KR20160082820A - Solid electrolyte and Light-transmittance variable panel and display device including the same - Google Patents

Abstract

Provided is a solid electrolyte which includes first and second oligomers polymerized by a thiolene reaction, thereby exhibiting excellent ionic conductivity, the penetration ratio, and flexibility. Also provided are a penetration-variable panel comprising the same and a display device.

Description

TECHNICAL FIELD [0001] The present invention relates to a solid electrolyte, a light-transmissive variable panel including the same, and a display device.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display device, and more particularly, to a solid electrolyte having high permeability, high ion conductivity, and high flexibility, and a light transmission variable panel and a display device including the solid electrolyte.

2. Description of the Related Art [0002] As an information society has developed, there has been a growing demand for a display device for displaying images. Recently, a liquid crystal display (LCD), a plasma display panel (PDP) Various flat display devices such as an organic light emitting diode (OLED) display device have been used.

Among these flat panel display devices, a liquid crystal display device and an organic light emitting diode display device are widely used.

The liquid crystal display device displays an image using the optical anisotropy and polarization properties of liquid crystal molecules. For example, in a liquid crystal display device, a liquid crystal layer including liquid crystal molecules is interposed between a pixel electrode and a common electrode, which are alternately arranged on a first substrate and a second substrate facing the first substrate.

On the other hand, the organic light emitting diode display device emits light by forming an organic light emitting layer between the anode and the cathode. Electrons injected from the anode and electrons injected from the cathode are combined in the organic light emitting layer to form excitons, and excitons are emitted from the excited state to the ground state.

In recent years, there is an increasing interest in a transparent display device whose front surface is transparent and which transmits light. Such a transparent display device is being applied to a so-called smart window.

However, since the transparent display device does not have a black state, the contrast ratio is lowered and the visibility of the image is poor. To improve this, a method of using a shield plate on one surface of the display panel has been proposed.

For example, when a voltage is applied to an electrode, an electrochromic device capable of controlling the transmittance by an oxidation-reduction reaction of the electrochromic material is used as a shading plate.

The electrochromic device comprises two substrates on which electrodes are formed and an electrochromic layer formed between the two substrates, and the electrochromic layer is composed of an electrolyte layer and an electrochromic material layer.

Conventionally, liquid electrolytes are mainly used. However, when the liquid electrolyte is used, the electrode material is corroded, the organic solvent is volatilized, and leakage of the liquid electrolyte occurs.

In order to solve the problem of the liquid electrolyte, a solid electrolyte has been proposed. The solid electrolyte includes a polymer and a lithium salt dissociated in the polymer. Polymers include polar elements such as oxygen and nitrogen, and these elements coordinate with the dissociated lithium ion to form a polymer-lithium ion complex.

The most widely studied solid electrolyte materials consist of polyethylene oxide (PEO) and a lithium salt. Such a PEO-based polymer electrolyte has an ionic conductivity of 10 ^-5 S / cm or more at a temperature above the melting point of PEO (67 to 72 ° C), but has an ionic conductivity of about 10 ^-8 S / cm at room temperature. That is, in the case of a crystalline polymer electrolyte such as PEO, the ionic conductivity is very low at a temperature below the melting point of the polymer.

Also, solid electrolytes mixed with polyethylene oxide (PEG) and polyethylene glycol (PEG) have been introduced. However, since the ionic conductivity is not high and the viscosity is too high, there is a problem of requiring a long vacuum drying process.

The solid electrolyte used in the electrochromic device should be transparent and have high ionic conductivity. In addition, flexibility must be high to prevent damage due to external impact.

However, when a polymer electrolyte such as PEO is used, the ion conductivity is too low at room temperature and the transmittance is also poor. Further, since the flexibility is not good, there is a problem that damage is caused by an external impact.

