WO2009154327A1 - Transparent ion conductive solution and manufacturing method thereof - Google Patents

Transparent ion conductive solution and manufacturing method thereof Download PDF

Info

Publication number
WO2009154327A1
WO2009154327A1 PCT/KR2008/004986 KR2008004986W WO2009154327A1 WO 2009154327 A1 WO2009154327 A1 WO 2009154327A1 KR 2008004986 W KR2008004986 W KR 2008004986W WO 2009154327 A1 WO2009154327 A1 WO 2009154327A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
nitric acid
ion conductive
ammonia water
solution
Prior art date
Application number
PCT/KR2008/004986
Other languages
French (fr)
Inventor
Kyung Sik Kim
Young Jin Kim
Original Assignee
Kyung Sik Kim
Young Jin Kim
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kyung Sik Kim, Young Jin Kim filed Critical Kyung Sik Kim
Publication of WO2009154327A1 publication Critical patent/WO2009154327A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • the present invention relates to a transparent ion conductive solution and a method of manufacturing the same, and more particularly, to a transparent ion conductive solution with good conductivity and transparency and a method of manufacturing the same.
  • the present invention is directed to a transparent ion conductive solution having good conductivity and transparency. Also, the present invention is directed to a method of manufacturing a transparent ion conductive solution having good conductivity and transparency.
  • One aspect of the present invention provides a transparent ion conductive solution formed of an 18.0 to 50.0% by weight nitric acid solution, 2.8 to 12.3% by weight bismuth metal powder, 0.2 to 1.2% by weight silver oxide, 13.9 to 39.8% by weight ammonia water, 0.7 to 3.7% by weight zinc oxide, 10.0 to 30.0% by weight ethanol, and 0.1 to 1.2% by weight triethylamine.
  • the transparent ion conductive solution may have a resistivity of about 1 x 10 '5 to 1 x 10 "6 ⁇ -cm and a pH value of 4 to 8.
  • Another aspect of the present invention provides a method of manufacturing a transparent ion conductive solution.
  • the method includes: a first step of dissolving 2.8 to 12.3% by weight bismuth metal powder and 0.2 to 1.2% by weight silver oxide in an 18.0 to 50.0% by weight nitric acid solution; a second step of dissolving 0.7 to 3.7% by weight zinc oxide and 10.0 to 30.0% by weight ethanol in 13.9 to 39.8% by weight ammonia water; a third step of stirring while adding the mixture obtained in the first step in certain amounts to the mixture obtained in the second step or stirring while adding the mixture obtained in the second step in certain amounts to the mixture obtained in the first step; and a fourth step of adding 0.1 to 1.2% by weight triethylamine to a final mixture of the mixtures obtained in the first and second steps.
  • the transparent ion conductive solution may be formed to have a resistivity of about l x lO "5 to I x IO "6 ⁇ -cm.
  • the concentrations of the nitric acid solution and the ammonia water may be controlled such that the transparent ion conductive solution has a pH value of 4 to 8.
  • the first step may include dissolving the bismuth metal powder in the nitric acid solution before dissolving silver oxide in the nitric acid solution in order to facilitate ionization of silver oxide.
  • the second step may include dissolving zinc oxide in the ammonia water before adding ethanol to the ammonia water.
  • a transparent ion conductive solution having excellent conductivity and transparency can be manufactured using nitric acid, bismuth metal powder, silver oxide, ammonia water, zinc oxide, ethanol, and triethylamine.
  • FIG. IA is a scanning electron microscope (SEM) photograph showing a case in which a film was formed using a method shown in Experimental example 2 using a nitric acid solution in which bismuth metal powder and silver oxide were dissolved, which was obtained according to Experimental example 1.
  • FIG. IB is a SEM photograph showing a case in which a film was formed using the method shown in Experimental example 2 using ammonia water containing zinc oxide and ethanol, which was obtained according to Experimental example 1.
  • FIG. 1C is a SEM photograph showing a case in which a film was formed using the method shown in Experimental example 2 using a transparent ion conductive solution, which was obtained according to Experimental example 1.
  • FIG. 2A shows a reference resistance of a multimeter.
  • FIG. 2B shows the resistance of distilled water.
  • FIG. 2C shows the resistance of an indium tin oxide (ITO) solution.
  • FIG. 2D shows the resistance of a transparent ion conductive solution obtained according to Experimental example 1, which was measured using a multimeter.
  • ITO indium tin oxide
  • a transparent ion conductive solution according to an exemplary embodiment of the present invention may contain 18.0 to 50.0% by weight nitric acid solution, 2.8 to 12.3% by weight bismuth metal powder, 0.2 to 1.2% by weight silver oxide, 13.9 to 39.8% by weight ammonia water, 0.7 to 3.7% by weight zinc oxide, 10.0 to 30.0% by weight ethanol, and 0.1 to 1.2% by weight triethylamine.
  • the transparent ion conductive solution according to the exemplary embodiment may have a resistivity of about 1 x 10 '5 to 1 x 10 "6 ⁇ -cm and thus, it may have good conductivity. Also, the transparent ion conductive solution is transparent due to a very high light transmittance, for example, a visible-light transmittance of about 80 to 99.99%. In addition, the transparent ion conductive solution may have a pH value of about 4 to 8.
  • a method of manufacturing a transparent ion conductive solution may include: a first step of dissolving 2.8 to 12.3% by weight bismuth metal powder and 0.2 to 1.2% by weight silver oxide in an 18.0 to 50.0% by weight nitric acid solution, a second step of dissolving 0.7 to 3.7% by weight zinc oxide and 10.0 to 30.0% by weight ethanol in a 13.9 to 39.8% by weight ammonia solution, stirring while adding the mixture obtained in the first step in certain amounts to the mixture obtained in the second step or stirring while adding the mixture obtained in the second step in certain amounts to the mixture obtained in the first step, and a step of adding 0.1 to 1.2% by weight triethylamine to a resultant mixture of the mixtures obtained in the first and second steps.
  • the nitric acid is a colorless liquid, which has a high hygroscopic property and generates heat.
