KR20240024612A - Electrochromic device and windows apparatus having the same - Google Patents

Abstract

Examples include a first substrate; a second substrate disposed on the first substrate; and an electrochromic portion disposed between the first substrate and the second substrate, and provides an electrochromic device having a light transmission change rate of less than 0.25 as measured by the following measurement method.

Description

Electrochromic device and window apparatus including the same {Electrochromic device and windows apparatus having the same}

Embodiments relate to electrochromic devices and window devices including the same.

Electrochromic film is a film whose color changes due to coloring and decolorization due to oxidation-reduction reactions at each anode and cathode due to an applied potential. It is a film that allows the user to artificially control visible light and infrared light, and is available in a variety of types. Inorganic oxides are used as electrode materials.

Various electrochromic films as described above have been developed and applied for patents. Looking at the contents of the patent applications, Korea Patent Publication No. 2001-0087586 discloses a film in which a conductive indium-tin oxide thin film is deposited on a glass film. MoO3, a reduced color oxide, is deposited on one of the two ITO films (1A, 1B), and WO3, a reduced color oxide, is deposited on the other, and then a lithium-based solid electrolyte, an alkali metal, is deposited on it. Polyaniline, a conductive polymer, is put between the two sheets and passed through a high-frequency compression roller to produce a film that changes from transparent to blue when voltage is applied. In Domestic Registered Utility Model Publication No. 0184841, indium-tinoxide is deposited on a glass film with a thickness of 005 mm. After that, WO3, a reduced coloring material, and IrO2, an oxidized coloring material, are deposited on both sides of the transition metal oxide film with α-PEO copolymer, a polymer solid electrolyte, in between, and combined with a high-frequency roller. Discoloration films are known.

Embodiments seek to provide an electrochromic device with improved durability and a window device including the same.

An electrochromic device according to an embodiment includes a first substrate; a second substrate disposed on the first substrate; and an electrochromic portion disposed between the first substrate and the second substrate, and the light transmission change rate measured by Measurement Method 1 below is less than 0.25.

[Measurement method 1]

Through the first substrate, pseudo-solar light is irradiated to the electrochromic portion at an intensity of 1000 W/m2 for 10 minutes, and the first light transmittance of the electrochromic element is measured before irradiation of the pseudo-solar light, and the pseudo-solar light is measured. After irradiation of sunlight, the second light transmittance of the electrochromic element is measured, and the light transmission change rate is the difference between the first light transmittance and the second light transmittance divided by the first light transmittance.

In the electrochromic device according to one embodiment, the haze change measured by Measurement Method 2 below may be less than 5.5%.

[Measurement method 2]

The first haze of the electrochromic device according to the embodiment is measured before irradiation of the pseudo-solar light, and the second haze of the electrochromic device according to the embodiment is measured after irradiation of the pseudo-solar light, and the haze change is determined by the second haze. It is a value obtained by subtracting the first haze from .

In an electrochromic device according to an embodiment, the L* change measured by Measurement Method 3 below may be less than 9.

[Measurement method 3]

The first L* of the first discoloration layer is measured before irradiation of the pseudo-solar light, and the second L* of the first discoloration layer is measured after the irradiation of the pseudo-solar light, and the L* change is the second L* It is the absolute value of the value obtained by subtracting the first L* from .

In the electrochromic device according to one embodiment, the a* change measured by measurement method 4 below may be less than 5.

[Measurement method 4]

The first a* of the first discoloration layer is measured before irradiation of the pseudo-solar light, and the second a* of the first discoloration layer is measured after the irradiation of the pseudo-solar light, and the a* change is the second a* It is the absolute value of the value obtained by subtracting the first a* from .

In an electrochromic device according to an embodiment, the change in b* measured by the measurement method below may be less than 10.

[Measurement Method 5]

The first b* of the first discoloration layer is measured before irradiation of the pseudo-solar light, the 2nd b* of the first discoloration layer is measured after the irradiation of the pseudo-solar light, and the b* change is the second b* It is the absolute value of the value obtained by subtracting the first b* from .

In one embodiment, the electrochromic unit includes a first transparent electrode disposed on the first substrate; a first discoloring layer disposed on the first transparent electrode; an optoelectronic reduction layer disposed on the first discoloration layer; An electrolyte layer disposed on the photoelectron reduction layer; a second discoloration layer disposed on the electrolyte layer; and a second transparent electrode disposed on the second color-changing layer, wherein the first color-changing layer includes an electrochromic material, and the photoelectron reduction layer has a lower band gap than the electrochromic material. It may contain an electron accepting material.

In one embodiment, the electrochromic material may include tungsten oxide, and the electron accepting material may include at least one from the group consisting of carbon black, carbon nanotubes, or graphene.

In one embodiment, the first light transmittance may be 50% to 85%, and the first haze may be 0.1% to 5%.

In one embodiment, the first L* may be from 80 to 100, the first a* may be from -2 to 1.5, and the first b* may be from 0.5 to 4.

In one embodiment, the photoelectron reduction layer may include the electron accepting material and a binder.

A window device according to an embodiment includes a frame; a window mounted on the frame; and an electrochromic element disposed in the window, wherein the electrochromic element includes: a first substrate; a second substrate disposed on the first substrate; and an electrochromic portion disposed between the first substrate and the second substrate, and the light transmission change rate measured by Measurement Method 1 below may be less than 0.25.

[Measurement method 1]

Through the first substrate, pseudo-solar light is irradiated to the electrochromic portion at an intensity of 1000 W/m2 for 10 minutes, and the first light transmittance of the electrochromic element is measured before irradiation of the pseudo-solar light, and the pseudo-solar light is measured. After irradiation of sunlight, the second light transmittance of the electrochromic element is measured, and the light transmission change rate is the difference between the first light transmittance and the second light transmittance divided by the first light transmittance.

The electrochromic device according to the embodiment has a light transmission change rate of less than 0.25. Accordingly, the electrochromic device according to the embodiment can reduce changes in transmittance caused by the external environment, such as external sunlight.

In other words, since the electrochromic device according to the embodiment can reduce the deviation in transmittance caused by external sunlight, the target transmittance during on and off can be easily controlled.

In addition, since the electrochromic device according to the embodiment includes a first laminate and a first color change layer with small haze change, L* change, a* change, and b* change, the appearance change due to external sunlight is small. You can. Accordingly, the electrochromic device according to the embodiment may have a consistent appearance even if the external environment changes.

Additionally, because the electrochromic device according to the embodiment includes the electron-accepting material, it may have a buffering effect against external light and/or driving voltage. Accordingly, the electrochromic device according to the embodiment may have improved durability.

In particular, the electrochromic device according to the embodiment reduces the change in transmittance with respect to external light and reduces the deviation in appearance, so it can be driven by a constant driving voltage. Accordingly, the electrochromic device according to the embodiment can reduce the driving voltage deviation and have improved durability.

1 is a cross-sectional view showing a cross-section of an electrochromic device according to an embodiment.
Figures 2 to 5 are diagrams showing a process for manufacturing an electrochromic device according to an embodiment.
Figure 6 is a cross-sectional view showing an electrochromic device according to another embodiment.
Figure 7 is a diagram illustrating a window device according to an embodiment.

In the description of the embodiment, when each part, surface, layer, or substrate is described as being formed “on” or “under” each part, surface, layer, or substrate, “On” and “under” include those formed “directly” or “indirectly” through other elements. In addition, the standards for the top or bottom of each component are explained based on the drawings. The size of each component in the drawings may be exaggerated for explanation and does not indicate the actual size.

1 is a cross-sectional view showing a cross-section of an electrochromic device according to an embodiment.

Referring to FIG. 1, the electrochromic device according to the embodiment includes a first substrate 100, a second substrate 200, and an electrochromic portion disposed between the first substrate 100 and the second substrate 200. Includes (11).

The electrochromic portion 11 includes a first transparent electrode 300, a second transparent electrode 400, a first color change layer 500, a photoelectron reduction layer 800, a second color change layer 600, and an electrolyte layer. Includes (700).

The first substrate 100, together with the second substrate 200, supports the electrochromic portion 11.

The first substrate 100, together with the second substrate 200, includes the first transparent electrode 300, the first color changing layer 500, the second color changing layer 600, and the second transparent electrode. (400) and supports the electrolyte layer (700).

In addition, the first substrate 100, together with the second substrate 200, includes the first transparent electrode 300, the first color change layer 500, the second color change layer 600, and the second transparent electrode 300. The electrode 400 and the electrolyte layer 700 are sandwiched. The first substrate 100, together with the second substrate 200, includes the first transparent electrode 300, the first color changing layer 500, the second color changing layer 600, and the second transparent electrode ( 400) and the electrolyte layer 700 can be protected from external physical and chemical shock.

