KR101570307B1 - Electrode For An Electrochemical Device, Method For Preparing The Same And Electrochemical Devices Comprising The Same - Google Patents

Abstract

The present invention relates to an electrode for an electrochemical device, a manufacturing method thereof, and an electrochemical device including the same. The electrode according to the present invention secures a long-term driving property, improves a response speed, prevents non-uniformity, and controls an operation voltage in the electrochemical device by spraying an inorganic nanostructure.

Description

Technical Field [0001] The present invention relates to an electrode for an electrochemical device, a method for manufacturing the electrode, and an electrochemical device including the same. [0002]

The present invention relates to an electrode for an electrochemical device, a method of manufacturing the same, and an electrochemical device including the same.

In electrochemical devices, reversible oxidation / reduction reaction of electroactive material takes place when voltage is applied, and it is accompanied with changes in optical characteristics including color, fluorescence, and refractive index, and ultimately, a device capable of controlling optical characteristics through voltage control . The structure of the electrochemical device is composed of working electrode where oxidation / reduction of electroactive material takes place, electrolyte for ion transfer, counter electrode to flow current, and improvement of electrochemical device characteristics through modification of component Research is being actively carried out.

The electrochromic device is a typical electrochemical device. The electrochromic material is controlled by the oxidation / reduction reaction and the color of the material is controlled, so that researches are being conducted to use it as a low power driving display and a smart window.

U.S. Patent No. 6,861,014 B2 discloses an electrochromic device capable of adsorbing an electrochromic material, viologen, on the surface of an inorganic nanostructure such as titanium oxide, tungsten oxide, molybdenum oxide, zinc oxide, and tin oxide, Respectively.

In addition, U.S. Patent No. 8,441,708 B2 discloses a method for producing nanostructure clusters having a size of 200 nm for electrochromic use. Conventional 20 nm nanoparticles have a surface area of 63 m ² / g whereas nanostructure clusters have a surface area of 105 m ² / g, which can increase the characteristics of electrochromism.

However, the nanostructure and the counter electrode are concentrated in the electrochromic device, and the response speed and the nonuniformity can be improved. However, there is no study on the cyclicity of the electrochromic device and the electrophoresis switching device, , And the role of counter electrode in electrochemiluminescence is not disclosed. In addition, the counter electrode is limited to a positive electrode driving material having an oxidation / reduction voltage range of 0 V to 3.0 V (vs. NHE), and thus has a problem in that it can not be applied to a cathode driving material.

U.S. Patent 6,861,014 B2 U.S. Patent No. 8,441,708 B2

Advanced Functional Materials, 22, 17, 3556-3561 (2012)

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides an electrode capable of effectively eliminating a charge imbalance generated in a working electrode and a method of manufacturing the same.

The present invention, in order to solve the above problems,

An electrically conductive electrode plate; And

And an inorganic nanostructure formed on one or both surfaces of the electrode plate,

Wherein the inorganic nanostructure has an average surface area ranging from 1 to 1000 m ² / g.

Further, in order to solve the above problems,

Preparing an inorganic nanoparticle paste;

Applying the inorganic nanoparticle paste to an electrically conductive electrode plate to form an inorganic nanostructure; And

And a step of heat-treating the electrode.

Further, the present invention provides a plasma display panel comprising: the electrode;

A working electrode arranged to face the electrode; And

And an electrolyte filled in a space between the two electrodes.

The electrode for an electrochemical device according to the present invention includes an inorganic nanostructure and thus can control an operating voltage, eliminate unevenness, improve response speed, reduce driving voltage and long-time driving property in an electrochemical device, It is possible to perform the oxidation drive and the reduction drive so as to cope with the unevenness of the electric charge, thereby preventing the decomposition of the electrochemical substance. The electrochemical device incorporating the electrode according to the present invention solves the problem of long-time driving that is essential for commercialization of optical characteristics control devices including electrochromic, electrophoretic, and electroluminescent devices, and provides a next generation display device having high efficiency and high stability characteristics, It can be used as core technology such as Windows.

1 is a cross-sectional view of an electrode according to one embodiment of the present invention.
2 is a cross-sectional view of an electrode according to another embodiment of the present invention.
3 is a cross-sectional view of an electrode according to another embodiment of the present invention.
4 is a photograph of an electrochromic device according to this disclosure.
5 is a photograph of an electric fluorescent device according to the present invention.
6 shows the stability test results of the electrochromic device according to the present invention.
7 shows the stability test result of the electrochromic device according to the comparative example.
8 is a graph showing the characteristics of an electric fluorescent device according to the present invention.
9 is a graph showing the characteristics of an electric fluorescent device according to a comparative example.
10 is a graph comparing electroluminescence characteristics of the example and the comparative example.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail.

It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terms first, second, etc. may be used to describe various elements, but the elements should not be limited by terms. Terms are used only for the purpose of distinguishing one component from another.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise.

In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Therefore, the configurations shown in the embodiments described herein are merely the most preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention. Therefore, various equivalents And variations.

Hereinafter, the electrode for an electrochemical device according to the present invention will be described in detail.

In the electrode according to the present invention,

An electrically conductive electrode plate; And

And an inorganic nanostructure formed on one or both surfaces of the electrode plate,

The inorganic nanostructure may have an average surface area ranging from 1 to 1000 m ² / g.

Specifically, the inorganic nanostructure may be formed on the conductive surface of the electroconductive electrode plate, or on both surfaces of the electroconductive electrode plate. The electrode according to the present invention includes the inorganic nanostructure, thereby maximizing the reaction surface area, thereby quickly eliminating the non-uniformity of charge. Further, the long-term stability and conversion rate improvement characteristics of the inorganic material can be exhibited.

As an example, the inorganic material constituting the inorganic nanostructure according to the present invention may have an average particle size of 1 to 200 nm, and specifically, 3 to 150 nm, 5 to 100 nm, 10 to 90 nm, Lt; / RTI > nm. When the average particle size of the inorganic substance is in the above range, it is possible to prevent the decrease of the transmittance and the light scattering, thereby improving the optical characteristics and forming a sufficient gap between the inorganic materials, thereby forming the inorganic nanostructure having a large surface area.