  • the nitric acid partially decomposes when it is irradiated with light.
  • the nitric acid has a melting point of about -42 ° C and a boiling point of about
  • the nitric acid has a specific gravity of about 1.502 and a refractive index of about 1.397. Since the nitric acid is mixed with water in an arbitrary mixture ratio, a predetermined concentration of nitric acid may be produced.
  • the nitric acid intensely reacts with and dissolves most metals other than noble metals, such as gold (Au), platinum (Pt), rhodium (Rh), and iridium (Ir), while the nitric acid does not corrode but floats iron (Fe), chrome (Cr), aluminum (Al), and calcium (Ca).
  • the nitric acid may be ionized into hydrogen and nitrogen ions in a solution and function as an electron-acceptor in an oxidation-reduction reaction.
  • the nitric acid solution may be used to ionize bismuth metal powder and silver oxide.
  • the transparent ion conductive solution becomes poor at dissolving bismuth metal powder and silver oxide.
  • the transparent ion conductive solution becomes highly electrically conductive. Therefore, 18.0 to 50.6% by weight nitric acid may be contained in the transparent ion conductive solution.
  • the bismuth metal powder is a light reddish, silvery white metal that has the lowest electrical conductivity and thermal conductivity among practical metals and is diamagnetic. Although the bismuth metal powder is not corroded by an acid having no oxidizing power, it is soluble in a hot concentrated sulfuric acid or nitric acid to produce salt. When less than 2.8% by weight bismuth metal powder is contained, only a small amount of ions may dissolve in the nitric acid solution. When more than 12.3% by weight bismuth metal powder is contained, the nitric acid solution may be saturated with ions and crystallized in a salt state. Therefore, 2.8 to 12.3% by weight bismuth metal powder may be dissolved in the nitric acid solution.
  • the formula of silver oxide is Ag 2 O, which is a dark brown or blackish brown heavy powder having a specific gravity of about 0.7220.
  • Silver oxide is unstable against heat and light. When silver oxide is heated, it starts to decompose at a temperature of about 160 ° C and rapidly decomposes at a temperature of about 250 to 300 ° C and emits oxygen.
  • Silver oxide is insoluble in water and ethanol, but it is easily soluble in a diluted nitric acid and ammonia water.
  • a silver oxide solution is strongly alkaline and absorbs carbon dioxide (CO 2 ) in the air.
  • Silver oxide may increase the amount of ions like the bismuth metal powder dissolved in the nitric acid solution.
  • nitric acid solution when less than 0.2% by weight silver oxide is contained, only a small amount of ions may dissolve in the nitric acid solution, while when more than 1.2% by weight silver oxide is contained, the nitric acid solution may be saturated with ions together with the bismuth metal powder and crystallized in a salt state. Therefore, 0.2 to 1.2% by weight silver oxide may be dissolved in the nitric acid solution.
  • the ammonia water is a water solution of ammonia (NH 3 ).
  • the ammonia water is a colorless transparent liquid, has an ammonia-like aroma and a stimulating taste, and exhibits alkalinity.
  • the ammonia water is used to dissolve zinc oxide. When less than 13.9% by weight ammonia water is used, zinc oxide is not easily soluble in the ammonia water. When more than 39.8% by weight ammonia water is used, the ammonia water may have a bad influence on controlling a pH concentration of the mixture of the solutions obtained in the first and second steps. Therefore, 13.9 to 39.8% by weight ammonia water may be used.
  • Zinc oxide which is a compound of oxygen and zinc, is a lightweight white powder and may be otherwise called zinc oxide or zinc white.
  • Zinc oxide melts at a melting point of about 1 ,975 °C under an applied pressure and at a melting point of about 1,720 ° C under an atmospheric pressure. Also, zinc oxide has a specific gravity of about 5.47 (non-crystalline) and about 5.78 (crystalline).
  • zinc oxide is heated to a temperature of about 300 ° C, it turns yellow. However, when zinc oxide is cooled off, it turns white again.
  • Zinc oxide is hardly soluble in water, but it is an amphoteric oxide that is soluble in watery acid and concentrated alkali. Zinc oxide is dissolved in the ammonia water to produce ions.
  • ethanol is C 2 H 5 OH, which is a colorless liquid with a peculiar smell and flavor.
  • Ethanol has a molecular weight of about 46.07, melts at a melting point of -114.3 °C, boils at a boiling point of about 78.4 °C, and has a specific gravity of about 0.7893.
  • Ethanol may be mixed with an organic solvent, such as other alcohol, ether, and chloroform, or water in an arbitrary ratio.
  • Ethanol may be mixed with the ammonia water containing zinc oxide in the second step and dilute the ammonia water in order to prevent occurrence of a direct intense acid-alkali reaction during mixture of the ammonia water containing zinc oxide and ethanol with the nitric acid solution containing bismuth metal powder and silver oxide obtained in the first step.
  • the nitric acid solution containing bismuth metal powder and silver oxide obtained in the first step may intensely react with the ammonia water containing zinc oxide obtained in the second step, thereby raising the temperature of the resultant mixture.
  • Triethylamine donates electrons to an electron-attracting material and is positively charged. Also, triethylamine functions to aid a material to be fallen out to fall out more effectively.
  • triethylamine When less than 0.1% by weight triethylamine is contained, it is difficult to stabilize ions in the mixture obtained by mixing the solutions obtained in the first and second steps.
  • triethylamine When more than 1.2% by weight triethylamine is contained, ions contained in the mixture obtained by mixing the solutions obtained in the first and second steps are unstably affected. Therefore, 0.1 to 1.2% by weight triethylamine may be contained.