The first substrate 100 may include polymer resin. The first substrate 100 may include at least one from the group consisting of polyester-based resin, polyimide-based resin, cyclic olefin polymer resin, polyethersulfone, polycarbonate, or polyolefin-based resin.

The first substrate 100 may include polyester resin as a main component. The first substrate 100 may include polyethylene terephthalate. The first substrate 100 may contain polyethylene terephthalate in an amount of about 90 wt% or more based on the total composition. The first substrate 100 may contain polyethylene terephthalate in an amount of about 95 wt% or more based on the total composition. The first substrate 100 may contain polyethylene terephthalate in an amount of about 97 wt% or more based on the total composition. The first substrate 100 may contain polyethylene terephthalate in an amount of about 98 wt% or more based on the total composition.

The first substrate 100 may include a uniaxially or biaxially stretched polyethylene terephthalate film. The first substrate 100 may include a polyethylene terephthalate film stretched about 2 to about 5 times in the longitudinal direction and/or the width direction.

The first substrate 100 may have high mechanical properties to reinforce the glass when applied to the windows of a building or vehicle.

The first substrate 100 may have a tensile strength of about 7 kgf/mm2 to about 40 kgf/mm2 in the longitudinal direction. The first substrate 100 may have a tensile strength of about 8 kgf/mm2 to about 35 kgf/mm2 in the longitudinal direction.

The first substrate 100 may have a tensile strength of about 7 kgf/mm2 to about 40 kgf/mm2 in the width direction. The first substrate 100 may have a tensile strength of about 8 kgf/mm2 to about 35 kgf/mm2 in the width direction.

The first substrate 100 may have a modulus of about 200 kgf/mm2 to about 400 kgf/mm2 in the longitudinal direction. The first substrate 100 may have a modulus of about 250 kgf/mm2 to about 350 kgf/mm2 in the longitudinal direction. The first substrate 100 may have a modulus of about 250 kgf/mm2 to about 270 kgf/mm2 in the longitudinal direction.

The first substrate 100 may have a modulus of about 200 kgf/mm2 to about 400 kgf/mm2 in the width direction. The first substrate 100 may have a modulus of about 250 kgf/mm2 to about 350 kgf/mm2 in the width direction. The first substrate 100 may have a modulus of about 250 kgf/mm2 to about 270 kgf/mm2 in the width direction.

The first substrate 100 may have an elongation at break of about 30% to about 150% in the longitudinal direction. The first substrate 100 may have an elongation at break of about 30% to about 130% in the longitudinal direction. The first substrate 100 may have an elongation at break of about 40% to about 120% in the longitudinal direction.

The first substrate 100 may have an elongation at break of about 30% to about 150% in the longitudinal direction. The first substrate 100 may have an elongation at break of about 30% to about 130% in the longitudinal direction. The first substrate 100 may have an elongation at break of about 40% to about 120% in the longitudinal direction.

The first substrate 100 may have an elongation at break of about 30% to about 150% in the width direction. The first substrate 100 may have an elongation at break of about 30% to about 130% in the width direction. The first substrate 100 may have an elongation at break of about 40% to about 120% in the width direction.

The modulus, the elongation at break and the tensile strength can be measured according to KS B 5521.

Additionally, the modulus, tensile strength, and elongation at break can be measured by ASTM D882.

Because the first substrate 100 has the improved mechanical strength as described above, the first transparent electrode 300, the second transparent electrode 400, the first color change layer 500, and the second color change layer (600) and the electrolyte layer 700 can be efficiently protected. Additionally, because the first substrate 100 has improved mechanical strength as described above, it can efficiently reinforce the mechanical strength of the glass to which it is to be attached.

Additionally, the first substrate 100 may have high chemical resistance. Accordingly, even if the electrolyte contained in the electrolyte leaks to the first substrate 100, damage to the surface of the first substrate 100 can be minimized.

The first substrate 100 may have improved optical properties. The total light transmittance of the first substrate 100 may be about 55% or more. The total light transmittance of the first substrate 100 may be about 70% or more. The total light transmittance of the first substrate 100 may be about 75% to about 99%. The total light transmittance of the first substrate 100 may be about 80% to about 99%.

The haze of the first substrate 100 may be less than about 20%. It may be from about 0.1% to about 20%. The haze of the first substrate 100 may be about 0.1% to about 10%. The haze of the first substrate 100 may be about 0.1% to about 7%.

The total light transmittance and the haze can be measured by ASTM D 1003, etc.

Since the first substrate 100 has appropriate total light transmittance and haze, the electrochromic device according to the embodiment can have improved optical properties. That is, because the first substrate 100 has appropriate transmittance and haze, the electrochromic device according to the embodiment is applied to the window, appropriately adjusting the transmittance, minimizing distortion of the image from the outside, and improving appearance. You can have

Additionally, the first substrate 100 may have an in-plane retardation of about 100 nm to about 4000 nm. The first substrate 100 may have an in-plane retardation of about 200 nm to about 3500 nm. The first substrate 100 may have an in-plane retardation of about 200 nm to about 3000 nm.

The first substrate 100 may have an in-plane retardation of about 7000 nm or more. The first substrate 100 may have an in-plane retardation of about 7000 nm to about 50000 nm. The first substrate 100 may have an in-plane retardation of about 8000 nm to about 20000 nm.

The in-plane phase difference can be derived from the refractive index and thickness depending on the direction of the first substrate 100.

Since the first substrate 100 has the above-described in-plane retardation, the electrochromic film according to the embodiment may have an improved appearance.

The thickness of the first substrate 100 may be about 10 μm to about 200 μm. The thickness of the first substrate 100 may be about 23 μm to about 150 μm. The thickness of the first substrate 100 may be about 30 μm to about 120 μm.

The first substrate 100 may include organic or inorganic filler. The organic or inorganic filler may function as an anti-blocking agent.

The average particle diameter of the filler may be about 0.1 μm to about 5 μm. The average particle diameter of the filler may be about 0.1 μm to about 3 μm. The average particle diameter of the filler may be about 0.1 μm to about 1 μm.

The filler may be selected from at least one group consisting of silica particles, barium sulfate particles, alumina particles, or titania particles.

Additionally, the filler may be included in the first substrate 100 in an amount of about 0.01 wt% to about 3 wt% based on the entire first substrate 100. The filler may be included in the first substrate 100 in an amount of about 0.05 wt% to about 2 wt% based on the entire first substrate 100.

The first substrate 100 may have a single-layer structure. For example, the first substrate 100 may be a single-layer polyester film.

The first substrate 100 may have a multilayer structure. For example, the first substrate 100 may be a multilayer co-extruded film. The multilayer coextruded structure may include a center layer, a first surface layer, and a second surface layer. The filler may be included in the first surface layer and the second surface layer.

The second substrate 200 faces the first substrate 100. The second substrate 200 is disposed on the first substrate 100. One end of the second substrate 200 may be arranged to be offset from one end of the first substrate 100 . The other end of the second substrate 200 may be arranged to be offset from the other end of the first substrate 100.

The second substrate 200 includes the first substrate 100, the first transparent electrode 300, the first color changing layer 500, the second color changing layer 600, and the second transparent electrode. (400) and supports the electrolyte layer (700).

In addition, the second substrate 200, together with the first substrate 100, includes the first transparent electrode 300, the first color changing layer 500, the second color changing layer 600, and the second transparent electrode 300. The electrode 400 and the electrolyte layer 700 are sandwiched. The second substrate 200, together with the first substrate 100, includes the first transparent electrode 300, the first color changing layer 500, the second color changing layer 600, and the second transparent electrode ( 400) and the electrolyte layer 700 can be protected from external physical and chemical shock.

The second substrate 200 may include polymer resin. The second substrate 200 may include at least one from the group consisting of polyester-based resin, polyimide-based resin, cyclic olefin polymer resin, polyethersulfone, polycarbonate, or polyolefin-based resin.

The second substrate 200 may include polyester resin as a main component. The second substrate 200 may include polyethylene terephthalate. The second substrate 200 may contain polyethylene terephthalate in an amount of about 90 wt% or more based on the total composition. The second substrate 200 may contain polyethylene terephthalate in an amount of about 95 wt% or more based on the total composition. The second substrate 200 may contain polyethylene terephthalate in an amount of about 97 wt% or more based on the total composition. The second substrate 200 may contain polyethylene terephthalate in an amount of about 98 wt% or more based on the total composition.

The second substrate 200 may include a uniaxially or biaxially stretched polyethylene terephthalate film. The second substrate 200 may include a polyethylene terephthalate film stretched about 2 to about 5 times in the longitudinal direction and/or the width direction.