As another example, the inorganic nanostructure according to the present invention includes an inorganic material, and the inorganic material can be used without limitation as long as it is a material having excellent light stability and electrochemical stability. Specifically, the inorganic nanostructure may include TiO ₂ , V ₂ O ₅ , Nb ₂ O ₅ , WO ₃ , Ta ₂ O ₅ , MoO ₃ , Fe ₂ O ₃ And WO < ₃ >. And

NiO, IrO _2, can include any one or more of at least one member second inorganic group is selected from the group consisting of VO _2, CoO, and MnO _2.

The inorganic material according to the present invention is excellent in light stability and electrochemical stability and has the effect of improving the light stability and long-term usability of the electrode according to the present invention.

As an example, the electrode for an electrochemical device according to the present invention can be used as a counter electrode in an electrochemical device, and the electrode for an electrochemical device has a voltage corresponding to an oxidation / reduction voltage of a working material .

For example, an electrode for an electrochemical device in which a cathode inorganic material of the same voltage is formed can be used as a counter electrode of a material for oxidation / reduction driving at the anode, and as a counter electrode of a material for oxidation / reduction driving at the cathode, An electrode for an electrochemical device in which a positive electrode inorganic material is formed can be used. The negative electrode inorganic material may be at least one selected from the first inorganic material group according to the present invention, and the positive electrode inorganic material may be at least one selected from the second inorganic material group according to the present invention. The inorganic material of the electrode for the electrochemical device can be selected according to the oxidation / reduction voltage of the driving material of the electrochemical device.

In addition, an electrode driven by a plurality of electrochemical reactions may use an electrode in which a plurality of inorganic materials corresponding to respective voltages are mixed. Therefore, the electrode according to the present invention can be used as a counter electrode in an electrochemical device, and both the anode driving material and the cathode driving material can be used, and the charge imbalance generated in the working electrode can be effectively absorbed from the whole voltage.

As an example, the inorganic nanostructure according to the present invention may have an average surface area in the range of 1 to 1000 m ² / g, specifically 1 to 1000 m ² / g, 10 to 800 m ² / g, 15 G to about 700 m ² / g, 20 to 600 m ² / g, 30 to 500 m ² / g, 50 to 200 m ² / g, or 300 to 1000 m ² / g.

The inorganic nanostructure may have a nanostructure of 500 nm or less, 400 nm or less, or 100 nm or less, and thus has a large surface area in the above range. Therefore, the contact area with the electrolyte is wide, and the electrochromic device enables fast electrochromism when applied to an electrochromic device. In addition, the electrode according to the present invention has an effect of quickly dissipating the non-uniformity of charge generated in the electrochemical reaction by including the inorganic nanostructure having the wide surface in the above-mentioned range. In addition, it prevents the application of more than necessary voltage, prevents the decomposition of the electrochemical substance, and minimizes the decomposition action of the substance even if it is driven for a long time. Therefore, by introducing the electrode for an electrochemical device according to the present invention into an electrochemical device, it is possible to exhibit the effects of improving the conversion speed, reducing the driving voltage, and improving the driving time.

As an example, the thickness of the inorganic nanostructure according to the present invention may range from 1 nm to 20 탆. Specifically, the thickness of the inorganic nanostructure may be 1 nm to 20 탆, 10 nm to 15 탆, 20 nm to 10 탆, or 30 nm to 1 탆. The thickness of the inorganic nanostructure can affect the optical characteristics of the electrochemical device. When the thickness is within the above range, the inorganic nanostructure has a sufficient optical density, exhibits an effect of improving durability, It is possible to improve the decoloring and discoloration response speed when applied. In addition, when the inorganic nanostructure is in the above range, the light transmittance can be lowered and the light scattering can be prevented.

As one example, there electroconductive electrode plate according to the present invention can have a surface area of an average of 1 to 1000 m ² / g range, more specifically from 1 to 1000 m ² / g, 10 to 800 m ² / g, 15 G to about 700 m ² / g, 20 to 600 m ² / g, 30 to 500 m ² / g, 50 to 200 m ² / g, or 300 to 1000 m ² / g.

When the average surface area of the electroconductive electrode plate is within the above range, the formation of the inorganic nanostructure can be facilitated and the contact area with the electrolyte can be widened, which can help to eliminate the charge imbalance quickly.

In addition, the thickness of the electrically conductive electrode plate may be 1 nm to 20 탆, 10 nm to 15 탆, 20 nm to 10 탆, or 30 nm to 1 탆. When the thickness of the electroconductive electrode plate is in the above range, the inorganic nanostructure can be easily formed.

In addition, the electrically conductive electrode plate may have a nanostructure of 500 nm or less. Further, the electrically conductive electrode plate may have a thickness of 1 to 500 nm, 1 to 450 nm, 5 to 400 nm, 10 to 350 nm, 15 to 300 nm, 15 to 250 nm, 20 to 200 nm, 25 to 150 nm Or nanostructures ranging from 30 to 100 nm. The nanostructure in the above range can enlarge the surface area of the electroconductive electrode plate and improve the effect of eliminating nonuniformity of the electrode and improving the response speed.

As another example, the electrically conductive electrode plate according to the present invention may include a high conductivity material, such as indium tin oxide (ITO), indium zinc oxide (IZO), fluorine containing tin oxide (FTO ), A transparent conductive oxide (TCO), an Au nanowire, and a silver nanowire.

The high conductivity material may have a nanostructure, specifically, a structure of 500 nm or less. The high conductivity material may also have a surface area of greater than 1 m ² / g, greater than 5 m ² / g, greater than 10 m ² / g, or greater than 50 m ² / g.

Specifically, the electroconductive electrode plate of the present invention may include a fluorine-containing tin oxide (FTO) transparent conductive film. The FTO transparent conductive film is excellent in heat resistance, chemical resistance and abrasion resistance, has low resistance and high transmittance, Has a stable characteristic even after heat treatment, and has a characteristic of generating heat when electricity is applied. Therefore, the FTO transparent conductive film has properties such as thermal stability, chemical durability, mechanical durability, and the like that have no change in transparency and electrical conductivity even at a high temperature process of about 500-600 ° C. Therefore, when used as a counter electrode such as an electrochemical device, it has chemical stability against electrolyte. Further, since it has a transmittance, a low resistance and a high haze, it is possible to produce a transparent conductive film with high efficiency.