  • the manufacture of the transparent ion conductive solution according to the exemplary embodiment of the present invention may include putting and dissolving 2.8 to 12.3% by weight bismuth metal powder and 0.2 to 1.2% by weight silver oxide in an 18.0 to 50.0% by weight nitric acid solution, putting and dissolving 0.7 to 3.7% by weight zinc oxide and 10.0 to 30.0% by weight ethanol in 13.9 to 39.8% by weight ammonia water, stirring the ammonia water containing zinc oxide and ethanol, adding the nitric acid solution containing the bismuth metal powder and silver oxide in small amounts to the ammonia water containing zinc oxide and ethanol to form a mixture, and adding 0.1 to 1.2% by weight triethylamine to the mixture.
  • the concentrations of the nitric acid solution and ammonia water may be controlled so that the transparent ion conductive solution can have a pH value of 4 to 8.
  • bismuth metal powder is dissolved in an 18.0 to 50.0% by weight nitric acid solution.
  • the bismuth metal powder is dissolved in the nitric acid solution before dissolving silver oxide in the nitric acid solution in order to increase a tendency for silver oxide to be ionized in the nitric acid solution.
  • 0.2 to 1.2% by weight silver oxide is added to the nitric acid solution.
  • the bismuth metal powder and silver oxide may be contained in the nitric acid solution in order to generate a larger number of ions in the nitric acid solution so that the transparent ion conductive solution can have good electrical conductivity.
  • 0.7 to 3.7% by weight zinc oxide and 10.0 to 30.0% by weight ethanol may be dissolved in 13.9 to 39.8% by weight ammonia water, and the ammonia water containing zinc oxide and ethanol may be stirred. In this case, a stirrer may rotate at a speed of about 50 to 500rpm.
  • zinc oxide may be added to and dissolved in 13.9 to 39.8% by weight ammonia water.
  • zinc oxide is dissolved in the ammonia water before adding ethanol to the ammonia water because ethanol may lower the concentration of zinc oxide and prevent zinc oxide from being easily ionized.
  • Zinc oxide may be contained in the ammonia water in order to generate a large number of ions in the ammonia water so that the transparent ion conductive solution can have good electrical conductivity.
  • ethanol When the mixture of zinc oxide with the ammonia water is completed, 10.0 to 30.0% by weight ethanol may be dissolved in the ammonia water and stirred. In this case, after zinc oxide is sufficiently dissolved and ionized in the ammonia water, ethanol may be contained and stirred in the ammonia water. While stirring the ammonia water containing zinc oxide and ethanol, the nitric acid solution in which the bismuth metal powder and silver oxide are dissolved may be added in small amounts to the ammonia water in order to prevent generation of an intense acid-alkali reaction due to a large amount of nitric acid solution and dilute the concentration.
  • the stirring process may be performed for about 2 to 30 minutes.
  • the nitric acid solution in which the bismuth metal powder and silver oxide are dissolved may be wholly added to and mixed with the ammonia water containing zinc oxide and ethanol.
  • the nitric acid solution in which the bismuth metal powder and silver oxide are dissolved may have a brown color by the bismuth metal powder, but it may become gradually transparent white as the ammonia water is added to the nitric acid solution.
  • triethylamine may be mixed with the mixture of the nitric acid solution in which the bismuth metal powder and silver oxide are dissolved with the ammonia water containing zinc oxide and ethanol. Triethylamine may donate electrons to an electron-attracting material and be positively charged. Also, triethylamine functions to aid a material (i.e., zinc) to be fallen out to fall out more effectively.
  • the nitric acid solution in which the bismuth metal powder and silver oxide are dissolved were added in small amounts to the ammonia water and mixed with the ammonia water.
  • the stirring process was performed for about 15 minutes.
  • the nitric acid solution in which the bismuth metal powder and silver oxide were dissolved were wholly added to and mixed with the ammonia water containing zinc oxide and ethanol.
  • 0.6% by weight triethylamine was mixed with a mixture of the nitric acid solution in which the bismuth metal powder and silver oxide were dissolved with the ammonia water containing zinc oxide and ethanol, thereby producing a transparent ion conductive solution.
  • the resultant transparent ion conductive solution had a resistivity of about l x lO '6 ⁇ -cm and a pH value of about 5.
  • the resistance of the transparent ion conductive solution obtained according to Experimental example 1 was measured using a multimeter (189 True RMS Multimeter manufactured by Fluke) as shown in FIG. 2D.
  • FIG. 2A shows the reference resistance of the multimeter
  • FIG. 2B shows the resistance of distilled water
  • FIG. 2C shows the resistance of an indium tin oxide (ITO) solution.
  • ITO indium tin oxide
  • the resistance of the transparent ion conductive solution measured using the multimeter was 4.39 ⁇ . Therefore, it can be seen that the transparent ion conductive solution according to the present invention has very high ion conductivity.
  • Experimental example 2 The transparent ion conductive solution obtained according to Experimental example 1 was coated to manufacture a transparent conductive film.
  • the transparent ion conductive solution was mixed with an acryl monomer, which is an acrylic binder, and an ultraviolet (UV)-curing agent, coated on a transparent overhead projector (OHP) film, irradiated with UV light for about 1 minute and cured.
  • an acryl monomer which is an acrylic binder
  • UV-curing agent coated on a transparent overhead projector (OHP) film
  • a mixture of the transparent conductive solution with the acryl monomer and UV- curing agent was coated to a thickness of about 20 ⁇ m.
  • FIG. 1C is a SEM photograph showing a case where the transparent conductive film was formed using the method shown in Experimental example 2 using the transparent ion conductive solution obtained according to Experimental example 1.
  • FIG. IA is a SEM photograph showing a case where a film was formed using the method shown in Experimental example 2 using the nitric acid solution in which the bismuth metal powder and silver oxide were dissolved, which was obtained according to Experimental example 1
  • FIG. IB is a SEM photograph showing a case where a film was formed using the method shown in Experimental example 2 using the ammonia containing zinc oxide and ethanol, which was obtained according to Experimental example 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