The second substrate 200 may have high mechanical properties to reinforce the glass when applied to the windows of a building or vehicle.

The second substrate 200 may have a tensile strength of about 7 kgf/mm2 to about 40 kgf/mm2 in the longitudinal direction. The second substrate 200 may have a tensile strength of about 8 kgf/mm2 to about 35 kgf/mm2 in the longitudinal direction.

The second substrate 200 may have a tensile strength of about 7 kgf/mm2 to about 40 kgf/mm2 in the width direction. The second substrate 200 may have a tensile strength of about 8 kgf/mm2 to about 35 kgf/mm2 in the width direction.

The second substrate 200 may have a modulus of about 200 kgf/mm2 to about 400 kgf/mm2 in the longitudinal direction. The second substrate 200 may have a modulus of about 250 kgf/mm2 to about 350 kgf/mm2 in the longitudinal direction. The second substrate 200 may have a modulus of about 250 kgf/mm2 to about 270 kgf/mm2 in the longitudinal direction.

The second substrate 200 may have a modulus of about 200 kgf/mm2 to about 400 kgf/mm2 in the width direction. The second substrate 200 may have a modulus of about 250 kgf/mm2 to about 350 kgf/mm2 in the width direction. The second substrate 200 may have a modulus of about 250 kgf/mm2 to about 270 kgf/mm2 in the width direction.

The second substrate 200 may have an elongation at break of about 30% to about 150% in the longitudinal direction. The second substrate 200 may have an elongation at break of about 30% to about 130% in the longitudinal direction. The second substrate 200 may have an elongation at break of about 40% to about 120% in the longitudinal direction.

The second substrate 200 may have an elongation at break of about 30% to about 150% in the longitudinal direction. The second substrate 200 may have an elongation at break of about 30% to about 130% in the longitudinal direction. The second substrate 200 may have an elongation at break of about 40% to about 120% in the longitudinal direction.

The second substrate 200 may have an elongation at break of about 30% to about 150% in the width direction. The second substrate 200 may have an elongation at break of about 30% to about 130% in the width direction. The second substrate 200 may have an elongation at break of about 40% to about 120% in the width direction.

Because the second substrate 200 has the improved mechanical strength as described above, the first transparent electrode 300, the second transparent electrode 400, the first color changing layer 500, and the second color changing layer (600) and the electrolyte layer 700 can be efficiently protected. Additionally, because the second substrate 200 has improved mechanical strength as described above, it can efficiently reinforce the mechanical strength of the glass to which it is to be attached.

Additionally, the second substrate 200 may have high chemical resistance. Accordingly, even if the electrolyte contained in the electrolyte leaks to the second substrate 200, damage to the surface of the second substrate 200 can be minimized.

The second substrate 200 may have improved optical properties. The total light transmittance of the second substrate 200 may be about 55% or more. The total light transmittance of the second substrate 200 may be about 70% or more. The total light transmittance of the second substrate 200 may be about 75% to about 99%. The total light transmittance of the second substrate 200 may be about 80% to about 99%.

The haze of the second substrate 200 may be less than about 20%. It may be from about 0.1% to about 20%. The haze of the second substrate 200 may be about 0.1% to about 10%. The haze of the second substrate 200 may be about 0.1% to about 7%.

Since the second substrate 200 has appropriate total light transmittance and haze, the electrochromic device according to the embodiment can have improved optical properties. That is, since the second substrate 200 has appropriate transmittance and haze, the electrochromic device according to the embodiment is applied to the window, appropriately adjusting the transmittance, minimizing distortion of the image from the outside, and improving appearance. You can have

Additionally, the second substrate 200 may have an in-plane retardation of about 100 nm to about 4000 nm. The second substrate 200 may have an in-plane retardation of about 200 nm to about 3500 nm. The second substrate 200 may have an in-plane retardation of about 200 nm to about 3000 nm.

The second substrate 200 may have an in-plane retardation of about 7000 nm or more. The second substrate 200 may have an in-plane retardation of about 7000 nm to about 50000 nm. The second substrate 200 may have an in-plane retardation of about 8000 nm to about 20000 nm.

The in-plane retardation may be derived from the refractive index and thickness of the second substrate 200 according to its direction.

Since the second substrate 200 has the above-described in-plane retardation, the electrochromic device according to the embodiment may have an improved appearance.

The thickness of the second substrate 200 may be about 10 μm to about 200 μm. The thickness of the first substrate 100 may be about 23㎛ to about 150㎛. The thickness of the first substrate 100 may be about 30 μm to about 120 μm.

The second substrate 200 may include organic or inorganic filler. The organic or inorganic filler may function as an anti-blocking agent.

The average particle diameter of the filler may be about 0.1 μm to about 5 μm. The average particle diameter of the filler may be about 0.1 μm to about 3 μm. The average particle diameter of the filler may be about 0.1 μm to about 1 μm.

The filler may be selected from at least one group consisting of silica particles, barium sulfate particles, alumina particles, or titania particles.

Additionally, the filler may be included in the second substrate 200 in an amount of about 0.01 wt% to about 3 wt% based on the entire second substrate 200. The filler may be included in the second substrate 200 in an amount of about 0.05 wt% to about 2 wt% based on the entire second substrate 200.

The second substrate 200 may have a single-layer structure. For example, the second substrate 200 may be a single-layer polyester film.

The second substrate 200 may have a multilayer structure. For example, the second substrate 200 may be a multilayer co-extruded film.

The first substrate 100 and the second substrate 200 may be flexible. Accordingly, the electrochromic device according to the embodiment may be flexible as a whole.

The first transparent electrode 300 is disposed on the first substrate 100. The first transparent electrode 300 may be formed by depositing on the first substrate 100. Additionally, a hard coating layer may be further included between the first transparent electrode 300 and the first substrate 100.

The first transparent electrode 300 is made of tin oxide, zinc oxide, silver (Ag), chromium (Cr), indium tin oxide (ITO), fluorine doped tin oxide (FTO), and aluminum. Aluminum doped Zinc Oxide (AZO), Gallium doped Zinc Oxide (GZO), Antimony doped Tin Oxide (ATO), Indium zinc oxide (IZO), It may include at least one from the group consisting of Niobium doped Titanium Oxide (NTO) or Cadmium Tin Oxide (CTO).

Additionally, the first transparent electrode 300 may include graphene, silver nanowire, and/or metal mesh.

The first transparent electrode 300 may have a total light transmittance of about 80% or more. The first transparent electrode 300 may have a total light transmittance of about 85% or more. The first transparent electrode 300 may have a total light transmittance of about 88% or more.

The first transparent electrode 300 may have a haze of less than about 10%. The first transparent electrode 300 may have a haze of less than about 7%. The first transparent electrode 300 may have a haze of less than about 5%.

The sheet resistance of the first transparent electrode 300 may be about 1Ω/sq to 60Ω/sq. The sheet resistance of the first transparent electrode 300 may be about 1Ω/sq to 40Ω/sq. The sheet resistance of the first transparent electrode 300 may be about 1Ω/sq to 30Ω/sq.

The thickness of the first transparent electrode 300 may be about 50 nm to about 50 μm. The thickness of the first transparent electrode 300 may be about 100 nm to about 10 μm. The thickness of the first transparent electrode 300 may be about 150 nm to about 5 μm.

The first transparent electrode 300 is electrically connected to the first color change layer 500. Additionally, the first transparent electrode 300 is electrically connected to the electrolyte layer 700 through the first discoloration layer 500.

The second transparent electrode 400 is disposed below the second substrate 200. The second transparent electrode 400 may be formed by depositing on the second substrate 200. Additionally, a hard coating layer may be further included between the second transparent electrode 400 and the second substrate 200.

The second transparent electrode 400 is made of tin oxide, zinc oxide, silver (Ag), chromium (Cr), indium tin oxide (ITO), fluorine doped tin oxide (FTO), and aluminum. Aluminum doped Zinc Oxide (AZO), Gallium doped Zinc Oxide (GZO), Antimony doped Tin Oxide (ATO), Indium zinc oxide (IZO), It may include at least one from the group consisting of Niobium doped Titanium Oxide (NTO) or Cadmium Tin Oxide (CTO).

Additionally, the second transparent electrode 400 may include graphene, silver nanowire, and/or metal mesh.

The second transparent electrode 400 may have a total light transmittance of about 80% or more. The second transparent electrode 400 may have a total light transmittance of about 85% or more. The second transparent electrode 400 may have a total light transmittance of about 88% or more.