Disclosure of the Invention The present invention aims at solving problems of electrode material corrosion, organic solvent volatilization, liquid leakage, and the like, which are caused when a liquid electrolyte is used, and low ion conductivity, permeability, and flexibility in a conventional solid electrolyte.

In order to solve the above problems, the present invention provides a solid electrolyte comprising a polymer matrix formed by polymerizing an ionic salt, a first oligomer represented by the following general formula (1) and a second oligomer represented by the following general formula (2) do.

[Chemical Formula 1]

(2)

(M1 + m2 = 1 in Formula (1) and m3 + m4 = 1 in Formula (2)).

In the solid electrolyte of the present invention, the polymer matrix is represented by the following formula and x + y = 1.

In the solid electrolyte of the present invention, x may be equal to or greater than y.

In the solid electrolyte of the present invention, the ionic salt may be a lithium salt.

According to another aspect of the present invention, there is provided a plasma display panel comprising first and second substrates facing each other, a first transparent electrode positioned on the first substrate, a second transparent electrode positioned on the second substrate, There is provided a transmissivity-variable panel comprising an electrochromic particle layer positioned between transparent and the second transparent electrode, and a solid electrolyte layer disposed between the second transparent electrode and the electrochromic particle layer.

In another aspect, the present invention provides a display device including the above-described transmissivity-variable panel and a display panel which is disposed on one side of the transmissivity-variable panel and includes a display portion and a transparent portion.

The solid electrolyte of the present invention can be produced by mixing a poly (silsesquioxane) back-bone with a first oligomer having an acrylate moiety and a poly (ethylene) glycol moiety bonded to each other And a second oligomer having a sialene (-SH) moiety bonded to a polysilsesquioxane backbone, the ionic conductivity, permeability, and flexibility of the polymer are improved.

That is, the ionic conductivity is greatly increased by the first oligomer, the free-volumne is formed in the polymer due to the polymerization of the first and second oligomers, the flexibility is increased, and the polymerization by the first and second oligomers The polymer has a high transmittance.

Therefore, the above-mentioned solid polymer and solid electrolyte including an ionic salt have high ion conductivity and permeability while solving problems such as liquid leakage in the liquid electrolyte. Further, since the flexibility is improved, the solid electrolyte layer is prevented from being damaged by an external impact or the like, and can be used for a flexible display device.

Further, the transmittance variable panel using the solid electrolyte and the electrochromic particles of the present invention has improved transmittance and reduced driving voltage.

Further, the power consumption of the display device including the variable transmissivity panel is reduced, and the visibility and the contrast ratio can be improved.

1A to 1D are photographs for explaining the transmittance and haze of a solid electrolyte.
2A to 2C are photographs for explaining the flexibility of the solid electrolyte.
3 is a schematic cross-sectional view of a transmissivity-variable panel according to an embodiment of the present invention.
4 is a schematic cross-sectional view of a display device including a transmissivity-variable panel according to an embodiment of the present invention.
5 is a schematic sectional view of the display panel of Fig.

Hereinafter, preferred embodiments according to the present invention will be described with reference to the drawings.

The solid electrolyte of the present invention comprises a polymer matrix formed by polymerizing a first oligomer represented by the following formula (1) and a second oligomer represented by the following formula (2), and an ionic salt.

The ionic salt may be a lithium salt, for example, LiPF ₆ , LiF, LiBR ₄ (R is a phenyl group or an alkyl group), LiSbF ₆ , LiAsF ₆ , LiBF ₄ , LiClO ₄ , LiCF ₃ SO ₃ , LiN ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiC ₆ F ₉ S ₃ , LiC ₈ F ₁₇ SO ₃ and LiAlCl ₄ .

[Chemical Formula 1]

(2)

M1 + m2 = 1 in Formula (1), and m3 + m4 = 1 in Formula (2). Further, m1 = (2/3) m2 and m3 = (2/3) m4.