A transparent ion conductive solution and a method of manufacturing the same are provided. The transparent ion conductive solution is formed of an 18.0 to 50.0% by weight nitric acid solution, 2.8 to 12.3% by weight bismuth metal powder, 0.2 to 1.2% by weight silver oxide, 13.9 to 39.8% by weight ammonia water, 0.7 to 3.7% by weight zinc oxide, 10.0 to 30.0% by weight ethanol, and 0.1 to 1.2% by weight triethylamine. The transparent ion conductive solution can have excellent conductivity and transparency.

Description

[DESCRIPTION] [Invention Title]
TRANSPARENT ION CONDUCTIVE SOLUTION AND MANUFACTURING
METHOD THEREOF [Technical Field]
The present invention relates to a transparent ion conductive solution and a method of manufacturing the same, and more particularly, to a transparent ion conductive solution with good conductivity and transparency and a method of manufacturing the same. [Background Art]
The electrical conductivity and transmittance of a conventional ion conductive solution may be affected by the density of ions with electrical conductivity in the ion conductive solution. Therefore, in spite of various efforts, it is still difficult to embody an ion conductive solution with high electrical conductivity and transmittance. [Disclosure]
[Technical Problem]
The present invention is directed to a transparent ion conductive solution having good conductivity and transparency. Also, the present invention is directed to a method of manufacturing a transparent ion conductive solution having good conductivity and transparency. [Technical Solution]
One aspect of the present invention provides a transparent ion conductive solution formed of an 18.0 to 50.0% by weight nitric acid solution, 2.8 to 12.3% by weight bismuth metal powder, 0.2 to 1.2% by weight silver oxide, 13.9 to 39.8% by weight ammonia water, 0.7 to 3.7% by weight zinc oxide, 10.0 to 30.0% by weight ethanol, and 0.1 to 1.2% by weight triethylamine. The transparent ion conductive solution may have a resistivity of about 1 x 10'5 to 1 x 10"6 Ω -cm and a pH value of 4 to 8.
Another aspect of the present invention provides a method of manufacturing a transparent ion conductive solution. The method includes: a first step of dissolving 2.8 to 12.3% by weight bismuth metal powder and 0.2 to 1.2% by weight silver oxide in an 18.0 to 50.0% by weight nitric acid solution; a second step of dissolving 0.7 to 3.7% by weight zinc oxide and 10.0 to 30.0% by weight ethanol in 13.9 to 39.8% by weight ammonia water; a third step of stirring while adding the mixture obtained in the first step in certain amounts to the mixture obtained in the second step or stirring while adding the mixture obtained in the second step in certain amounts to the mixture obtained in the first step; and a fourth step of adding 0.1 to 1.2% by weight triethylamine to a final mixture of the mixtures obtained in the first and second steps. The transparent ion conductive solution may be formed to have a resistivity of about l x lO"5 to I x IO"6 Ω -cm. The concentrations of the nitric acid solution and the ammonia water may be controlled such that the transparent ion conductive solution has a pH value of 4 to 8. The first step may include dissolving the bismuth metal powder in the nitric acid solution before dissolving silver oxide in the nitric acid solution in order to facilitate ionization of silver oxide. The second step may include dissolving zinc oxide in the ammonia water before adding ethanol to the ammonia water. [Advantageous Effects] According to the present invention, a transparent ion conductive solution having excellent conductivity and transparency can be manufactured using nitric acid, bismuth metal powder, silver oxide, ammonia water, zinc oxide, ethanol, and triethylamine. [ Description of Drawings ]
FIG. IA is a scanning electron microscope (SEM) photograph showing a case in which a film was formed using a method shown in Experimental example 2 using a nitric acid solution in which bismuth metal powder and silver oxide were dissolved, which was obtained according to Experimental example 1. FIG. IB is a SEM photograph showing a case in which a film was formed using the method shown in Experimental example 2 using ammonia water containing zinc oxide and ethanol, which was obtained according to Experimental example 1.
FIG. 1C is a SEM photograph showing a case in which a film was formed using the method shown in Experimental example 2 using a transparent ion conductive solution, which was obtained according to Experimental example 1. FIG. 2A shows a reference resistance of a multimeter. FIG. 2B shows the resistance of distilled water. FIG. 2C shows the resistance of an indium tin oxide (ITO) solution. FIG. 2D shows the resistance of a transparent ion conductive solution obtained according to Experimental example 1, which was measured using a multimeter. [Mode for Invention]
Hereinafter, exemplary embodiments of the present invention will be described in detail. However, the present invention is not limited to the exemplary embodiments disclosed below, but can be implemented in various types. Therefore, the present exemplary embodiments are provided for complete disclosure of the present invention and to fully inform the scope of the present invention to those ordinarily skilled in the art. A transparent ion conductive solution according to an exemplary embodiment of the present invention may contain 18.0 to 50.0% by weight nitric acid solution, 2.8 to 12.3% by weight bismuth metal powder, 0.2 to 1.2% by weight silver oxide, 13.9 to 39.8% by weight ammonia water, 0.7 to 3.7% by weight zinc oxide, 10.0 to 30.0% by weight ethanol, and 0.1 to 1.2% by weight triethylamine. The transparent ion conductive solution according to the exemplary embodiment may have a resistivity of about 1 x 10'5 to 1 x 10"6 Ω -cm and thus, it may have good conductivity. Also, the transparent ion conductive solution is transparent due to a very high light transmittance, for example, a visible-light transmittance of about 80 to 99.99%. In addition, the transparent ion conductive solution may have a pH value of about 4 to 8.
A method of manufacturing a transparent ion conductive solution according to an exemplary embodiment of the present invention may include: a first step of dissolving 2.8 to 12.3% by weight bismuth metal powder and 0.2 to 1.2% by weight silver oxide in an 18.0 to 50.0% by weight nitric acid solution, a second step of dissolving 0.7 to 3.7% by weight zinc oxide and 10.0 to 30.0% by weight ethanol in a 13.9 to 39.8% by weight ammonia solution, stirring while adding the mixture obtained in the first step in certain amounts to the mixture obtained in the second step or stirring while adding the mixture obtained in the second step in certain amounts to the mixture obtained in the first step, and a step of adding 0.1 to 1.2% by weight triethylamine to a resultant mixture of the mixtures obtained in the first and second steps.
The nitric acid is a colorless liquid, which has a high hygroscopic property and generates heat. The nitric acid partially decomposes when it is irradiated with light. The nitric acid has a melting point of about -42 °C and a boiling point of about
86 °C (the nitric acid partially decomposes into water and nitrogen pentoxide (N2O5)).