Further, since the FTO transparent conductive film of the present invention is excellent in heat resistance and chemical resistance, it has an advantage that it can be applied in various conditions, and has an advantage in that the modification is small in accordance with environmental changes.

As another example, the electrically conductive electrode plate may be in the form of a transparent conductive film formed on a substrate. As the substrate, a usual glass substrate or a plastic substrate can be used, and the kind thereof is not particularly limited.

As one example, the electrode according to the present invention may be a counter electrode. The present invention has the effect of rapidly dissipating the imbalance of the charge generated during the electrochemical reaction of the working electrode by providing the counter electrode having the inorganic nanostructure formed therein. Therefore, it is possible to prevent the application of more than necessary voltage and to prevent decomposition of the electrochemical substance.

Hereinafter, a method of manufacturing an electrode for an electrochemical device according to the present invention will be described in detail.

In the method for manufacturing an electrode for an electrochemical device according to the present invention,

Preparing an inorganic nanoparticle paste;

Applying the inorganic nanoparticle paste to an electrically conductive electrode plate to form an inorganic nanostructure; And

And a heat treatment step.

In the step of preparing the inorganic nanoparticle paste according to the present invention, the inorganic nanoparticle paste can be produced, for example, by dissolving an inorganic substance and a polymer for a binder in a solvent. The binder polymer and the solvent contained in the inorganic nanoparticle paste are not particularly limited as they can be selected and used as commonly used in the art to which the present invention belongs.

Specifically, the solvent can be produced using an alcohol and ethanol or another solvent. The solvent used may be different depending on the kind of the inorganic substance, and if it is a substance capable of dissolving the inorganic substance, a suitable solvent can be selected and used as needed. The solvent can be appropriately selected and used by those skilled in the art in consideration of the chemical reaction and the combination of molecules. In the present invention, terpineol may be used as a solvent.

In addition, the concentration and pH of the inorganic nanoparticle paste may vary depending on the type of the inorganic material used and may vary depending on what method is used. Therefore, those skilled in the art can easily determine the appropriate concentration and pH as needed.

As an example, in the step of forming the inorganic nanostructure on the electroconductive electrode plate, the method of applying the inorganic nanoparticle paste may be any commonly used method, and is not particularly limited. For example, the formation of the inorganic nanostructure on the electrically conductive electrode plate can be formed by a method such as screen printing, spin coating, sol-gel process, electrochemical synthesis, and electrospinning.

The heat-treating step according to the present invention may be carried out at a temperature in the range of 100 to 700 占 폚 for 10 minutes to 3 hours. Specifically, the temperature range may be 100 to 200 ° C, 140 to 500 ° C, 200 to 700 ° C, 250 to 650 ° C, 300 to 600 ° C, or 350 to 550 ° C, 10 minutes to 3 hours, Min, from 15 minutes to 120 minutes, from 20 minutes to 100 minutes, or from 25 minutes to 60 minutes.

When the heat treatment is carried out at the temperature and time in the above range, it is possible to manufacture an electrode having an effect of further facilitating the formation of the inorganic nanostructure and excellent in light stability and electrochemical stability.

Hereinafter, the electrochemical device according to the present invention will be described in detail.

In the electrochemical device according to the present invention,

An electrode according to the present invention;

A working electrode arranged to face the electrode; And

And an electrolyte filled in the space between the two electrodes.

The electrochemical device according to the present invention is an element capable of controlling optical characteristics by oxidation / reduction of an electrochemical material and includes, for example, an electrochromic device, an electric fluorescent device, an electroluminescent device, and an electrochemical diffraction optical device can do.

In addition, the electrochemical device may mean a device that controls an optical characteristic by controlling an electrochemical reaction with a direct current or an alternating voltage within ± 5 V. Specifically, an electrochromic device capable of controlling a color change, An electroluminescent device capable of controlling light emission and an electroluminescent device capable of emitting light.

As an example, an electrochemical device according to the present invention includes: a first electrode; A second electrode spaced apart from the first electrode and driven by oxidation / reduction; And a two-electrode device including an electrolyte positioned between the electrodes. At least one of the first electrode and the second electrode may be an electrode including the inorganic nanostructure according to the present invention. Specifically, as shown in Fig. 1, the two-electrode element includes a working electrode 2; A spacer 4; A counter electrode 6; Inorganic nanostructure 10; An electrolyte (8); And a power supply 12.

The electrochemical device according to the present invention may further include a reference electrode. The reference electrode may be disposed between the counter electrode and the working electrode. In addition, the reference electrode may be introduced to set a reference voltage of a voltage applied to the working electrode, and can be used without limitation as long as it is commonly used in the art. For example, silver wire, Ag / AgCl, a normal hydrogen electrode, and a saturated calomel electrode may be used.

As an example, an electrochemical device according to the present invention includes: a first electrode; A second electrode spaced apart from the first electrode and driven by oxidation / reduction; Working electrode; And a three-electrode element including an electrolyte. At least one of the first electrode and the second electrode may be an electrode including the inorganic nanostructure according to the present invention. Specifically, the three-electrode element includes a working electrode 22; A spacer 24; A counter electrode (26); Inorganic nanostructure 30; A reference electrode 34; An electrolyte (28); And a power supply 32.

Also, an electrochemical device according to the present invention includes: a first electrode; A second electrode spaced apart from the first electrode; A third electrode spaced apart from the first electrode and the second electrode; And a structure of a transistor type including an electrolyte. The first electrode, the second electrode, and the third electrode may have a patterned structure on the substrate, and each may serve as a source, a drain, and a gate. At least one of the first electrode, the second electrode and the third electrode may be an electrode including the inorganic nanostructure according to the present invention. Specifically, as shown in FIG. 3, the three-electrode element includes a first electrode 40; A second electrode (42); A third electrode (44); A substrate 46; An electrolyte 50; And a power supply 48.