The second transparent electrode 400 may have a haze of less than about 10%. The second transparent electrode 400 may have a haze of less than about 7%. The second transparent electrode 400 may have a haze of less than about 5%.

The sheet resistance of the second transparent electrode 400 may be about 1Ω/sq to 60Ω/sq. The sheet resistance of the second transparent electrode 400 may be about 1Ω/sq to 40Ω/sq. The sheet resistance of the second transparent electrode 400 may be about 1Ω/sq to 30Ω/sq.

The thickness of the second transparent electrode 400 may be about 50 nm to about 50 μm. The thickness of the second transparent electrode 400 may be about 100 nm to about 10 μm. The thickness of the second transparent electrode 400 may be about 150 nm to about 5 μm.

The second transparent electrode 400 is electrically connected to the second color change layer 600. Additionally, the second transparent electrode 400 is electrically connected to the electrolyte layer 700 through the second discoloration layer 600.

The first discoloration layer 500 is disposed on the first transparent electrode 300. The first discoloration layer 500 may be placed directly on the upper surface of the first transparent electrode 300. The first discoloration layer 500 may be directly electrically connected to the first transparent electrode 300.

The first discoloration layer 500 is electrically connected to the first transparent electrode 300. The first discoloration layer 500 may be directly connected to the first transparent electrode 300. Additionally, the first discoloration layer 500 is electrically connected to the electrolyte layer 700. The first discoloration layer 500 may be electrically connected to the electrolyte layer 700.

The first color changing layer 500 may change color by receiving electrons. The first color changing layer 500 may include a first electrochromic material that changes color when supplied with electrons. The first electrochromic material is tungsten oxide, niobium pentaoxide, vanadium pentaoxide, titanium oxide, molybdenum oxide, vilogen, or poly(3,4-ethylenedioxythiophene). ;PEDOT) may include at least one from the group.

The first color changing layer 500 may include the first electrochromic material in particle form. The tungsten oxide, niobium pentaoxide, vanadium pentaoxide, titanium oxide, and molybdenum oxide may be particles having an average particle diameter of about 1 nm to about 200 nm. The average particle diameter of the first electrochromic material may be about 5 nm to about 100 nm. The average particle diameter of the first electrochromic material may be about 10 nm to about 50 nm.

The first color changing layer 500 may include the first electrochromic material in an amount of about 70 wt% to about 98 wt% based on the total weight of the first color changing layer 500. The first color changing layer 500 may include the first electrochromic material in an amount of about 80 wt% to about 96 wt% based on the total weight of the first color changing layer 500. The first color changing layer 500 may include the first electrochromic material in an amount of about 85 wt% to about 94 wt% based on the total weight of the first color changing layer 500.

Since the first color changing layer 500 includes the first electrochromic material in the average particle diameter and weight range, the electrochromic device according to the embodiment may have improved optical and electrochromic properties.

Additionally, the first discoloration layer 500 may further include a binder. The binder may be an inorganic binder. The binder may include silica gel. The binder may be formed of silica sol containing tetramethoxysilane or methyltrimethoxysilane.

The first discoloring layer 500 may include the binder in an amount of about 1 wt% to 20 wt% based on the total weight of the first discoloring layer 500. The first discoloring layer 500 may include the binder in an amount of about 5 wt% to 15 wt% based on the total weight of the first discoloring layer 500. The first discoloring layer 500 may include the binder in an amount of about 7 wt% to 13 wt% based on the total weight of the first discoloring layer 500.

The photoelectron reduction layer 800 is disposed on the first color change layer 500. The photoelectron reduction layer 800 is disposed on the first color change layer 500. The photoelectron reduction layer 800 may be directly disposed on the upper surface of the first color change layer 500. The photoelectron reduction layer 800 may be in direct contact with the upper surface of the first color change layer 500.

The photoelectron reduction layer 800 is disposed below the electrolyte layer 700. The photoelectron reduction layer 800 is disposed between the first discoloration layer 500 and the electrolyte layer 700. The photoelectron reduction layer 800 is in direct contact with the lower surface of the electrolyte layer 700. The photoelectron reduction layer 800 is electrically connected to the first color change layer 500 and the electrolyte layer 700.

The photoelectron reduction layer 800 further includes an electron accepting material. The electron accepting material may accept electrons generated from the first electrochromic material.

The electron accepting material may include at least one from the group consisting of carbon black, carbon nanotubes, or graphene.

The photoelectron reduction layer 800 may include the electron accepting material in the form of particles. The average particle diameter of the electron accepting material may be from about 1 nm to about 200 nm. The average particle diameter of the electron accepting material may be from about 5 nm to about 100 nm. The average particle diameter of the electron accepting material may be about 10 nm to about 50 nm.

The average particle diameter of the first electrochromic material and the electron accepting material may be measured by dynamic light scattering. Additionally, the average particle diameter of the first electrochromic material and the electron accepting material may be a D50 average particle diameter.

The nitrogen adsorption surface area of the electron accepting material may be about 50 m2/g to about 200 m2/g. The nitrogen adsorption surface area of the electron accepting material may be about 70 m2/g to about 150 m2/g. The nitrogen adsorption surface area may be a specific surface area calculated by the low-temperature nitrogen adsorption method (JIS K6217).

The tinting strength of the electron accepting material may be about 100% to about 150%. The coloring power of the electron accepting material can be measured according to JIS K6217.

Oil adsorption of the electron accepting material may be about 50 cm3/100g to about 150 cm3/100g. Oil adsorption of the electron accepting material can be measured according to JIS K6221.

The acid value (pH value) of the electron accepting material may be about 3.0 to about 4.0. The acid value of the electron-accepting material can be measured using a glass electrode pH meter after the electron-accepting material is mixed with distilled water.

The photoelectron reduction layer 800 may include the electron accepting material in an amount of about 80 wt% to 99 wt% based on the total weight of the photoelectron reduction layer 800. The photoelectron reduction layer 800 may include the electron accepting material in an amount of about 85 wt% to about 95 wt% based on the total weight of the photoelectron reduction layer 800. The photoelectron reduction layer 800 may include the electron accepting material in an amount of about 87 wt% to 93 wt% based on the total weight of the photoelectron reduction layer 800.

The photoelectron reduction layer 800 may further include the binder. The photoelectron reduction binder may be an inorganic binder. The binder may include silica gel. The binder may be formed of silica sol containing tetramethoxysilane or methyltrimethoxysilane.

The photoelectron reduction layer 800 may include the binder in an amount of about 1 wt% to 20 wt% based on the total weight of the photoelectron reduction layer 800. The photoelectron reduction layer 800 may include the binder in an amount of about 5 wt% to 15 wt% based on the total weight of the photoelectron reduction layer 800. The photoelectron reduction layer 800 may include the binder in an amount of about 7 wt% to 13 wt% based on the total weight of the photoelectron reduction layer 800.

Since the photoelectron reduction layer 800 includes the electron accepting material within the average particle diameter and weight range, the electrochromic device according to the embodiment may have improved optical and electrochromic properties.

The electron accepting material may have a smaller bandgap than the first electrochromic material.

The band gap of the first electrochromic material may be about 2.0 eV to about 3.5 eV. The band gap of the first electrochromic material may be about 2.2 eV to about 3.2 eV. The band gap of the first electrochromic material may be about 2.3 eV to about 3.0 eV.

The band gap of the electron accepting material may be about 1.0 eV to about 3.0 eV. The band gap of the electron accepting material may be about 1.5 eV to about 2.6 eV. The band gap of the electron accepting material may be about 1.8 eV to about 2.4 eV.

The difference between the conduction band of the first electrochromic material and the conduction band of the electron accepting material may be less than about 0.5 eV. The difference between the conduction band of the first electrochromic material and the conduction band of the electron accepting material may be less than about 0.4 eV. The difference between the conduction band of the first electrochromic material and the conduction band of the electron accepting material may be less than about 0.3 eV.

When external light, such as sunlight, is irradiated to the first color changing layer 500, the first electrochromic material may be excited, and the first electrochromic material may photochange. At this time, the excited electrons of the first electrochromic material may be transferred to the photoelectron reduction layer 800. Accordingly, the electron-accepting material can suppress photodiscoloration of the first electrochromic material.

Electrons transferred to the photoelectron reduction layer 800 may be transferred to the first transparent electrode 300, etc.

The thickness of the optoelectronic reduction layer 800 may be about 5 nm to about 200 nm. The thickness of the optoelectronic reduction layer 800 may be about 5 nm to about 100 nm. The thickness of the optoelectronic reduction layer 800 may be about 5 nm to about 50 nm.