The nitric acid has a specific gravity of about 1.502 and a refractive index of about 1.397. Since the nitric acid is mixed with water in an arbitrary mixture ratio, a predetermined concentration of nitric acid may be produced. The nitric acid intensely reacts with and dissolves most metals other than noble metals, such as gold (Au), platinum (Pt), rhodium (Rh), and iridium (Ir), while the nitric acid does not corrode but floats iron (Fe), chrome (Cr), aluminum (Al), and calcium (Ca). The nitric acid may be ionized into hydrogen and nitrogen ions in a solution and function as an electron-acceptor in an oxidation-reduction reaction. The nitric acid solution may be used to ionize bismuth metal powder and silver oxide. When less than 18.0% by weight nitric acid is contained, the transparent ion conductive solution becomes poor at dissolving bismuth metal powder and silver oxide. When more than 50.0% by weight nitric acid is contained, the transparent ion conductive solution becomes highly electrically conductive. Therefore, 18.0 to 50.6% by weight nitric acid may be contained in the transparent ion conductive solution.
The bismuth metal powder is a light reddish, silvery white metal that has the lowest electrical conductivity and thermal conductivity among practical metals and is diamagnetic. Although the bismuth metal powder is not corroded by an acid having no oxidizing power, it is soluble in a hot concentrated sulfuric acid or nitric acid to produce salt. When less than 2.8% by weight bismuth metal powder is contained, only a small amount of ions may dissolve in the nitric acid solution. When more than 12.3% by weight bismuth metal powder is contained, the nitric acid solution may be saturated with ions and crystallized in a salt state. Therefore, 2.8 to 12.3% by weight bismuth metal powder may be dissolved in the nitric acid solution. The formula of silver oxide is Ag2O, which is a dark brown or blackish brown heavy powder having a specific gravity of about 0.7220. Silver oxide is unstable against heat and light. When silver oxide is heated, it starts to decompose at a temperature of about 160°C and rapidly decomposes at a temperature of about 250 to 300 °C and emits oxygen. Silver oxide is insoluble in water and ethanol, but it is easily soluble in a diluted nitric acid and ammonia water. A silver oxide solution is strongly alkaline and absorbs carbon dioxide (CO2) in the air. Silver oxide may increase the amount of ions like the bismuth metal powder dissolved in the nitric acid solution. Thus, when less than 0.2% by weight silver oxide is contained, only a small amount of ions may dissolve in the nitric acid solution, while when more than 1.2% by weight silver oxide is contained, the nitric acid solution may be saturated with ions together with the bismuth metal powder and crystallized in a salt state. Therefore, 0.2 to 1.2% by weight silver oxide may be dissolved in the nitric acid solution.
The ammonia water is a water solution of ammonia (NH3). The ammonia water is a colorless transparent liquid, has an ammonia-like aroma and a stimulating taste, and exhibits alkalinity. The ammonia water is used to dissolve zinc oxide. When less than 13.9% by weight ammonia water is used, zinc oxide is not easily soluble in the ammonia water. When more than 39.8% by weight ammonia water is used, the ammonia water may have a bad influence on controlling a pH concentration of the mixture of the solutions obtained in the first and second steps. Therefore, 13.9 to 39.8% by weight ammonia water may be used.
Zinc oxide, which is a compound of oxygen and zinc, is a lightweight white powder and may be otherwise called zinc oxide or zinc white. Zinc oxide melts at a melting point of about 1 ,975 °C under an applied pressure and at a melting point of about 1,720 °C under an atmospheric pressure. Also, zinc oxide has a specific gravity of about 5.47 (non-crystalline) and about 5.78 (crystalline). When zinc oxide is heated to a temperature of about 300 °C, it turns yellow. However, when zinc oxide is cooled off, it turns white again. Zinc oxide is hardly soluble in water, but it is an amphoteric oxide that is soluble in watery acid and concentrated alkali. Zinc oxide is dissolved in the ammonia water to produce ions. When less than 0.7% by weight zinc oxide is dissolved in the ammonia water, only a small amount of ions are produced in the ammonia water, while when more than 3.7% by weight zinc oxide is dissolved in the ammonia water, zinc oxide is not completely dissolved in the ammonia water. Therefore, 0.7 to 3.7% by weight zinc oxide may be contained in the ammonia water.
The formula of ethanol is C2H5OH, which is a colorless liquid with a peculiar smell and flavor. Ethanol has a molecular weight of about 46.07, melts at a melting point of -114.3 °C, boils at a boiling point of about 78.4 °C, and has a specific gravity of about 0.7893. Ethanol may be mixed with an organic solvent, such as other alcohol, ether, and chloroform, or water in an arbitrary ratio. Ethanol may be mixed with the ammonia water containing zinc oxide in the second step and dilute the ammonia water in order to prevent occurrence of a direct intense acid-alkali reaction during mixture of the ammonia water containing zinc oxide and ethanol with the nitric acid solution containing bismuth metal powder and silver oxide obtained in the first step. When less than 10.0% by weight ethanol in a mixing ratio is contained, the nitric acid solution containing bismuth metal powder and silver oxide obtained in the first step may intensely react with the ammonia water containing zinc oxide obtained in the second step, thereby raising the temperature of the resultant mixture. When more than 30.0% by weight ethanol is contained, a time taken to cause a reaction of the solution obtained in the first step with the solution obtained in the second step may be affected. Therefore, 10.0 to 30.0% by weight ethanol may be contained in the ammonia water. Triethylamine donates electrons to an electron-attracting material and is positively charged. Also, triethylamine functions to aid a material to be fallen out to fall out more effectively. When less than 0.1% by weight triethylamine is contained, it is difficult to stabilize ions in the mixture obtained by mixing the solutions obtained in the first and second steps. When more than 1.2% by weight triethylamine is contained, ions contained in the mixture obtained by mixing the solutions obtained in the first and second steps are unstably affected. Therefore, 0.1 to 1.2% by weight triethylamine may be contained.
The manufacture of the transparent ion conductive solution according to the exemplary embodiment of the present invention may include putting and dissolving 2.8 to 12.3% by weight bismuth metal powder and 0.2 to 1.2% by weight silver oxide in an 18.0 to 50.0% by weight nitric acid solution, putting and dissolving 0.7 to 3.7% by weight zinc oxide and 10.0 to 30.0% by weight ethanol in 13.9 to 39.8% by weight ammonia water, stirring the ammonia water containing zinc oxide and ethanol, adding the nitric acid solution containing the bismuth metal powder and silver oxide in small amounts to the ammonia water containing zinc oxide and ethanol to form a mixture, and adding 0.1 to 1.2% by weight triethylamine to the mixture. In this case, the concentrations of the nitric acid solution and ammonia water may be controlled so that the transparent ion conductive solution can have a pH value of 4 to 8.
Hereinafter, a method of manufacturing the transparent ion conductive solution will be described in more detail.
2.8 to 12.3% by weight bismuth metal powder and 0.2 to 1.2% by weight silver oxide are dissolved in an 18.0 to 50.0% by weight nitric acid solution.
Specifically, to begin with, 2.8 to 12.3% by weight bismuth metal powder is dissolved in an 18.0 to 50.0% by weight nitric acid solution. In this case, the bismuth metal powder is dissolved in the nitric acid solution before dissolving silver oxide in the nitric acid solution in order to increase a tendency for silver oxide to be ionized in the nitric acid solution.