As one example, the working electrode according to the present invention may include a high-conductivity material and can be used without limitation as long as it is commonly used in the art. Specifically, for example, indium tin oxide (ITO) And may include at least one selected from the group consisting of indium zinc oxide (IZO), fluorine-containing tin oxide (FTO), transparent conductive oxide (TCO), gold nanowire and silver nanowire.

As one example, the electrochemical device according to the present invention may use a spacer having an adhesive force to bond the first electrode and the second electrode. The spacer is not particularly limited as long as it can facilitate adhesion of the two electrodes, for example, surlyn can be used. The thickness of the spacer may be 30 to 250 占 퐉, 40 to 200 占 퐉, 50 to 180 占 퐉, or 60 to 100 占 퐉.

An electrolyte may be injected into the space inside the spacer to produce an electrochemical device.

As an example, the electrolyte according to the present invention may have an ionic conductivity at room temperature in the range of 1 to 12 mS / cm.

The electrolyte according to the present invention may be in the form of an electrolyte salt dissolved in a solvent and may be in the form of a liquid electrolyte, a gel electrolyte, a solid electrolyte, and a polyelectrolyte. More specifically, Lt; / RTI >

Also, the electrolyte according to the present invention may have a thickness ranging from 30 to 250 mu m. The thickness of the electrolyte may be specifically from 40 to 200 mu m, from 50 to 180 mu m, or from 60 to 100 mu m

Also, the electrolyte according to the present invention can be produced by reacting tetrabutylammonium hexafluorophosphate (TBAPF ₆ , n-Bu ₄ NPF ₆ ), lithium bistrifluoromethane sulfonimidate (LiTFSI, C ₂ F ₆ LiNO ₄ S ₂ ) tetrabutylammonium EO bonded (TBAI), tetrabutylammonium perchlorate _{(TBAP, n-Bu 4 NClO} 4), lithium perchlorate (LiClO _4), borate (NaBF _4), phosphate (LiPF ₆₎ as a lithium hexafluoro sodium tetrafluoroborate , Lithium tetrafluoroborate (LiBF ₄ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), potassium hexacyanoferrate (K ₄ Fe (CN) ₆ ) and lithium bisperfluoroethanesulfonyl (LiBETI, LiN (SO ₂ C ₂ F ₅ ) ₂ ).

The electrolyte according to the present invention may also be used in the form of a solution or dispersion of the electrolyte solution in a solvent such as methylene chloride, chloroform, acetonitrile, ethylene carbonate, propylene carbonate, tetrahydrofuran, butylene carbonate, polyethylene glycol, ethylene glycol, tetrachloroethene, And at least one solvent selected from the group consisting of

Also, the electrolyte according to the present invention may include an organic material having at least one kind selected from the group consisting of an acryloyl group, an epoxy group, a vinyl group and a methacryloyl group.

Best Mode for Carrying Out the Invention Hereinafter, the present invention will be described in more detail with reference to examples and drawings based on the above description. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Example  1 to 10: Manufacture of electrochromic device

1) Working electrode manufacturing

ITO glass (0.7 T, 15 Ω / sq) or ITO film (30 Ω / sq), which is a conductive transparent electrode, was used as the substrate of the working electrode used in Examples 1 to 10, and a conductive polymer solution was applied to the substrate at 1,600 rpm , And then heated at 65 DEG C for 2 hours to prepare an electrochromic thin film.

The conductive polymer solution may include poly (3,4-ethylenedioxythiophene) (hereinafter referred to as PEDOT), poly (3-hexylthiophene) (Hereinafter referred to as "P3HT") and 3,4-propylenedioxythiophene (hereinafter referred to as "ProDOT") were used. The conductive polymer solutions used in Examples 1 to 10 are summarized in Table 1 below.

2) Production of counter electrode

As a counter electrode substrate used in Examples 1 to 7, FTO glass (Philkington, 2.2 T, 8 Ω / sq), which is a conductive transparent electrode, was used. As the counter electrode substrate used in Examples 8 to 10, an ITO film 30 Ω / sq) was used.

2-1) Preparation of counter electrodes using screen printing: Examples 1, 3 and 5

In order to perform screen printing, an inorganic nanoparticle paste including nanoparticles (average particle size: 20 nm), polymer for binder (ethylcellulose) and solvent (terpineol, Terpineol) was prepared. As the inorganic material used as the nanoparticles, TiO _{2 in} Example 1, MoO _{3 in} Example ₃ , and Nb ₂ O ₅ in Example 5 were used. The prepared inorganic nanoparticle paste was coated on the surface of the conductive transparent electrode (FTO glass) by a screen printing method and then heat-treated at 500 ° C for 30 minutes to prepare a nanostructured counter electrode having an inorganic nanostructure. The thickness of the inorganic nanostructure was 8 탆 for Example 1, 3 탆 for Example 3, and 2 탆 for Example 5.

2-2) Preparation of counter electrode using spin-coating method: Examples 2 and 4

In order to perform spin coating, inorganic nanoparticle pastes including nanoparticles (average particle size: 20 nm), polymer for binder (ethylcellulose) and solvents (terpineol, Terpineol) were prepared. As the inorganic material used as the nanoparticles, TiO ₂ of Example ₂ and V ₂ O ₅ of Example 4 were used. 1 g of the inorganic nanoparticle paste was dispersed in 3.5 g of ethanol to prepare a solution. A solution in which the inorganic nanoparticle paste was dispersed was spin-coated on the FTO glass at 1,000 rpm to 3,000 rpm. Thereafter, the nanostructured counter electrode having an inorganic nanostructure formed thereon was heat-treated at 500 DEG C for 30 minutes. The thickness of the inorganic nanostructure was 300 nm in Example 2 and 200 nm in Example 4. [

2-3) Preparation of a counter electrode using electrospinning: Examples 6 and 7

35 g of dimethylformamide (DMF), 6.5 wt% of poly (vinylacetate), PVAc, Mw 850000 g / mol), titanium (IV) propoxide ) propoxide) and 5.2 wt% acetic acid was applied to the substrate by applying a voltage of 15 kV. Then, the substrate was heat-treated at 120 ^° C for 10 minutes and heat-treated at 450 ^° C for 30 minutes to prepare a nanostructure counter electrode.