The second color change layer 600 is disposed below the second transparent electrode 400. The second discoloration layer 600 may be directly disposed on the lower surface of the second transparent electrode 400. The second discoloration layer 600 may be directly electrically connected to the second transparent electrode 400.

The second color changing layer 600 is electrically connected to the second transparent electrode 400. The second color change layer 600 may be directly connected to the second transparent electrode 400. Additionally, the second discoloration layer 600 is electrically connected to the electrolyte layer 700. The second discoloration layer 600 may be electrically connected to the electrolyte layer 700.

The second color changing layer 600 may change color as it loses electrons. The second color changing layer 600 may include a second electrochromic material that is oxidized and changes color while losing electrons. The second discoloration layer 600 may include at least one from the group consisting of Prussian blue, nickel oxide, and iridium oxide.

The second color changing layer 600 may include the second electrochromic material in particle form. The Prussian blue, nickel oxide, and iridium oxide may be particles having a particle size of about 1 nm to about 200 nm.

Additionally, the second discoloration layer 600 may further include the binder.

The second substrate 200, the second transparent electrode 400, and the second color change layer 600 are included in the second laminate. That is, the second laminate includes the second substrate 200, the second transparent electrode 400, and the second discoloration layer 600. The second laminate may be composed of the second substrate 200, the second transparent electrode 400, and the second discoloration layer 600.

The electrolyte layer 700 is disposed on the first discoloration layer 500. Additionally, the electrolyte layer 700 is disposed below the second discoloration layer 600. The electrolyte layer 700 is disposed between the first discoloring layer 500 and the second discoloring layer 600.

The electrolyte layer 700 may include a solid polymer electrolyte containing metal ions or an inorganic hydrate. The electrolyte layer 700 may include lithium ions (Li+), sodium ions (Na+), potassium ions (K+), etc.

Specifically, Poly-AMPS, PEO/LiCF ₃ SO ₃ , etc. can be used as the solid polymer electrolyte, and Sb ₂ O ₅ .4H ₂ O, etc. can be used as the inorganic hydrate.

Additionally, the electrolyte layer 700 is configured to provide electrolyte ions involved in electrochromic reaction. The electrolyte ion may be, for example, a monovalent cation such as H+, Li+, Na+, K+, Rb+, or Cs+.

The electrolyte layer 700 may include an electrolyte. As examples of the electrolyte, liquid electrolyte, gel polymer electrolyte, or inorganic solid electrolyte can be used without limitation. Additionally, the electrolyte may be used in the form of a single layer or film so that it can be stacked together with the electrode or substrate.

The type of electrolyte salt used in the electrolyte layer 700 is not particularly limited as long as it can contain a compound capable of providing monovalent cations, that is, H+, Li+, Na+, K+, Rb+, or Cs+. For example, the electrolyte layer 700 includes LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCl, LiBr, LiI, LiB ₁₀ Cl ₁₀ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiAsF ₆ , LiSbF ₆ , Lithium salt compounds such as LiAlCl ₄ , CH ₃ SO ₃ Li, CF ₃ SO ₃ Li or (CF ₃ SO ₂ ) ₂ NLi; Alternatively, it may include a sodium salt compound such as NaClO ₄ .

In one example, the electrolyte layer 700 may include a Cl or F element-containing compound as an electrolyte salt. Specifically, the electrolyte layer 700 is LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCl, LiB ₁₀ Cl ₁₀ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiAsF ₆ , LiSbF ₆ , LiAlCl ₄ , CF ₃ It may include one or more electrolyte salts selected from SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, and NaClO ₄ .

The electrolyte may further include a carbonate compound as a solvent. Since carbonate-based compounds have a high dielectric constant, ionic conductivity can be increased. As a non-limiting example, a solvent such as propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or ethylmethyl carbonate (EMC) may be used as a carbonate-based compound.

In another example, when the electrolyte layer 700 includes a gel polymer electrolyte, the electrolyte layer 700 may include poly-vinyl sulfonic acid, poly-styrene sulfonic acid, ), Poly-ethylene sulfonic acid, Poly-2-acrylamido-2methyl-propane sulfonic acid, Poly-perfluoro sulfonic acid acid), poly-toluene sulfonic acid, poly-vinyl alcohol, poly-ethylene imine, poly-vinyl pyrrolidone, poly -Ethylene oxide (Poly-ethylene oxide (PEO)), poly-propylene oxide (PPO), poly-(ethylene oxide, siloxane) (PEOS), poly- (ethylene glycol, siloxane)(poly-(ethylene glycol, siloxane)), poly-(propylene oxide, siloxane)(poly-(propylene oxide, siloxane)), poly-(ethylene oxide, methyl methacrylate)(poly- (ethylene oxide, methyl methacrylate) (PEO-PMMA)), poly-(ethylene oxide, acrylic acid) (PEO PAA)), poly-(propylene glycol, methyl methacrylate)( It may include polymers such as poly-(propylene glycol, methyl methacrylate) (PPG PMMA)), poly-ethylene succinate, or poly-ethylene adipate. In one example, a mixture of two or more or a copolymer of two or more of the polymers listed above may be used as the polymer electrolyte.

Additionally, the electrolyte layer 700 may include a curable resin that can be hardened by ultraviolet ray irradiation or heat. The curable resin may be at least one selected from the group consisting of acrylate-based oligomers, polyethylene glycol-based oligomers, urethane-based oligomers, polyester-based oligomers, polyethylene glycol dimethyl, or polyethylene glycol diacrylate. Additionally, the electrolyte layer 700 may include a photocuring initiator and/or a thermal curing initiator.

The thickness of the electrolyte layer 700 may be about 10 ㎛ to about 200 ㎛. The thickness of the electrolyte layer 700 may be about 50 μm to about 150 μm.

The electrolyte layer 700 may have a transmittance in the range of 60% to 95%. Specifically, the electrolyte layer 700 may have a transmittance of 60% to 95% for visible light in the wavelength range of 380 nm to 780 nm, more specifically, 400 nm wavelength or 550 nm wavelength. The transmittance can be measured using a known haze meter (HM).

The electrochromic device according to the embodiment may further include a sealing portion (not shown).

The sealing portion includes a curable resin. The sealing part may include a thermosetting resin and/or a photo-curing resin.

Examples of the thermosetting resin include epoxy resin, melamine resin, urea resin, or unsaturated polyester resin. In addition, examples of the epoxy resin include phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, biphenyl novolak-type epoxy resin, trisphenol novolak-type epoxy resin, dicyclopentadiene novolak-type epoxy resin, and bisphenol A type. Epoxy resin, bisphenol F type epoxy resin, 2, 2'-diaryrbisphenol A type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, propylene oxide added bisphenol A type epoxy resin, biphenyl form Examples include epoxy resins, naphthalene type epoxy resins, resorcinol type epoxy resins, and glycidyl amines.

Additionally, the sealing part may further include a heat curing agent. Hydrazide compounds such as 1, 3-bis [hydrazinocarbonoethyl 5-isopropyl hydantoin] and adipic acid dihydrazide; dicyandiamide, guanidine derivatives, 1-cyanide Noethyl-2-phenylimidazole, N-[2-(2-methyl-1-imidazolyl) ethyl]urea, 2, 4-diamino-6-[2'-methylimidazolyl (1') ]-Ethyl-s-Thorazine, N, N'-Bis(2-methyl-1-imidazolyl ethyl) urea, N, N'-(2-methyl-1-imidazolyl ethyl)-aziformami , 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 2-imidazoline-2-thiol, 2, 2'-thiogethanethiol, addition products of various amines with epoxy resins, etc. You can.

The first sealing part may include a photo-curable resin. Examples of the photo-curable resin include acrylate-based resins such as urethane acrylate. Additionally, the sealing part may further include a photo curing initiator. The photo curing initiator may be at least one selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.

Additionally, the sealing portion may further include a moisture absorbent such as zeolite and/or silica. Additionally, the sealing portion may further include an inorganic filler. The inorganic filler may be a material with high insulating properties, transparency, and durability. Examples of the inorganic filler include silicon, aluminum, zirconia, or mixtures thereof.

Additionally, the electrochromic device according to the embodiment may further include a first bus bar (not shown) and a second bus bar (not shown).

The first bus bar may be disposed on the first transparent electrode 300. The first bus bar may be connected to the first transparent electrode 300.

The first bus bar may be electrically connected to the first transparent electrode 300. The first bus bar may be in direct contact with the upper surface of the first transparent electrode 300. The first bus bar may be connected to the first transparent electrode 300 through solder.

The second bus bar is disposed below the second transparent electrode 400. The second bus bar is connected to the second transparent electrode 400.