When the mixture of the bismuth metal powder with the nitric acid solution is completed, 0.2 to 1.2% by weight silver oxide is added to the nitric acid solution. Here, care must be taken for the nitric acid solution not to be saturated with ions and the bismuth metal powder and easily crystallized in a salt state. The bismuth metal powder and silver oxide may be contained in the nitric acid solution in order to generate a larger number of ions in the nitric acid solution so that the transparent ion conductive solution can have good electrical conductivity. 0.7 to 3.7% by weight zinc oxide and 10.0 to 30.0% by weight ethanol may be dissolved in 13.9 to 39.8% by weight ammonia water, and the ammonia water containing zinc oxide and ethanol may be stirred. In this case, a stirrer may rotate at a speed of about 50 to 500rpm.
Specifically, 0.7 to 3.7% by weight zinc oxide may be added to and dissolved in 13.9 to 39.8% by weight ammonia water. In this case, zinc oxide is dissolved in the ammonia water before adding ethanol to the ammonia water because ethanol may lower the concentration of zinc oxide and prevent zinc oxide from being easily ionized. Zinc oxide may be contained in the ammonia water in order to generate a large number of ions in the ammonia water so that the transparent ion conductive solution can have good electrical conductivity.
When the mixture of zinc oxide with the ammonia water is completed, 10.0 to 30.0% by weight ethanol may be dissolved in the ammonia water and stirred. In this case, after zinc oxide is sufficiently dissolved and ionized in the ammonia water, ethanol may be contained and stirred in the ammonia water. While stirring the ammonia water containing zinc oxide and ethanol, the nitric acid solution in which the bismuth metal powder and silver oxide are dissolved may be added in small amounts to the ammonia water in order to prevent generation of an intense acid-alkali reaction due to a large amount of nitric acid solution and dilute the concentration. Here, care must be taken for the ammonia water and the nitric acid solution not to intensely react with each other not to raise the temperature of the mixture of the ammonia water and the nitric acid solution. The stirring process may be performed for about 2 to 30 minutes. During the stirring process, the nitric acid solution in which the bismuth metal powder and silver oxide are dissolved may be wholly added to and mixed with the ammonia water containing zinc oxide and ethanol. The nitric acid solution in which the bismuth metal powder and silver oxide are dissolved may have a brown color by the bismuth metal powder, but it may become gradually transparent white as the ammonia water is added to the nitric acid solution. It is understood that as the bismuth metal powder reacts with ethanol, the nitric acid solution loses the brown color and wears a white color. 0.1 to 1.2% by weight triethylamine may be mixed with the mixture of the nitric acid solution in which the bismuth metal powder and silver oxide are dissolved with the ammonia water containing zinc oxide and ethanol. Triethylamine may donate electrons to an electron-attracting material and be positively charged. Also, triethylamine functions to aid a material (i.e., zinc) to be fallen out to fall out more effectively.
As known from the above exemplary embodiment, in the transparent ion conductive solution according to the present invention, bismuth metal powder, silver oxide, and zinc oxide are ionized and exhibit good electrical conductivity. The present invention will now be described in more detail with reference to the following experimental examples. However, the invention should not be construed as limited to the experimental examples set forth herein. Experimental example 1
6.08% by weight bismuth metal powder with an average grain size of about 100 /ΛH was dissolved in a 42.0% by weight nitric acid solution with a concentration of 69%, and 0.62% by weight silver oxide with an average grain size of about 100 μm was added to and dissolved in the nitric acid solution.
1.8% by weight zinc oxide with an average grain size of about 80 /^ was added to and sufficiently dissolved in 33.8% by weight ammonia water with a concentration of 28%, and 15.1% by weight ethanol was added to the ammonia water and stirred. In this case, a stirrer rotated at a speed of about 200rpm.
While stirring the ammonia water containing zinc oxide and ethanol, the nitric acid solution in which the bismuth metal powder and silver oxide are dissolved were added in small amounts to the ammonia water and mixed with the ammonia water. The stirring process was performed for about 15 minutes. During the stirring process, the nitric acid solution in which the bismuth metal powder and silver oxide were dissolved were wholly added to and mixed with the ammonia water containing zinc oxide and ethanol. 0.6% by weight triethylamine was mixed with a mixture of the nitric acid solution in which the bismuth metal powder and silver oxide were dissolved with the ammonia water containing zinc oxide and ethanol, thereby producing a transparent ion conductive solution.
The resultant transparent ion conductive solution had a resistivity of about l x lO'6Ω -cm and a pH value of about 5. The resistance of the transparent ion conductive solution obtained according to Experimental example 1 was measured using a multimeter (189 True RMS Multimeter manufactured by Fluke) as shown in FIG. 2D. To compare with FIG. 2D, FIG. 2A shows the reference resistance of the multimeter, FIG. 2B shows the resistance of distilled water, and FIG. 2C shows the resistance of an indium tin oxide (ITO) solution. As shown in FIG. 2D, the resistance of the transparent ion conductive solution measured using the multimeter was 4.39Ω. Therefore, it can be seen that the transparent ion conductive solution according to the present invention has very high ion conductivity. Experimental example 2 The transparent ion conductive solution obtained according to Experimental example 1 was coated to manufacture a transparent conductive film.
In order to manufacture the transparent conductive film, the transparent ion conductive solution was mixed with an acryl monomer, which is an acrylic binder, and an ultraviolet (UV)-curing agent, coated on a transparent overhead projector (OHP) film, irradiated with UV light for about 1 minute and cured. In this case, a mixture of the transparent conductive solution with the acryl monomer and UV- curing agent was coated to a thickness of about 20 μm.
The resultant transparent conductive film was observed using a scanning electron microscope (SEM) as shown in FIG. 1C. FIG. 1C is a SEM photograph showing a case where the transparent conductive film was formed using the method shown in Experimental example 2 using the transparent ion conductive solution obtained according to Experimental example 1. By comparison, FIG. IA is a SEM photograph showing a case where a film was formed using the method shown in Experimental example 2 using the nitric acid solution in which the bismuth metal powder and silver oxide were dissolved, which was obtained according to Experimental example 1, and FIG. IB is a SEM photograph showing a case where a film was formed using the method shown in Experimental example 2 using the ammonia containing zinc oxide and ethanol, which was obtained according to Experimental example 1. While the invention has been shown and described with reference to certain exemplary embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