In the following example, the cathode-nano structure counter electrode used to correspond to the cathode electrochemical material was prepared by adding MoO ₃ and V ₂ O ₅ of the same mass as the precursor of the corresponding inorganic material instead of TiO ₂ in the above-mentioned manufacturing method.

The thickness of the inorganic nanostructure formed by the above method was 100 nm in Example 6 and 200 nm in Example 7. [

2-4) Preparation of counter electrode using low temperature process: Examples 8, 9 and 10

A nanoparticle dispersion liquid containing 0.55 g of TiO ₂ nanoparticles (average particle size: 20 nm) and 10 ml of isopropanol (IPA) was spin-coated on the ITO film at 1,000 rpm to 3,000 rpm. In the following examples, the negative electrode nanostructure counter electrode used to correspond to the positive electrode electrochemical material was prepared by adding MoO ₃ and V ₂ O ₅ of the same mass as the inorganic substance instead of TiO ₂ in the above manufacturing method. Thereafter, the substrate was heat-treated at 150 ° C for 30 minutes to prepare a nanostructure counter electrode having an inorganic nanostructure. The thickness of the inorganic nanostructure was 50 nm in Example 8, 80 nm in Example 9, and 50 nm in Example 10.

3) Device fabrication

After the conductive surfaces of the working electrode and the counter electrode prepared by the above method were opposed to each other, they were adhered using a spacer (Surlyn, Dupont 1702) having an adhesive force. The thickness of the spacer was 80 mu m. Propylene carbonate (PC) in which 0.1 to 1 M of tetrabutylammonium perchlorate (TBAP) was dissolved was used as the electrolytes of Examples 1, 2, 8 and 10, and electrolytes of Examples 3 to 5 Propylene carbonate (PC) in which 0.1 to 1 M of lithium perchlorate (LiClO ₄ ) was dissolved was used. Examples 6, 7 and 9 used 1-ethyl-3- Methylimidazolium hexafluorophospate (C ₆ H ₁₁ N ₂ PF ₆ , hereinafter referred to as EMIM-PF ₆ ) was used as a solvent. The electrolyte was injected into the space inside the spacer and the outside of the device was bonded to produce an electrochromic device.

4 is a photograph of an electrochromic device according to Example 1. Fig.

The counter electrodes, the working electrode, and the electrolytes used in the electrochromic device of Examples 1 to 10 are summarized in Table 1 below.

division Working electrode (thickness) Nanostructured counter electrode Electrolyte Conductive electrode Inorganic nanostructure Example 1 ITO glass + PEDOT thin film
(120 nm) FTO glass TiO ₂ Screen printing
(Thickness: 8 占 퐉) TBAP 0.1 M
in PC Example 2 ITO glass + PEDOT thin film
(120 nm) FTO glass TiO ₂ Spin coating
(Thickness: 300 nm) TBAP 0.2 M
in PC Example 3 ITO Film + PEDOT Thin Film
(120 nm) FTO glass MoO ₃ Screen printing
(Thickness: 3 占 퐉) LiClO ₄ 0.5 M
in PC Example 4 ITO Film + PEDOT Thin Film
(120 nm) FTO glass V ₂ O ₅ Spin coating
(Thickness: 200 nm) LiClO ₄ 1 M
in PC Example 5 ITO glass + P3HT thin film
(120 nm) FTO glass Nb ₂ O ₅ Screen printing
(Thickness: 2 占 퐉) LiClO ₄ 0.7 M
in PC Example 6 ITO Film + ProDOT Thin Film
(120 nm) FTO glass + Ag nanowire MoO ₃ Electric radiation
(Thickness: 100 nm) Ionic liquid
(EMIM-PF ₆ ) Example 7 ITO glass + ProDOT thin film
(120 nm) FTO glass + Ag nanowire V ₂ O ₅ Electric radiation
(Thickness: 200 nm) Ionic liquid
(EMIM-PF ₆ ) Example 8 ITO glass + ProDOT thin film
(120 nm) ITO film TiO ₂ Spin coating
(Thickness: 50 nm) TBAP 0.2 M
in PC Example 9 ITO film + PEDOT thin film
(100 nm) ITO film MoO ₃ spin coating
(Thickness: 80 nm) Ionic liquid
(EMIM-PF ₆ ) Example 10 ITO film + ProDOT thin film
(120 nm) ITO film V ₂ O ₅ spin coating
(Thickness: 50 nm) TBAP 0.2 M
in PC

Example  11 to 17: Manufacture of an electric fluorescent device

1) Working electrode manufacturing

ITO glass (0.7 T, 15 Ω / sq) or ITO film (30 Ω / sq), which is a conductive transparent electrode, was used as the substrate of the working electrode used in Examples 11 to 17. In Examples 11, 12 and 16, a solution in which 1% by weight of a poly (fluorene) polymer was dissolved in chloroform was used. Examples 13, 14, 15 and 17 were poly (1,3,4-oxadiazole) A working electrode was prepared by spin coating the ITO glass at 500 rpm to 2,000 rpm using a solution of poly (1,3,4-oxadiazole) polymer in 1% by weight of chloroform. The polymer solutions used in the examples are summarized in Table 2 below.

2) Production of counter electrode

As a counter electrode substrate, FTO glass (Philkington, 2.2 T, 8 Ω / sq) was used as a conductive transparent electrode. ITO film (30 Ω / sq) Were used.

2-1) Preparation of counter electrodes using screen printing: Examples 11 and 15

In order to perform screen printing, an inorganic nanoparticle paste including nanoparticles (average particle size: 20 nm), polymer for binder (ethylcellulose) and solvent (terpineol, Terpineol) was prepared. As the inorganic material used as the nanoparticles, TiO _{2 of} Example 11 and VO ₂ of Example 15 were used. The prepared inorganic nanoparticle paste was coated on the FTO glass surface by a screen printing method and then heat-treated at 500 ° C for 30 minutes to prepare a nanostructure counter electrode having an inorganic nanostructure. The thickness of the inorganic nanostructure was 8 占 퐉 for Example 11 and 7 占 퐉 for Example 15.