The second bus bar may be electrically connected to the second transparent electrode 400. The second bus bar may be in direct contact with the lower surface of the second transparent electrode 400. The second bus bar may be connected to the second transparent electrode 400 through solder.

The first bus bar and/or the second bus bar may include metal. The first bus bar and/or the second bus bar may include a metal ribbon. The first bus bar and/or the second bus bar may include conductive paste. The first bus bar and/or the second bus bar may include a binder and a conductive filler.

The electrochromic device according to the embodiment can be manufactured by the following method. Figures 2 to 5 are cross-sectional views showing the process of manufacturing an electrochromic device according to an embodiment.

Referring to FIG. 2, a first transparent electrode 300 is formed on the first substrate 100. The first transparent electrode 300 may be formed through a vacuum deposition process. A metal oxide such as indium tin oxide may be deposited on the first substrate 100 through a sputtering process or the like to form the first transparent electrode 300.

The first transparent electrode 300 may be formed through a coating process. A nano metal wire may be coated with a binder on the first substrate 100 to form the first transparent electrode 300. A conductive polymer may be coated on the first substrate 100 to form the first transparent electrode 300.

Additionally, the first transparent electrode 300 may be formed through a patterning process. A metal layer may be formed on the first substrate 100 by a sputtering process, etc., and the metal layer may be patterned to form a first transparent electrode 300 layer including a metal mesh on the first substrate 100. there is.

Afterwards, a first discoloration layer 500 is formed on the first transparent electrode 300 layer. The first discoloration layer 500 may be formed through a sol-gel coating process. A first sol solution containing a first electrochromic material, a binder, and a solvent may be coated on the first transparent electrode 300 layer. A sol-gel reaction may occur in the coated first sol solution, and the first discoloration layer 500 may be formed.

The first sol solution may include the first electrochromic material in particle form in an amount of about 5 wt% to about 30 wt% based on the total solution weight. The first sol solution may include the binder in an amount of about 0.5 wt% to about 5 wt% based on the total solution weight. The first sol solution may include the solvent in an amount of about 70 wt% to about 95 wt% based on the total weight of the solution.

The first sol solution may further include a dispersant.

The solvent may be at least one selected from the group consisting of alcohols, ethers, ketones, esters, or aromatic hydrocarbons. The solvent is ethanol, propanol, butanol, hexanol, cyclohexanol, diacetone alcohol, ethylene glycol, diethylene glycol, glycerin, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol modobutyl ether. , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclohexanone, acetoacetate ester, methyl acetate, ethyl acetate, At least one or more may be selected from the group consisting of n-propyl acetate and i-butyl acetate.

As described above, the binder may be an inorganic binder.

Referring to FIG. 3, a photoelectron reduction layer 800 is formed on the first discoloration layer 500. In order to form the photoelectron reduction layer 800, a third sol solution is prepared.

The sol solution includes an electron accepting material, a binder, and a solvent.

The third sol solution may include the electron accepting material in particle form in an amount of about 5 wt% to about 30 wt% based on the total solution weight. The third sol solution may include the binder in an amount of about 0.5 wt% to about 5 wt% based on the total solution weight. The third sol solution may include the solvent in an amount of about 70 wt% to about 95 wt% based on the total solution weight.

The third sol solution may further include a dispersant.

The solvent may be at least one selected from the group consisting of alcohols, ethers, ketones, esters, or aromatic hydrocarbons. The solvent is ethanol, propanol, butanol, hexanol, cyclohexanol, diacetone alcohol, ethylene glycol, diethylene glycol, glycerin, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol modobutyl ether. , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclohexanone, acetoacetate ester, methyl acetate, ethyl acetate, At least one or more may be selected from the group consisting of n-propyl acetate and i-butyl acetate.

The third sol solution is coated on the first discoloration layer 500. A sol-gel reaction proceeds in the third sol solution coated on the first discoloration layer 500. Accordingly, the photoelectron receiving layer is formed on the first discoloration layer 500.

Afterwards, an electrolyte composition for forming the electrolyte layer 700 is formed.

The electrolyte composition may include a metal salt, an electrolyte, a photo-curing resin, and a photo-curing initiator. The photo-curable resin includes hexandiol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), ethylene glycol diacrylate (EGDA), and trimethylolpropane triacrylate. TMPTA), trimethylolpropane ethoxylated triacrylate (TMPEOTA), glycerol propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PETA), or Dipenta At least one may be selected from the group consisting of dipentaerythritol hexaacrylate (DPHA).

The metal salt, the electrolyte, and the photo curing initiator may be as described above.

The electrolyte composition is coated on the optoelectronic reduction layer 800. Accordingly, an electrolyte composition coating layer 701 is formed on the photoelectron reduction layer 800.

Referring to FIG. 4, a second transparent electrode 400 is formed on the second substrate 200.

The second transparent electrode 400 may be formed through a vacuum deposition process. A metal oxide such as indium tin oxide may be deposited on the second substrate 200 through a sputtering process or the like to form the second transparent electrode 400.

The second transparent electrode 400 may be formed through a coating process. A nano metal wire may be coated with a binder on the second substrate 200 to form the second transparent electrode 400. A conductive polymer may be coated on the second substrate 200 to form the second transparent electrode 400.

Additionally, the second transparent electrode 400 may be formed through a patterning process. A metal layer may be formed on the second substrate 200 by a sputtering process, etc., and the metal layer may be patterned to form a second transparent electrode layer 400 including a metal mesh on the second substrate 200. there is.

Thereafter, a second discoloration layer 600 is formed on the second transparent electrode 400 layer. The second discoloration layer 600 may be formed through a sol-gel coating process. A second sol solution containing a second electrochromic material, a binder, and a solvent may be coated on the second transparent electrode 400 layer. A sol-gel reaction may occur in the coated second sol solution, and the second discoloration layer 600 may be formed.

The second sol solution may include the second discoloring material in particle form in an amount of about 5 wt% to about 30 wt% based on the total weight of the solution. The second sol solution may include the binder in an amount of about 0.5 wt% to about 5 wt% based on the total solution weight. The second sol solution may include the solvent in an amount of about 70 wt% to about 95 wt% based on the total weight of the solution.

The second sol solution may further include a dispersant.

Referring to FIG. 5, the second substrate 200, the second transparent electrode 400, and the second discoloration layer 600 are stacked on the coated electrolyte composition layer 701. At this time, the second discoloration layer 600 is in direct contact with the coated electrolyte composition layer 701.

Thereafter, the coated electrolyte composition layer 701 is cured by light, and a first laminate including the first substrate 100, the first transparent electrode 300, and the first discoloration layer 500 is formed. and a second laminate including the second substrate 200, the second transparent electrode 400, and the second color change layer 600 are laminated to each other. That is, the first laminate and the second laminate may be adhered to each other by the electrolyte layer 700.

Additionally, the electrochromic device according to the embodiment may have light transmittance. Here, the light transmittance may refer to the light transmittance based on a state in which the electrochromic device is not electrochromic. Additionally, the light transmittance may mean total light transmittance.

The light transmittance of the electrochromic device may be about 50% to about 90%. The light transmittance of the electrochromic device may be about 55% to about 88%. The light transmittance of the electrochromic device may be about 68% to about 86%.

An electrochromic device according to an embodiment may have a light transmission change rate. The light transmittance change rate is the rate of change in light transmittance after exposure to pseudo-sunlight compared to the initial light transmittance.

The light transmission change rate can be measured by measurement method 1 below.

[Measurement method 1]

Through the first substrate 100, pseudo-solar light is irradiated to the electrochromic unit 11 at an intensity of about 1000 W/m2 for 10 minutes, and before irradiation of the pseudo-solar light, the first light of the electrochromic element The transmittance is measured, and the second light transmittance of the electrochromic element is measured after irradiation of the pseudo-solar light, and the light transmittance change rate is calculated by dividing the difference between the first light transmittance and the second light transmittance by the first light transmittance. It is a value.

The light transmission change rate (ΔTR) can be expressed by Equation 1 below.

[Formula 1]

△TR = ( T1 - T2 ) / T1

Here, T1 is the initial light transmittance of the electrochromic device, and T2 is the pseudo-solar light transmitted through the first substrate 100 to the first color changing layer 500 at an intensity of about 1000 W/m2. This is the light transmittance of the electrochromic device after irradiation for 10 minutes.

The pseudo-solar light may be artificial light having a spectrum similar to that of sunlight. The pseudo-solar light can be implemented by a solar simulator.