[CLAIMS]
[Claim 1 ]
A transparent ion conductive solution formed of an 18.0 to 50.0% by weight nitric acid solution,
2.8 to 12.
3% by weight bismuth metal powder, 0.2 to 1.2% by weight silver oxide, 13.9 to 39.8% by weight ammonia water, 0.7 to 3.7% by weight zinc oxide, 10.0 to 30.0% by weight ethanol, and 0.1 to 1.2% by weight triethylamine. [Claim 2]
The transparent ion conductive solution according to claim 1, which has a resistivity of about 1 x 10"5 to 1 x 10"6 Ω • cm . [Claim 3]
The transparent ion conductive solution according to claim 2, which has a pH value of 4 to 8.
[Claim 4] A method of manufacturing a transparent ion conductive solution, comprising: a first step of dissolving 2.8 to 12.3% by weight bismuth metal powder and 0.2 to 1.2% by weight silver oxide in an 18.0 to 50.0% by weight nitric acid solution; a second step of dissolving 0.7 to 3.7% by weight zinc oxide and 10.0 to 30.0% by weight ethanol in 13.9 to 39.8% by weight ammonia water; a third step of stirring while adding the mixture obtained in the first step in certain amounts to the mixture obtained in the second step or stirring while adding the mixture obtained in the second step in certain amounts to the mixture obtained in the first step; and a fourth step of adding 0.1 to 1.2% by weight triethylamine to a final mixture of the mixtures obtained in the first and second steps.
[Claim 5]
The method according to claim 4, wherein the transparent ion conductive solution is formed to have a resistivity of about 1 x 10"5 to 1 x 10"6 Ω -cm.
[Claim 6]
The method according to claim 4, wherein the concentrations of the nitric acid solution and the ammonia water are controlled such that the transparent ion conductive solution has a pH value of 4 to 8. [Claim 7]
The method according to claim 4, wherein the first step comprises dissolving the bismuth metal powder in the nitric acid solution before dissolving silver oxide in the nitric acid solution in order to facilitate ionization of silver oxide. [Claim 8] The method according to claim 4, wherein the second step comprises dissolving zinc oxide in the ammonia water before adding ethanol to the ammonia water.
PCT/KR2008/004986 2008-06-18 2008-08-26 Transparent ion conductive solution and manufacturing method thereof WO2009154327A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020080057248A KR101012662B1 (en) 2008-06-18 2008-06-18 Transparent ion conductive solution and manufacturing method thereof
KR10-2008-0057248 2008-06-18