That is, the first oligomer has a structure in which an acrylate moiety and a poly (ethylene glycol) moiety are bonded to a poly (silsesquioxane) backbone, The second oligomer has a structure in which a thiolene (-SH) moiety is bonded to the polysilsesquioxane backbone.

The ionic conductivity is greatly improved by the polyethylene glycol moiety of the first oligomer, and the first and second oligomers form a copolymer by the reaction of the acrylate moiety and the thiolene moiety to form a fee-volumne And flexibility is improved. Further, since the benzene ring is substituted for the silsesquioxane, the degree of freedom of the molecule is increased and the flexibility is further improved.

The copolymer formed by the thiolene reaction between the first oligomer of the general formula (1) and the second oligomer of the general formula (2) may be represented by the following general formula (3).

(3)

In formula (3), x + y = 1.

As described above, the solid electrolyte of the present invention has advantages in terms of ionic conductivity, transmittance, and flexibility, including an ionic salt such as a lithium salt, a copolymer formed by polymerization of an oligomer of Formula 1 and an oligomer of Formula 2 .

The solid electrolyte layer of the present invention comprises an electrolyte solution (electrolyte composition) comprising a first oligomer of Formula 1, a second oligomer of Formula 2, a solution containing an ionic salt, and a photoinitiator and / And then curing.

The electrolyte composition may further comprise a plasticizer. For example, plasticizers of propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl nitrile (acetonitrile, benzonitrile, acrylonitrile, and propionitrile) may be used.

Thus, the solid electrolyte layer comprises a copolymer of Formula (III) wherein the first oligomer and the second oligomer are polymerized, and an ionic salt.

[Production of Solid Electrolyte Layer]

[Experimental Example]

The sol solution in which the oligomer of Chemical Formula 1 and / or the oligomer of Chemical Formula 2 was mixed was mixed with propylene carbonate (PC) solution containing 1.5 M Li salt at a weight ratio of 3: 7. Then, an electrolyte solution was prepared by adding a TPO photoinitiator (2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide) at a mass ratio of 0.3% to the oligomer mixture.

Thereafter, an electrolyte solution was coated and cured by irradiating light of 1050 mJ / cm < 2 > to form a solid electrolyte layer.

[Experimental Example 1]

An electrolyte solution was prepared using only the oligomer of formula (2) without the oligomer of formula (1) to form a solid electrolyte layer.

[Experimental Example 2]

An electrolyte solution was prepared using both the oligomer of Formula 1 and the oligomer of Formula 2 to form a solid electrolyte layer. (Mass ratio: oligomer of Formula 1 < oligomer of Formula 2)

[Experimental Example 3]

An electrolyte solution was prepared using both the oligomer of Formula 1 and the oligomer of Formula 2 to form a solid electrolyte layer. (Mass ratio: oligomer of Formula 1 = oligomer of Formula 2)

[Experimental Example 4]

An electrolyte solution was prepared using both the oligomer of Formula 1 and the oligomer of Formula 2 to form a solid electrolyte layer. (Mass ratio: oligomer of formula 1> oligomer of formula 2)

[Experimental Example 5]

An electrolyte solution was prepared using only the oligomer of formula (1) without the oligomer of formula (2) to form a solid electrolyte layer.

Table 1 shows the ion conductivity according to the composition of the electrolyte layer formed through Experimental Examples 1 to 5.

As shown in Table 1, when the oligomer mass ratio of Formula 1 is equal to or greater than the oligomer mass ratio of Formula 2 (Experimental Examples 3 and 4), the ion conductivity is increased.

As described above, since the polyethylene glycol moiety substituted for the oligomer of Formula 1 contributes to the ionic conductivity, the solid electrolyte layer is formed only by the oligomer of Formula 2 without the oligomer of Formula 1 (Experimental Example 1) (Example 2) in which a solid electrolyte layer including an oligomer of 1 is formed, the solid electrolyte layer has a low ionic conductivity.