The light transmission change rate of the electrochromic device according to the embodiment may be less than about 0.25. The light transmission change rate of the electrochromic device according to the embodiment may be 0 to about 0.30. The light transmission change rate of the electrochromic device according to the embodiment may be 0 to about 0.25. The light transmittance change rate of the electrochromic device according to the embodiment may be about 0.01 to about 0.20. The light transmission change rate of the electrochromic device according to the embodiment may be about 0.02 to about 0.18. The light transmission change rate of the electrochromic device according to the embodiment may be about 0.03 to about 0.15.

The light transmittance of the electrochromic device according to the embodiment may be about 45% to about 90%. The light transmittance of the electrochromic device according to the embodiment may be about 50% to about 85%. The light transmittance of the electrochromic device according to the embodiment may be about 60% to about 80%.

The light transmittance after the similar solar light is irradiated to the electrochromic device according to the embodiment may be about 40% to about 80%. The light transmittance after the pseudo-sunlight is irradiated to the electrochromic device according to the embodiment may be about 45% to about 80%. The light transmittance after the pseudo-sunlight is irradiated to the electrochromic device according to the embodiment may be about 50% to about 70%.

The electrochromic device according to the embodiment has the light transmission change rate as described above. Accordingly, the electrochromic device according to the embodiment can reduce changes in transmittance caused by external sunlight, etc.

That is, since the electrochromic device according to the embodiment can reduce the deviation in transmittance caused by external sunlight, it is possible to easily control the target transmittance during on and off.

An electrochromic device according to an embodiment may have haze.

The haze may refer to the haze in a state in which the electrochromic device according to the embodiment is not photochromic or electrochromic.

The haze of the electrochromic device according to the embodiment may be less than about 5%. The haze of the electrochromic device according to the embodiment may be less than about 4%. The haze of the electrochromic device according to the embodiment may be less than about 3%. The haze of the electrochromic device according to the embodiment may be less than about 2%.

Electrochromic devices according to embodiments may have haze changes.

The haze change can be measured by Measurement Method 2 below.

[Measurement method 2]

The first haze of the electrochromic device according to the embodiment is measured before irradiation of the pseudo-solar light, and the second haze of the electrochromic device according to the embodiment is measured after irradiation of the pseudo-solar light, and the haze change is determined by the second haze. It is a value obtained by subtracting the first haze from .

The haze change of the electrochromic device according to the embodiment may be less than 5.5%. The haze change of the electrochromic device according to the embodiment may be less than 5%. The haze change of the electrochromic device according to the embodiment may be less than 4%. The haze change of the electrochromic device according to the embodiment may be less than 3%. The haze change of the electrochromic device according to the embodiment may be less than 2%.

In the electrochromic device according to the embodiment, the haze after irradiation of the pseudo-solar light may be less than about 6%. In the electrochromic device according to the embodiment, the haze after irradiation of the pseudo-solar light may be less than about 5%. In the electrochromic device according to the embodiment, the haze after irradiation of the pseudo-solar light may be less than about 4%. In the electrochromic device according to the embodiment, the haze after irradiation of the pseudo-solar light may be less than about 3%.

The light transmittance may be total light transmittance. The total light transmittance may be the light transmittance in a wavelength range of about 380 nm to about 780 nm.

The light transmittance and haze can be measured by ASTM D1003.

An electrochromic device according to an embodiment may have L*, a*, and b*.

L* of the electrochromic device according to the embodiment may be about 70 to about 100. L* of the electrochromic device according to the embodiment may be about 80 to about 100. L* of the electrochromic device according to the embodiment may be about 91 to about 100. The L* can be measured in a state in which the electrochromic device according to the embodiment does not photochromic and/or electrochromic.

An electrochromic device according to an embodiment may have a change in L*.

The L* change can be measured by measurement method 3 below.

[Measurement method 3]

The first L* of the electrochromic device according to the embodiment is measured before the pseudo-solar light irradiation, and the second L* of the electrochromic device according to the embodiment is measured after the pseudo-solar light irradiation, and the L* change is It is the absolute value of the value obtained by subtracting the first L* from the second L*.

The L* change can be expressed as Equation 2 below.

[Formula 2]

L*change = │2nd L* - 1st L*│

The L* change of the electrochromic device according to the embodiment may be less than 7. The L* change of the electrochromic device may be less than 6. The L* change of the electrochromic device according to the embodiment may be less than 5. The L* change of the electrochromic device according to the embodiment may be less than 4.

In the electrochromic device according to the embodiment, L* after irradiation of the pseudo-solar light may be about 70 to about 95. In the electrochromic device according to the embodiment, L* after irradiation of the pseudo-solar light may be about 76 to about 94.

a* of the electrochromic device according to the embodiment may be -3 to 2. a* of the electrochromic device according to the embodiment may be -2.5 to 1.5. a* of the electrochromic device according to the embodiment may be -2 to 1. The a* can be measured in a state in which the electrochromic device according to the embodiment does not photochromic and/or electrochromic.

The electrochromic device according to the embodiment may have a* change.

The a* change can be measured by measurement method 4 below.

[Measurement method 4]

The first a* of the electrochromic device according to the embodiment is measured before the pseudo-solar light irradiation, the second a* of the electrochromic device according to the embodiment is measured after the pseudo-solar light irradiation, and the a* change is It is the value obtained by subtracting the first a* from the second a*.

The a* change of the electrochromic device according to the example can be expressed by Equation 3 below.

[Formula 3]

a*change = │2nd a* - 1st a*│

The a* change of the electrochromic device according to the embodiment may be less than 6. The a* change of the electrochromic device according to the embodiment may be less than 5. The a* change of the electrochromic device according to the embodiment may be less than 2. The a* change of the electrochromic device according to the embodiment may be less than 3. The a* change of the electrochromic device according to the embodiment may be less than 1.8. The a* change of the electrochromic device according to the embodiment may be less than 1.6. The a* change of the electrochromic device according to the embodiment may be less than 1.5.

In the electrochromic device according to the embodiment, a* after irradiation of the pseudo-solar light may be about -5 to about 0. In the electrochromic device according to the embodiment, a* after irradiation of the pseudo-solar light may be about -4.5 to about 0.

b* of the electrochromic device according to the embodiment may be 0 to 4. b* of the electrochromic device according to the embodiment may be 0.1 to 3.5. b* of the electrochromic device according to the embodiment may be 0.5 to 3. The b* can be measured in a state in which the electrochromic device according to the embodiment does not photochromic and/or electrochromic.

The electrochromic device according to the embodiment may have b* change.

The b*change can be measured by measurement method 5 below.

[Measurement Method 5]

The first b* of the electrochromic device according to the embodiment is measured before the pseudo-solar light irradiation, the second b* of the electrochromic device according to the embodiment is measured after the pseudo-solar light irradiation, and the b* change is It is the value obtained by subtracting the first b* from the second b*.

The b*change can be calculated using Equation 4 below.

[Formula 4]

b* change = │2nd b* - 1st b*│

The b* change of the electrochromic device according to the embodiment may be less than 10. The b*change of the electrochromic device according to the embodiment may be less than 8. The b*change of the electrochromic device according to the embodiment may be less than 7. The b* change of the electrochromic device according to the embodiment may be less than 2.8. The b* change of the electrochromic device according to the embodiment may be less than 2.6. The b* change of the electrochromic device according to the embodiment may be less than 2.5.

b* after the pseudo-solar light is irradiated to the electrochromic device according to the embodiment may be about -5 to about 3. b* after the pseudo-sunlight is irradiated to the electrochromic device according to the embodiment may be about -4.5 to about 2.

The L*, the a*, and the b* can be measured by a colorimeter.

The electrochromic device according to the embodiment may have a haze change as described above. Additionally, the electrochromic device according to the embodiment may have the L* change, the a* change, and the b* change.

Accordingly, the electrochromic device according to the embodiment can reduce changes in appearance due to external sunlight. Accordingly, the electrochromic device according to the embodiment may have a consistent appearance even if the external environment changes.

Additionally, because the electrochromic device according to the embodiment includes the electron-accepting material, it may have a buffering effect against external light and driving voltage. Accordingly, the electrochromic device according to the embodiment may have improved durability.

Figure 6 is a cross-sectional view showing an electrochromic device according to another embodiment.

Referring to FIG. 6, the photoelectron reduction layer may be formed integrally with the first discoloration layer 501. The first color change layer 501 may include the electron accepting material.

The first color changing layer 501 is disposed on the first transparent electrode 300. The first discoloration layer 501 may be placed directly on the top surface of the first transparent electrode 300. The first color change layer 501 may be directly electrically connected to the first transparent electrode 300.

The first color changing layer 501 is electrically connected to the first transparent electrode 300. The first discoloration layer 501 may be directly connected to the first transparent electrode 300. Additionally, the first discoloration layer 501 is electrically connected to the electrolyte layer 700. The first discoloration layer 501 may be electrically connected to the electrolyte layer 700.