Publications (1)

Publication Number Publication Date
WO2009154327A1 true WO2009154327A1 (en) 2009-12-23

Family

ID=41434226

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2008/004986 WO2009154327A1 (en) 2008-06-18 2008-08-26 Transparent ion conductive solution and manufacturing method thereof

Country Status (2)

Country Link
KR (1) KR101012662B1 (en)
WO (1) WO2009154327A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101012662B1 (en) * 2008-06-18 2011-02-09 김영진 Transparent ion conductive solution and manufacturing method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5725965A (en) * 1995-04-25 1998-03-10 Gas Research Institute Stable high conductivity functionally gradient compositionally layered solid state electrolytes and membranes
US6297002B1 (en) * 1999-05-24 2001-10-02 Fuji Photo Film Co., Ltd. Photothermographic material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101012662B1 (en) * 2008-06-18 2011-02-09 김영진 Transparent ion conductive solution and manufacturing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5725965A (en) * 1995-04-25 1998-03-10 Gas Research Institute Stable high conductivity functionally gradient compositionally layered solid state electrolytes and membranes
US6297002B1 (en) * 1999-05-24 2001-10-02 Fuji Photo Film Co., Ltd. Photothermographic material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101012662B1 (en) * 2008-06-18 2011-02-09 김영진 Transparent ion conductive solution and manufacturing method thereof

Also Published As

Publication number Publication date
KR20090131400A (en) 2009-12-29
KR101012662B1 (en) 2011-02-09

Similar Documents

Publication Publication Date Title
Huang et al. Simplifying the creation of hollow metallic nanostructures: one‐pot synthesis of hollow palladium/platinum single‐crystalline nanocubes
TWI541327B (en) Chrome-free methods of etching organic polymers with mixed acid solutions
JP5580153B2 (en) Metal fine particle dispersion, metal fine particle, production method of metal fine particle dispersion, etc.
JP2020076155A (en) Silver-coated copper powder and method for producing the same
JP2007335120A (en) Material for contact part or battery component, and battery using it
TW201133613A (en) Surface uevenness forming method using plasma-etching process and electrode member
Jia et al. Ion Pre‐Embedding Engineering of δ‐MnO2 for Chemically Self‐Charging Aqueous Zinc Ions Batteries
JP2020164401A (en) Solution containing lithium, niobium complex and nitrous acid and method for manufacturing the same, and method for manufacturing lithium secondary battery active material
US2306927A (en) Voltaic cell
CN1876281B (en) Copper powder
WO2009154327A1 (en) Transparent ion conductive solution and manufacturing method thereof
JP5992150B2 (en) Semiconductor substrate product manufacturing method, thin film removing solution and kit used therefor
WO2005114674A1 (en) Transparent conductive material, transparent conductive paste, transparent conductive film and transparent electrode
EP1771604A2 (en) Method for the production of nickel oxide surfaces having increased conductivity
CN102872864B (en) Preparation method for iridium catalyst
CN101780403A (en) Method for preparing metal/titanium dioxide composite material
JP4706835B2 (en) Method for producing gold fine particles
Kegel et al. Zno nanorod-arrays as photo-(electro) chemical materials: Strategies designed to overcome the material's natural limitations
JP2009009924A (en) Manufacturing method for mixed electrode-catalyst material of solid electrolyte fuel cell
Midya et al. Effect of microheterogeneous environments of CTAB, Triton X‐100, and Tween 20 on the oxidative degradation of d‐fructose by nanoparticles of MnO2
CN105951099A (en) Micro-etching solution for microsection production experiment in circuit board industry, and preparation method
JP5335328B2 (en) Method for producing conductive tin oxide powder
RU2390583C2 (en) Method of preparing concentrate of silver oxides
US3539469A (en) Method of manufacturing a silver catalyst for fuel cells by immersion coating
JPH0727851B2 (en) Method for manufacturing solid electrolytic capacitor

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08811479

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08811479

Country of ref document: EP

Kind code of ref document: A1