2-2) Preparation of counter electrode using spin coating method: Examples 12 to 14

Example 12 used TiO ₂ , Example 13 used NiO, and Example 14 used IrO ₂ as inorganic materials used as nanoparticles for spin coating. Using the nanoparticles, 1 g of the inorganic nanoparticle paste prepared in the same manner as in 2-1) was dispersed in 3.5 g of ethanol to prepare a solution. The above solution was used to spin coat the FTO glass at 1,000 rpm to 3,000 rpm. Thereafter, the nanostructured counter electrode having an inorganic nanostructure formed thereon was heat-treated at 500 DEG C for 30 minutes. The thickness of the inorganic nanostructure was 300 nm in Example 12, and 50 nm in Examples 13 and 14.

2-3) Preparation of counter electrode using low-temperature process: Examples 16 to 17

The nanoparticle dispersion liquid containing 0.55 g of TiO ₂ or NiO nanoparticles (average particle size: 20 nm) and 10 ml of isopropanol (IPA) was spin-coated on the ITO film at 1,000 rpm to 3,000 rpm. Thereafter, the substrate was heat-treated at 150 ° C for 30 minutes to prepare a nanostructure counter electrode having an inorganic nanostructure. The thickness of the inorganic nanostructure was 50 nm in Example 16 and 70 nm in Example 17.

3) Device fabrication

After the conductive surfaces of the working electrode and the counter electrode prepared by the above method were opposed to each other, they were adhered using a spacer (Surlyn, Dupont 1702) having an adhesive force. The thickness of the spacer was 80 mu m. At this time, an electric fluorescent electrolyte in which an electric fluorescent substance was dissolved was used as an electrolyte used. The above-mentioned electric fluorescent substance was prepared by synthesizing a tetrazine-based compound with a technique described in " Advanced Functional Materials, 22, 17, 3556-3561 (2012) ", and a 0.1 to 1 M lithium (bistrifluoro The electrophoretic electrolyte was prepared by dissolving the tetrazine compound in a concentration of 0.005 M in propylene carbonate (PC) electrolyte in which lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) was dissolved. When the fluorescent material was not contained in the electrolyte, a PC solution in which 0.1 to 1 M of LiTFSI was dissolved was used as an electrolyte. Examples 13 to 14 are examples of an ionic liquid, 1-ethyl-3-methylimide (Triflumethylsulfonyl) imide (EMIM-TFSI) was used.

The electrolyte was injected into the space inside the spacer, and the outside of the device was surrounded with epoxy to produce an electric fluorescent device

5 is a photograph of an electrochromic device according to Example 11. Fig.

The counter electrodes, the working electrode and the electrolyte used in the production of the electric fluorescent devices of Examples 11 to 17 are summarized in Table 2 below.

division Working electrode Nanostructured counter electrode Electrolyte Conductive electrode Inorganic nanostructure Example 11 ITO glass + Poly (fluorene) FTO glass TiO ₂ Screen printing
(Thickness: 8 占 퐉) LiTFSI 0.1 M
in PC Example 12 ITO Film + Poly (fluorene) FTO glass TiO ₂ Spin coating
(Thickness: 300 nm) LiTFSI 0.2 M
in PC Example 13 ITO glass + Poly (Oxadiazole) FTO glass NiO Spin coating
(Thickness: 50 nm) Ionic liquid
(EMIM-TFSI) Example 14 ITO Film + Poly (Oxadiazole) FTO glass IrO ₂ spin coating
(Thickness: 50 nm) Ionic liquid
(EMIM-TFSI) Example 15 ITO glass + Poly (Oxadiazole) FTO glass VO ₂ screen printing
(Thickness: 7 mu m) Ionic liquid
(EMIM-TFSI) Example 16 ITO film + Poly (fluorene) ITO film TiO ₂ Spin coating
(Thickness: 50 nm) LiTFSI 0.2 M
in PC Example 17 ITO film + Poly (Oxadiazole) ITO Film NiO Spin coating
(Thickness: 70 nm) LiTFSI 0.2 M
in PC

Example  18 to 26: Electroluminescent device manufacture

1) Working electrode manufacturing

ITO glass (0.7 T, 15 Ω / sq) or ITO film (30 Ω / sq) was used as the substrate of the working electrode used in Examples 18 to 26, Were used.

2) Production of counter electrode

As the substrate of the counter electrode, FTO glass (Philkington, 2.2 T, 8 Ω / sq), which is a conductive transparent electrode, was used.

The inorganic materials used as nanoparticles to perform spin coating and the mixing ratios are as shown in Table 3 below. Using the nanoparticles shown in Table 3 below, inorganic nanoparticle pastes including nanoparticles (average particle size: 20 nm), polymer for binder (ethylcellulose) and solvent (terpineol, Terpineol) were prepared. 1 g of the inorganic nanoparticle paste prepared above was dispersed in 3.5 g of ethanol to prepare a solution. The above solution was used to spin coat the FTO glass at 1,000 rpm to 3,000 rpm. Thereafter, the nanostructured counter electrode having an inorganic nanostructure formed thereon was heat-treated at 500 DEG C for 30 minutes.

3) Device fabrication

After the conductive surfaces of the working electrode and the counter electrode prepared by the above method were opposed to each other, they were adhered using a spacer (Surlyn, Dupont 1702) having an adhesive force. The thickness of the spacer was 80 mu m.

The electrolyte used in Examples 18 to 26 was n-methyl pyrrolidone (NMP) in which 0.1 M of Ru (bpy) ₃ (PF ₆ ) ₂ was dissolved.

The electrolyte was injected into the space inside the spacer and the outside of the device was surrounded with epoxy to prepare an electroluminescent device.