Further, in the case where a solid electrolyte layer containing only the oligomer of the formula (1) is formed without the oligomer of the formula (2) (Experimental Example 5), the ionic conductivity decreases and the flexibility becomes worse.

Accordingly, the solid electrolyte of the present invention comprises both the oligomer of formula (1) and the oligomer of formula (2), and has a mass ratio of the oligomer of formula (1) equal to or greater than the mass ratio of the oligomer of formula (2), and has a high ionic conductivity. That is, in the formula (3), x may be equal to or greater than y. (x? y)

[Comparative Example 1]

_{LiClO 4 2g, PEO (polyethyleneoxide)} (Mw 60k) 1.9g, PEG (polyethylene glycol) (MW 4000) 1.9g, methanol 4.8g stirring for 12 hours at a temperature 45 ~ 50 ° C to prepare a solid electrolyte solution.

The electrolyte solution was dried in a vacuum to form an electrolyte layer. At this time, a vacuum drying step of 2 hours for forming the electrolyte layer was required.

[Comparative Example 2]

A 1.5M Li salt-containing propylene carbonate solution and trimethylolpropane ethoxylate triacrylate were mixed at a mass ratio of 85:15, and an electrolyte solution was prepared by adding 0.3 to 1 wt% of TPO photoinitiator to the oligomer.

An electrolyte solution was coated thereon, and light of 1100 mJ / cm &lt; 2 &gt; was irradiated to form an electrolyte layer.

[Comparative Example 3]

An electrolyte solution was prepared by mixing a propylene carbonate solution containing 1.5 M Li salt, methoxypolyethylene glycol monoacrylate, and polyethylene glycol dimethacylate in a mass ratio of 6: 3: 1 and then adding 0.3 to 1 wt% of TPO photoinitiator to the oligomer.

An electrolyte solution was coated thereon, and light of 1300 mJ / cm 2 was irradiated to form an electrolyte layer.

The ionic conductivity (room temperature), transmittance, haze, and radius of curvature of the electrolyte layer prepared in Experimental Example 4 and Comparative Examples 1 to 3 were measured and the measurement results are shown in Table 2.

1A to 1D show photographs showing transmittance and haze characteristics of Experimental Example 4 and Comparative Examples 1 to 3, respectively, and the curvature radii of the Experimental Example 4, Comparative Examples 2 and 3, That is, a photograph showing the flexibility is shown in Figs. 2A to 2C. In the case of Comparative Example 1, it was impossible to measure the radius of curvature due to the gel state.

As shown in Table 2 and FIGS. 1A to 1D and 2A to 2C, the solid electrolyte including the copolymer formed by polymerizing the oligomer of Formula 1 and the oligomer of Formula 2 as in the present invention has high ion conductivity And has advantages in terms of transmittance, haze and flexibility.

3 is a schematic cross-sectional view of a transmissivity-variable panel according to an embodiment of the present invention.

3, the variable transmission panel 100 according to an embodiment of the present invention includes first and second substrates 110 and 120 facing each other, first and second substrates 110 and 120, And a first transparent electrode 130 positioned between the first substrate 110 and the electrochromic layer 140. The electrochromic layer 140 includes a first electrochromic layer 142 and a first electrochromic layer 142, And a second transparent electrode 150 positioned between the second substrate 120 and the electrochromic layer 140.

Each of the first substrate 110 and the second substrate 120 may be made of glass or plastic. For example, each of the first substrate 110 and the second substrate 120 may be formed of polyethylene terephthalate (PET) or polyethylene naphthalate (PEN).

Each of the first transparent electrode 130 and the second transparent electrode 150 is made of a transparent conductive material. For example, the first transparent electrode 130 and the second transparent electrode 150 may be formed of indium-tin-oxide (ITO) or indium-zinc-oxide (IZO) &Lt; / RTI &gt; The variable transmissivity panel of the present invention is formed of a transparent conductive material because the transmissivity must be high in the transmissive mode. Alternatively, when the transmissive panel is formed of a low resistance metal material such as aluminum, the transmissive panel may have a small thickness.

