 (6)

Reacting titanium tetrachloride (TiCl 4 ) with water to produce a TiOCl 2 aqueous solution;
Reacting the TiOCl 2 aqueous solution with ammonia water to produce a first mixed solution containing titanium hydroxide (Ti (OH) 2 );
Placing an ion exchange membrane between the first mixed solution and the water, and applying an electric current to generate an anatase sol in the first mixed solution;
Coating the anatase sol on a substrate; ≪ / RTI > by weight of anatase sol. The method of claim 1,
Wherein the step of reacting the titanium tetrachloride (TiCl 4 ) with water to produce a TiOCl 2 aqueous solution is performed in a nitrogen gas atmosphere. The method of claim 1,
Wherein a Ti electrode is used for the first mixed solution and a Pt electrode is used for the anatase sol in the step of generating the anatase sol in the first mixed solution. The method of claim 1,
In the step of producing the TiOCl 2 aqueous solution, titanium tetrachloride (TiCl 4 ) is supplied from a first vessel, the aqueous solution of TiOCl 2 is produced in a first reactor, the first vessel and the first reactor are connected by piping , And the titanium tetrachloride (TiCl 4 ) is pressurized by the nitrogen gas supplied to the first vessel and supplied to the first reactor. 5. The method of claim 4,
Wherein the step of forming the TiOCl 2 aqueous solution comprises cooling at least a part of the first reactor with a refrigerant containing ice to cool the TiOCl 2 aqueous solution. In a solar cell electrode comprising a porous coating layer,
Wherein the porous coating layer is formed using the anatase sol prepared by the method according to any one of claims 1 to 5.
KR1020160161772A 2016-11-30 2016-11-30 Forming method of porous coating layer using anatase sol KR101883076B1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008188583A (en) 2007-02-06 2008-08-21 Minoru Shiromizu Method for manufacturing photocatalyst body by peroxo-modified anatase sol
WO2012017752A1 (en) * 2010-08-02 2012-02-09 昭和電工株式会社 Titanium oxide sol and process for producing same, ultrafine particulate titanium oxide, process for producing same, and uses of same
KR101280153B1 (en) * 2012-01-03 2013-06-28 군산대학교산학협력단 Method for preparing nano crystalline anatase titanium dioxide powder
KR101290400B1 (en) * 2012-01-27 2013-07-26 군산대학교산학협력단 Apparatus for preparing nano crystalline anatase titanium dioxide powder
JP2018008583A (en) * 2016-07-12 2018-01-18 株式会社デンソー Vehicular dust measurement system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008188583A (en) 2007-02-06 2008-08-21 Minoru Shiromizu Method for manufacturing photocatalyst body by peroxo-modified anatase sol
WO2012017752A1 (en) * 2010-08-02 2012-02-09 昭和電工株式会社 Titanium oxide sol and process for producing same, ultrafine particulate titanium oxide, process for producing same, and uses of same
KR101280153B1 (en) * 2012-01-03 2013-06-28 군산대학교산학협력단 Method for preparing nano crystalline anatase titanium dioxide powder
KR101290400B1 (en) * 2012-01-27 2013-07-26 군산대학교산학협력단 Apparatus for preparing nano crystalline anatase titanium dioxide powder
JP2018008583A (en) * 2016-07-12 2018-01-18 株式会社デンソー Vehicular dust measurement system

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