The counter electrodes, the working electrode, and the electrolyte used in the fabrication of the electroluminescent device of Examples 18 to 26 are summarized in Table 3 below.

division Working electrode Nanostructured counter electrode Electrolyte
(Including electroluminescent materials) Conductive electrode Inorganic nanostructure Example 18 FTO glass FTO glass TiO ₂ spin coating
(Thickness: 200 nm) _{Ru (bpy) 3 (PF 6} ) 2 0.1 M
in NMP Example 19 FTO glass FTO glass TiO ₂ , NiO mixed spin coating
(Mixing ratio: 9: 1) _{Ru (bpy) 3 (PF 6} ) 2 0.1 M
in NMP Example 20 FTO glass FTO glass TiO ₂ , NiO mixed spin coating
(Mixing ratio: 8: 2) _{Ru (bpy) 3 (PF 6} ) 2 0.1 M
in NMP Example 21 FTO glass FTO glass TiO ₂ , NiO mixed spin coating
(Mixing ratio: 7: 3) _{Ru (bpy) 3 (PF 6} ) 2 0.1 M
in NMP Example 22 FTO glass FTO glass TiO ₂ , NiO mixed spin coating
(Mixing ratio: 5: 5) _{Ru (bpy) 3 (PF 6} ) 2 0.1 M
in NMP Example 23 ITO Film FTO glass MoO ₃ , NiO mixed spin coating
(Mixing ratio: 5: 5) _{Ru (bpy) 3 (PF 6} ) 2 0.1 M
in NMP Example 24 ITO glass FTO glass MoO ₃ , IrO ₂ mixed spin coating
(Mixing ratio: 5: 5) _{Ru (bpy) 3 (PF 6} ) 2 0.1 M
in NMP Example 25 ITO glass FTO glass V ₂ O ₅ , CoO mixed spin coating
(Mixing ratio: 5: 5) _{Ru (bpy) 3 (PF 6} ) 2 0.1 M
in NMP Example 26 ITO Film FTO glass V ₂ O _{5 ,} NiO mixed spin coating
(Ratio: 5: 5) _{Ru (bpy) 3 (PF 6} ) 2 0.1 M
in NMP

Comparative Example  1: Manufacture of electrochromic device without inorganic nanostructure

Was prepared in the same manner as in Example 1, except that the inorganic nanostructure was not formed on the surface of the counter electrode.

Comparative Example  2: Manufacture of an electric fluorescent device without inorganic nanostructure

Except that the inorganic nanostructure was not formed on the surface of the counter electrode.

Comparative Example  3: Fabrication of electroluminescent device without inorganic nanostructure

Was prepared in the same manner as in Example 18, except that the inorganic nanostructure was not formed on the surface of the counter electrode.

The respective counter electrodes, working electrodes and electrolytes used in the manufacture of the devices of Comparative Examples 1 to 3 are summarized in Table 4 below.

division Nanostructured counter electrode Working electrode Electrolyte Conductive electrode Inorganic nanostructure Comparative Example 1 FTO glass - ITO glass + PEDOT thin film (120 nm) TBAP 0.1 M
in PC Comparative Example 2 FTO glass - ITO glass + Poly (fluorene) LiTFSI 0.1 M
in PC Comparative Example 3 FTO glass - FTO glass _{Ru (bpy) 3 (PF 6} ) 2 0.1 M
in NMP

Experimental Example 1 : Evaluation of electrochromic characteristics

Experiments for evaluating the characteristics of the electrochromic device according to Example 1 and Comparative Example 1 were conducted.

As a device for measuring the transmittance of the electrochromic device, a UV-Vis spectrometer (PerkinElmer, lambda 750) was used. The voltage applied to the device was controlled with a potentiostat (model CHI 624B (CH Instruments, Inc.)). (V _colored ), and the _bleaching voltage (V _bleached ) were measured.

The measurement results are shown in Table 5, Fig. 6 and Fig.

division Driving voltage Stability test Example 1 V _colored = -2.2 V
V _bleached = 2.0 V 20,000 Example 2 V _colored = -2.2 V
V _bleached = 2.0 V 10,000 Example 3 V _colored = -2.2 V
V _bleached = 2.0 V 8,000 Example 4 V _colored = -2.2 V
V _bleached = 2.0 V 15,000 Example 5 V _colored = -2.5 V
V _bleached = 2.5 V 5,000 Example 6 V _colored = -2.5 V
V _bleached = 2.5 V 7,000 Example 7 V _colored = -2.5 V
V _bleached = 2.5 V 3,000 Example 8 V _colored = -2.5 V
V _bleached = 2.5 V 2,000 Example 9 V _colored = -2.5 V
V _bleached = 2.5 V 1,500 Example 10 V _colored = -2.5 V
V _bleached = 2.5 V 3,000 Comparative Example 1 V _colored = -3.0 V
V _bleached = 3.0 V 700

Referring to Table 5, in Examples 1 to 10, light transmittance was stable even after 1,500 to 20,000 cycles, whereas in Comparative Example 1, it was about 700 cycles, indicating low stability compared with the Examples.

6 is a result of measuring the transmittance of Example 1, and the light transmittance was steadily and uniformly changed from 5% to 60%. There was no change in discoloration characteristics even after 20,000 cycles.

7 shows the result of measuring the transmittance of Comparative Example 1. As shown in Fig. 7, in Comparative Example 1, the change in light transmittance between the discoloration and the discoloration was greatly reduced as the cycle did not progress.

Therefore, it has been confirmed that the electrochromic device according to the present invention can be stably driven even when used for a long period of time by using a counter electrode coated with an inorganic nanostructure.

Experimental Example 2 : Evaluation of electric fluorescence characteristics

Experiments were conducted to evaluate the characteristics of the electric fluorescent devices according to Examples 11 to 17 and Comparative Example 2.

As a device for evaluating the characteristics of the electric fluorescent device, a fluorescence spectrophotometer (PerkinElmer, LS55) was used. The voltage applied to the electric fluorescent device was controlled with a potentiostat (model CHI 624B (CH Instruments, Inc.)). Fluorescence intensities were measured while applying extinction voltage (V _quenched ) and recovery voltage (V _recovered ) at which extinction and recovery of fluorescence occurs.