The electrochromic layer 140 is disposed between the first and second substrates 110 and 120, that is, between the first and second transparent electrodes 130 and 150, and includes the electrochromic particles 142 and the solid electrolyte 144, .

The electrochromic particles 142 include a shell (not shown) that surrounds a core (not shown) and a core (not shown).

The core (not shown) may be made of a dielectric material. For example, the core may be made of indium-tin-oxide (ITO) or titanium oxide (TiO2).

The shell (not shown) is made of an electrochromic material. When a voltage is applied, the shell is discolored by an oxidation-reduction reaction so that the electrochromic layer 140 can be used to change the transmittance.

The solid electrolyte 144 includes an ionic salt, which is an ion conductor, and a polymer matrix.

The ionic salt may be a lithium salt, for example, LiPF ₆ , LiF, LiBR ₄ (R is a phenyl group or an alkyl group), LiSbF ₆ , LiAsF ₆ , LiBF ₄ , LiClO ₄ , LiCF ₃ SO ₃ , LiN ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiC ₆ F ₉ S ₃ , LiC ₈ F ₁₇ SO ₃ and LiAlCl ₄ .

The polymer matrix is a copolymer in which the formula (1) is formed by polymerization of an oligomer and an oligomer of the formula (2), that is, the polymer of the formula (3). That is, the solid electrolyte 144 of the present invention is formed by mixing an acrylate moiety and a poly (ethylene) glycol moiety on a poly (silsesquioxane) backbone And a copolymer in which a first oligomer having a bonded structure and a second oligomer having a structure in which a thiolene (-SH) moiety is bonded to a polysilsesquioxane backbone are polymerized by a thiol reaction.

As described above, the solid electrolyte of the present invention has advantages in terms of ionic conductivity, transmittance, and flexibility, including an ionic salt such as a lithium salt, a copolymer formed by polymerization of an oligomer of Formula 1 and an oligomer of Formula 2 .

Further, the solid electrolyte 144 is formed by using an electrolyte solution containing an oligomer of the formula (I) having a mass ratio equal to or greater than the mass ratio of the oligomer of formula (2), which is advantageous in terms of ion conductivity and flexibility.

The variable transmissivity panel 100 having such a structure has a transmission state or a blocking state by the application of a voltage.

That is, in a state where no voltage is applied to the first and second transparent electrodes 130 and 150, since the electrochromic particles 142 are transparent, the variable transmissivity panel 100 transmits light. On the other hand, when a voltage is applied to the first and second transparent electrodes 130 and 150, the shell (not shown) made of the electrochromic material is discolored, and the light transmittance varying panel 100 blocks light.

At this time, since the solid electrolyte 144 has a high ion conductivity, the variable transmissivity panel 100 of the present invention has a fast response speed.

Further, since the solid electrolyte 144 has a high transmittance, the transmittance of the variable transmittance panel 100 is also improved. In addition, since the solid electrolyte 144 has excellent flexibility, it is possible to prevent damage to the variable transmissivity panel 100 and can be used in a flexible display device.

As described above, the transmissivity-variable panel 100 of the present invention varies in transmittance depending on whether a voltage is applied or not, and can be applied to a so-called transparent display device as described later, thereby improving visibility and contrast ratio of the transparent display device.

4 is a schematic cross-sectional view of a display device including a transmissivity-variable panel according to an embodiment of the present invention.

4, the display device 200 includes a transparent display panel 210 and a transmissivity-variable panel 220 disposed on one side of the transparent display panel 210. As shown in FIG.

The transparent display panel 210 includes a plurality of pixels, and each pixel includes a display portion 212, a circuit portion 214, and a transparent portion 216. The display unit 212 is driven by a voltage or a signal supplied through the circuit unit 214 to display an image. The transparent display panel 210 may be a liquid crystal panel or a light emitting diode panel.

The case where the transparent display panel 210 is a light emitting diode panel will be briefly described.

5, which is a schematic cross-sectional view of the display panel of FIG. 4, the transparent display panel 210 includes a third substrate 301 and a fourth substrate 302 facing each other, (Not shown) is formed between the light emitting diodes 301 and 302, and the display element is a light emitting diode D.

Each of the third substrate 301 and the second substrate 302 may be made of glass or plastic. For example, each of the third substrate 301 and the second substrate 302 may be formed of polyethylene terephthalate (PET) or polyethylene naphthalate (PEN).

A gate wiring (not shown) and a data wiring (not shown) are formed on the third substrate 301 to define a pixel region P and are parallel to a gate wiring (not shown) or a data wiring (not shown) (Not shown) is formed. The display portion 212, the driver 214, and the transparent portion 216 are defined in each pixel region P. [

A switching thin film transistor (not shown) is formed in each pixel region P at the intersection of the gate wiring (not shown) and the data wiring (not shown).

Also, a driving thin film transistor DTr is formed, which is connected to a switching thin film transistor (not shown) and a power supply wiring (not shown).

The driving thin film transistor DTr includes a semiconductor layer 310, a gate electrode 320, and source and drain electrodes 331 and 333. The switching thin film transistor may have a structure similar to that of the driving transistor DTr.

The semiconductor layer 310 includes source and drain regions SR and DR located on both sides of the channel region CR and the channel region CR. The semiconductor layer 310 may be formed of polycrystalline silicon.

Meanwhile, a buffer layer (not shown) may be formed between the semiconductor layer 310 and the third substrate 301.

On the semiconductor layer 310, a gate insulating film 315 is formed. The gate insulating film 315 may be made of an inorganic insulating material such as silicon oxide or silicon nitride.

On the gate insulating film 315, a gate electrode 320 is formed corresponding to the channel region CR. The gate electrode 320 may be made of a low-resistance metal material such as copper or aluminum.

On the gate electrode 320, an interlayer insulating film 325 is formed. A semiconductor contact hole 335 may be formed in the interlayer insulating film 225 and the gate insulating film 315 to expose the source region SR and the drain region DR, respectively. The interlayer insulating film 325 may be made of an inorganic insulating material such as silicon oxide or silicon nitride.

On the interlayer insulating film 325, the source electrode and the drain electrode 331 and 333 are formed. The source and drain electrodes 231 and 233 are in contact with the source region and the drain region SR and DR of the semiconductor layer 310 through the corresponding semiconductor contact hole 235, respectively.

A protective layer 340 may be formed on the source and drain electrodes 331 and 333. The protective layer 340 may be formed of an inorganic insulating material such as silicon oxide or silicon nitride or an organic insulating material such as photoacryl. A drain contact hole 341 exposing the drain electrode 333 is formed in the protection layer 340.

The light emitting diode D is positioned on the protective layer 340 and is electrically connected to the driving thin film transistor DTr through the drain contact hole 341.

In the above-described example, the case where the transistor using the semiconductor layer 310 made of crystalline silicon is formed is taken as an example. As another example, a transistor having an inverted staggered structure using amorphous silicon as a semiconductor layer may be used. As another example, an oxide transistor using an oxide semiconductor may be used.

Although not shown, a storage capacitor is formed in each pixel region P.

The light emitting diode D may include first and second electrodes 351 and 353 and an organic light emitting layer 352 formed between the first and second electrodes 351 and 353.

Here, the first and second electrodes 351 and 353 are configured to have a transparent characteristic. In this regard, the first and second electrodes 251 and 253 may be formed of a transparent conductive material. For example, one of oxide-based transparent conductive materials such as ITO, IZO, GZO, and IGZO may be used. At this time, one of the first and second electrodes 351 and 353 is an anode and the other is a cathode. The positive electrode is made of a material having a relatively large work function value, and the negative electrode is made of a material having a relatively low work function value.