The measurement results are shown in Table 6, Fig. 8 and Fig.

division Driving voltage Stability test Example 11 V _quenched = 2.0 V
V _recovered = -2.2 V 2,000 Example 12 V _quenched = 2.0 V
V _recovered = -2.2 V 2,000 Example 13 V _quenched = -3.0 V
V _recovered = 3.0 V 50 Example 14 V _quenched = -2.5 V
V _recovered = 2.5 V 1,000 Example 15 V _quenched = -2.5 V
V _recovered = 2.5 V 1,000 Example 16 V _quenched = -2.5 V
V _recovered = 2.5 V 300 Example 17 V _quenched = -2.5 V
V _recovered = 2.5 V 500 Comparative Example 2 V _quenched = -2.5 V
V _recovered = 2.5 V 20

Referring to Table 6, the fluorescence intensity was changed according to the applied voltage, and the voltages were switched between 5 seconds and 60 seconds, respectively. As a result, in Examples 11 and 12 according to the present invention, Respectively. However, in Comparative Example 2, the number of switching times is less than 20, indicating that the stability is very low.

Fig. 8 shows a result of measurement of the fluorescence intensity of Example 11, showing high stability.

Fig. 9 shows the result of measuring the fluorescence intensity of Comparative Example 2. As shown in Fig. 9, in Comparative Example 2, the stability of the fluorescence intensity was greatly reduced since the cycle did not proceed much.

Therefore, it has been confirmed that the electric fluorescent device according to the present invention can be stably driven even when used for a long period of time by using a counter electrode coated with an inorganic nanostructure.

Experimental Example 3 : Evaluation of electroluminescence characteristics

Experiments were conducted to evaluate the characteristics of the electroluminescent device according to Examples 18 to 26 and Comparative Example 3.

As a device for evaluating the characteristics of the electroluminescent device, emission intensity was measured using a spectroradiometer (CS-2000, Konica Minolta). The voltage applied to the device was controlled by Function Generators (Agilent 33210A). The voltage of the device was applied from 2 V to 4 V AC and the emission intensity and the light duration were measured at a frequency of 50 Hz.

The measurement results are shown in Table 7 and FIG.

division Driving voltage
(Frequency) Light quantity (a.u.) Light duration Example 18 AC 2.5 V
(50 Hz) 6.3 7 min continuous Example 19 AC 2.5 V
(50 Hz) 12.2 Lasting 5 min Example 20 AC 2.5 V
(50 Hz) 16.5 60 min continuous Example 21 AC 2.5 V
(50 Hz) 7.5 60 min continuous Example 22 AC 3 V
(50 Hz) 6.2 7 min continuous Example 23 AC 3 V
(50 Hz) 7.5 Lasting 5 min Example 24 AC 3 V
(50 Hz) 15 Lasts 10 min Example 25 AC 3 V
(50 Hz) 8 15 min lasting Example 26 AC 3 V
(50 Hz) 10 Lasting 5 min Comparative Example 3 AC 2 V
(50 Hz) 9.2 2 min continuous

According to Table 7, the light intensity (a.u.) of the embodiment of the present invention was as high as 6.2 to 16.5, and the light duration was 5 to 60 minutes. In particular, Example 20 contained 16.5 a.u. , And this amount of light was maintained for about 60 minutes. However, in the case of Comparative Example 3, the light amount was 9.2 a.u. And the light duration was about 2 minutes.

In Fig. 10, A is Example 18 and B is Comparative Example 3. Referring to FIG. 10, it can be seen that the phosphor A of Example 18 maintains a constant amount of light even after 300 seconds, whereas the phosphor B of Comparative Example 3 sharply decreases the light amount from 100 seconds.

Therefore, it can be seen that the electroluminescent device according to the present invention effectively increases the light quantity and the light duration by applying the inorganic nanostructure on the surface of the counter electrode.

100: 2 electrode element
200: 3 electrode element
300: transistor
2, 22: Working electrode 4, 24: Spacer
6, 26: counter electrode 8, 28, 50: electrolyte
10, 30: inorganic nanostructure 12, 32, 48: power source
40: first electrode 42: second electrode
44: third electrode 46: substrate

Claims (9)

An electrically conductive electrode plate; And
And an inorganic nanostructure formed on one or both surfaces of the electrode plate,
Wherein the inorganic nanostructure has a surface area on the average of 30 to 500 m ² / g,
The electrochemical device is an electroluminescent or electro fluorescent switching device,
Wherein the inorganic nanostructure of the electroluminescent element satisfies the following Condition 1 or Condition 2:
[Condition 1]
V ₂ O _5, and MoO ₃ ; And
IrO _2, and CoO;
[Condition 2]
TiO ₂ and NiO in a weight ratio of 9: 1 to 7: 3.
delete delete The method according to claim 1,
The electrochemical device is an electro-fluorescence switching device,
Wherein the inorganic nanostructure of the electro-optical switching element comprises:
IrO _2, and CoO. The counter electrode for an electrochemical device according to claim 1,
delete The method according to claim 1,
Wherein the thickness of the inorganic nanostructure ranges from 1 nm to 20 占 퐉.
A method of manufacturing a counter electrode for an electrochemical device,
Preparing an inorganic nanoparticle paste;
Applying the inorganic nanoparticle paste to an electrically conductive electrode plate to form an inorganic nanostructure having an average surface area in the range of 30 to 500 m ² / g; And
Comprising the step of heat treating,
The electrochemical device is an electroluminescent or electro fluorescent switching device,
When the electrochemical device is an electroluminescent device,
Wherein the inorganic nanostructure satisfies the following Condition 1 or Condition 2,
When the electrochemical device is an electro-optical switching device,
Wherein the inorganic nanostructure comprises at least one selected from the group consisting of IrO ₂ and CoO.
[Condition 1]
V ₂ O _5, and MoO ₃ ; And
IrO ₂ , and CoO;
[Condition 2]
TiO ₂ and NiO in a weight ratio of 9: 1 to 7: 3.
8. The method of claim 7,
The heat-
At a temperature in the range of 100 to 700 占 폚 for 10 minutes to 3 hours.
10. A counter electrode according to any one of claims 1, 4, and 6;
A working electrode arranged to face the electrode; And
And an electrolyte filled in a space between the two electrodes.

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