The first electrode 351 is connected to the drain electrode 333 of the driving thin film transistor DTr through the drain contact hole 341 and is patterned in units of the pixel region P. [ The second electrode 353 is integrally formed corresponding to the entire pixel region P of the display panel 310 (FIG. 5).

On the other hand, on the first electrode 351, a bank 360 having an opening per pixel region P may be formed. The bank 360 serves to distinguish adjacent pixel regions P from each other.

An organic light emitting layer 352 is formed for each pixel region P corresponding to the opening of the bank 360. [ The organic light emitting layer 352 functions to emit light by the combination of holes and electrons supplied from the first and second electrodes 351 and 353.

The organic light emitting layer 352 may include a light emitting material layer that substantially emits light. On the other hand, in order to increase the luminous efficiency, the organic light emitting layer 352 may have a multi-layer structure. For example, the organic light emitting layer may further include a hole injecting layer, a hole transporting layer, an electron injecting layer, and an electron transporting layer in addition to the light emitting material layer.

The light emitting diode D having the above-described configuration generates light of a corresponding brightness according to a signal applied to the gate electrode 320 of the driving thin film transistor DTr.

In addition, the fourth substrate 302 is an encapsulation substrate and covers the driving thin film transistor DTr. Although not shown, a barrier layer may be formed between the fourth substrate 302 and the driving thin film transistor DTr to prevent penetration of moisture or the like.

5, the region where the driving element such as the driving thin film transistor DTr is formed corresponds to the driving portion (214 of FIG. 4), and the region where the light emitting diode D is formed corresponds to the display portion (212 of FIG. 4). On the other hand, light is transmitted through the transparent portion (216 in Fig. 4) without forming the driving element and the display element. Also, the display unit 212 and the driving unit 214 may be regions overlapping each other.

Referring again to FIG. 4, the transmittance variable panel 220 includes first and second substrates 232 and 234 opposed to each other, and an electrochromic particle A first transparent electrode 230 positioned between the first substrate 232 and the electrochromic layer 240 and a second transparent electrode 240 disposed between the first substrate 232 and the electrochromic layer 240. The electrochromic layer 240 includes a first substrate 232, And the second transparent electrode 250 positioned between the electrochromic layer 240 and the electrochromic layer 240.

Each of the first substrate 232 and the second substrate 234 may be made of glass or plastic. For example, each of the first substrate 232 and the second substrate 234 may be formed of polyethylene terephthalate (PET) or polyethylene naphthalate (PEN).

4 and 5, the first substrate 232 of the variable transmissivity panel 220 and the fourth substrate 302 of the display panel 210 are shown to have the same configuration, but different substrates are used, So that the transmissivity variable panel 220 and the display panel 210 can be stacked.

Each of the first transparent electrode 230 and the second transparent electrode 250 is made of a transparent conductive material. For example, each of the first transparent electrode 230 and the second transparent electrode 250 may be made of ITO.

The electrochromic layer 240 is disposed between the first and second substrates 232 and 234, that is, between the first and second transparent electrodes 230 and 250, and the electrochromic particles 242 and the solid electrolyte 244, .

The electrochromic particles 242 include a core and a shell. The core may comprise a dielectric material, for example the core may be indium-tin-oxide (ITO) or titanium oxide (TiO2). In addition, the shell is made of an electrochromic material. When a voltage is applied, the shell is discolored by an oxidation-reduction reaction, so that the transmittance of the electrochromic layer 240 can be varied.

The solid electrolyte 244 comprises an ionic salt and a polymeric matrix.

The ionic salt may be a lithium salt, for example, LiPF ₆ , LiF, LiBR ₄ (R is a phenyl group or an alkyl group), LiSbF ₆ , LiAsF ₆ , LiBF ₄ , LiClO ₄ , LiCF ₃ SO ₃ , LiN ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiC ₆ F ₉ S ₃ , LiC ₈ F ₁₇ SO ₃ and LiAlCl ₄ .

The polymer matrix is a copolymer in which the formula (1) is formed by polymerization of an oligomer and an oligomer of the formula (2), that is, the polymer of the formula (3). That is, the solid electrolyte 144 of the present invention is formed by mixing an acrylate moiety and a poly (ethylene) glycol moiety on a poly (silsesquioxane) backbone And a copolymer in which a first oligomer having a bonded structure and a second oligomer having a structure in which a thiolene (-SH) moiety is bonded to a polysilsesquioxane backbone are polymerized by a thiol reaction.

The variable transmissivity panel 220 having such a structure has a transmission state or a blocking state by the application of a voltage.

That is, since the electrochromic particles 242 are transparent in a state where no voltage is applied to the first and second transparent electrodes 230 and 250, the transmittance variable panel 220 transmits light. On the other hand, when a voltage is applied to the first and second transparent electrodes 230 and 250, the shell of the electrochromic particles 242 is discolored, and the transmittance variable panel 220 blocks light.

In other words, since the electrochromic particles 142 have a transparent state in a state in which no voltage is applied to the first and second transparent electrodes 230 and 250, the transmittance variable panel 220 becomes the transparent mode, The light of the portion 216 is transmitted.

However, when a voltage is applied to the first and second transparent electrodes 230 and 250, the electrochromic particles 142 are discolored, so that the transmittance variable panel 220 is in a cutoff mode to cut off the light.

Therefore, the display device 200 of the present invention including the transmissive variable panel 220 is used as a so-called transparent display device.

As described above, as described above, the solid electrolyte of the present invention includes an ionic salt such as a lithium salt, a copolymer formed by polymerization of an oligomer of the formula (1) and an oligomer of the formula (2), and has a high ionic conductivity, It has an advantage in terms of.

Further, the solid electrolyte 144 is formed by using an electrolyte solution containing an oligomer of the formula (I) having a mass ratio equal to or greater than the mass ratio of the oligomer of formula (2), which is advantageous in terms of ion conductivity and flexibility.

Accordingly, the display device 200 including the variable transmissivity panel 220 of the present invention speeds up the transmissive mode and the intercept mode changing speed. Further, since the transmittance variable panel 220 has a high transmittance, the visibility and the contrast ratio of the display device 200 are improved.

Further, since the transmissivity-variable panel 220 has high flexibility, the display device 200 can be made to have a flexible characteristic.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. It can be understood that

100, 220: Transmittance variable panel 110, 120, 232, 234, 301, 302:
130, 150, 230, 250: transparent electrode 140, 240: electrochromic layer
142, 242: electrochromic particles 144, 244: solid electrolyte
200: display device 210: display panel

Claims (6)

An ionic salt;
A polymer matrix formed by polymerizing a first oligomer represented by the following formula (1) and a second oligomer represented by the following formula (2)
&Lt; / RTI &gt;
[Chemical Formula 1]

(2)

(M1 + m2 = 1 in Formula (1) and m3 + m4 = 1 in Formula (2)).
The method according to claim 1,
Wherein the polymer matrix is represented by the following formula and x + y = 1.

3. The method of claim 2,
x is a solid electrolyte greater than or equal to y.
The method according to claim 1,
Wherein the ionic salt is a lithium salt.
A first substrate and a second substrate facing each other;
A first transparent electrode disposed on the first substrate;
A second transparent electrode disposed on the second substrate;
An electrochromic particle layer positioned between the first transparent electrode and the second transparent electrode;
A solid electrolyte layer comprising a solid electrolyte of any one of claims 1 to 4 positioned between the second transparent electrode and the electrochromic particle layer,
And a transmissive panel.
A transmissive variable panel according to claim 5;
The display panel including a display portion and a transparent portion, the display panel being positioned on one side of the transmissivity-
.

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