The first color changing layer 501 may change color by receiving electrons. The first color changing layer 501 may include a first electrochromic material that changes color when supplied with electrons. The first electrochromic material is tungsten oxide, niobium pentaoxide, vanadium pentaoxide, titanium oxide, molybdenum oxide, vilogen, or poly(3,4-ethylenedioxythiophene). ;PEDOT) may include at least one from the group.

The first color changing layer 501 may include the first electrochromic material in particle form. The tungsten oxide, niobium pentaoxide, vanadium pentaoxide, titanium oxide, and molybdenum oxide may be particles having an average particle diameter of about 1 nm to about 200 nm. The average particle diameter of the first electrochromic material may be about 5 nm to about 100 nm. The average particle diameter of the first electrochromic material may be about 10 nm to about 50 nm.

The first color changing layer 501 may include the first electrochromic material in an amount of about 70 wt% to about 98 wt% based on the total weight of the first color changing layer 501. The first color changing layer 501 may include the first electrochromic material in an amount of about 80 wt% to about 96 wt% based on the total weight of the first color changing layer 500. The first color changing layer 501 may include the first electrochromic material in an amount of about 85 wt% to about 94 wt% based on the total weight of the first color changing layer 501.

Since the first color changing layer 501 includes the first electrochromic material in the average particle diameter and weight range, the first laminate and the electrochromic device according to the embodiment have improved optical properties and electrochromic properties. You can have it.

Additionally, the first discoloration layer 501 may further include a binder. The binder may be an inorganic binder. The binder may include silica gel. The binder may be formed of silica sol containing tetramethoxysilane or methyltrimethoxysilane.

The first discoloring layer 501 may include the binder in an amount of about 1 wt% to 20 wt% based on the total weight of the first discoloring layer 501. The first discoloring layer 501 may include the binder in an amount of about 5 wt% to 15 wt% based on the total weight of the first discoloring layer 501. The first discoloring layer 501 may include the binder in an amount of about 7 wt% to 13 wt% based on the total weight of the first discoloring layer 501.

The first color changing layer 501 further includes an electron accepting material. The electron accepting material may accept electrons generated from the first electrochromic material.

The electron accepting material may include at least one from the group consisting of carbon black, carbon nanotubes, or graphene.

The first color change layer 501 may include the electron accepting material in the form of particles. The average particle diameter of the electron accepting material may be about 1 nm to about 200 nm. The average particle diameter of the electron accepting material may be from about 5 nm to about 100 nm. The average particle diameter of the electron accepting material may be about 10 nm to about 50 nm.

The average particle diameter of the first electrochromic material and the electron accepting material may be measured by dynamic light scattering. Additionally, the average particle diameter of the first electrochromic material and the electron accepting material may be a D50 average particle diameter.

The nitrogen adsorption surface area of the electron accepting material may be about 50 m2/g to about 200 m2/g. The nitrogen adsorption surface area of the electron accepting material may be about 70 m2/g to about 150 m2/g. The nitrogen adsorption surface area may be a specific surface area calculated by the low-temperature nitrogen adsorption method (JIS K6217).

The tinting strength of the electron accepting material may be about 100% to about 150%. The coloring power of the electron accepting material can be measured according to JIS K6217.

Oil adsorption of the electron accepting material may be about 50 cm3/100g to about 150 cm3/100g. Oil adsorption of the electron accepting material can be measured according to JIS K6221.

The acid value (pH value) of the electron accepting material may be about 3.0 to about 4.0. The acid value of the electron-accepting material can be measured using a glass electrode pH meter after the electron-accepting material is mixed with distilled water.

The first color changing layer 501 may include the electron accepting material in an amount of about 0.5 wt% to 7 wt% based on the total weight of the first color changing layer 501. The first color changing layer 501 may include the electron accepting material in an amount of about 0.7 wt% to 5 wt% based on the total weight of the first color changing layer 501. The first color changing layer 501 may include the electron accepting material in an amount of about 0.8 wt% to 3 wt% based on the total weight of the first color changing layer 500.

Since the first color changing layer 501 includes the electron accepting material within the average particle diameter and weight range, the electrochromic device according to the embodiment may have improved optical and electrochromic properties.

The weight ratio of the first electrochromic material and the electron accepting material included in the first color changing layer 501 may be about 20:1 to about 5:1. The weight ratio of the first electrochromic material and the electron accepting material included in the first color changing layer 501 may be about 15:1 to about 8:1. The weight ratio of the first electrochromic material and the electron accepting material included in the first color changing layer 501 may be about 13:1 to about 7:1.

Additionally, the ratio of the average particle diameter of the first electrochromic material and the average particle diameter of the electron accepting material may be about 0.7:1 to about 1.5:1. The ratio of the average particle diameter of the first electrochromic material and the average particle diameter of the electron accepting material may be about 0.8:1 to about 1.4:1.

Since the first electrochromic material and the electron accepting material have the above weight ratio and the above average particle size ratio, the first laminate and the electrochromic device according to the embodiment have improved optical properties and electrochromic properties. You can.

The electron accepting material may have a smaller bandgap than the first electrochromic material.

The band gap of the first electrochromic material may be about 2.0 eV to about 3.5 eV. The band gap of the first electrochromic material may be about 2.2 eV to about 3.2 eV. The band gap of the first electrochromic material may be about 2.3 eV to about 3.0 eV.

The band gap of the electron accepting material may be about 1.0 eV to about 3.0 eV. The band gap of the electron accepting material may be about 1.5 eV to about 2.6 eV. The band gap of the electron accepting material may be about 1.8 eV to about 2.4 eV.

The difference between the conduction band of the first electrochromic material and the conduction band of the electron accepting material may be about 0.5 eV or less. The difference between the conduction band of the first electrochromic material and the conduction band of the electron accepting material may be about 0.4 eV or less. The difference between the conduction band of the first electrochromic material and the conduction band of the electron accepting material may be about 0.3 eV or less.

When external light, such as sunlight, is irradiated to the first color changing layer 501, the first electrochromic material may be excited, and the first electrochromic material may photochange. At this time, because the electron-accepting material is disposed around the first electrochromic material, the excited electrons of the first electrochromic material can be transferred to the electron-accepting material. Accordingly, the electron-accepting material can suppress photodiscoloration of the first electrochromic material.

Electrons transferred to the electron accepting material may be transferred to the first transparent electrode 300, etc.

FIG. 7 is a diagram illustrating a window device 1 according to an embodiment.

Referring to FIG. 7, the window device 1 according to the embodiment includes the electrochromic element 10, a frame 20, windows 31, 32, and 33, a plug-in component 40, and a power source 50. Includes.

The frame 20 may be composed of one or more pieces. For example, the frame 20 may be composed of one or more materials such as vinyl, PVC, aluminum (Al), steel, or fiberglass. The frame 20 fixes the windows 31, 32, and 33 and seals the space between the windows 31, 32, and 33. also,

The frame 20 may hold or include pieces of foam or other material. The frame 20 includes a spacer, and the spacer can be placed between adjacent windows 31, 32, and 33. Additionally, the spacer, together with the adhesive sealant, can airtightly seal the space between the windows 31, 32, and 33.

The windows 31, 32, 33 are fixed to the frame 20. The windows 31, 32, and 33 may be glass panes. The windows 31, 32, 33 are made of conventional silicon oxide (SOx) glass, such as soda lime glass or float glass, consisting of approximately 75% silica (SiO2) plus Na2O, CaO, and some minor additives. It may be a glass substrate of the system. However, any material with suitable optical, electrical, thermal, and mechanical properties may be used. The windows 31, 32, 33 can also be made of, for example, other glass materials, plastics and thermoplastics (e.g. poly(methyl methacrylate), polystyrene, polycarbonate, allyl diglycol carbonate, SAN (styrene acrylonitrile copolymer), poly(4-methyl-1-pentene), polyester, polyamide), or mirror materials. The windows 31, 32, and 33 may include tempered glass.

The windows 31, 32, and 33 may include a first window 31, a second window 32, and a third window 33. The first window 31 and the third window 33 may be disposed on the outermost side, and the second window 32 may be disposed between the first window 31 and the third window 33. there is.

The electrochromic element 10 is disposed between the first window 31 and the second window 32. The electrochromic element 10 may be laminated to the first window 31 and the second window 32.

The electrochromic element 10 may be laminated to the first window 31 using a first polyvinyl butyral sheet. That is, the first polyvinyl butyral sheet may be disposed on the first window 31 and the electrochromic element 10 and laminated on the first window 31 and the electrochromic element 10. .

The electrochromic element 10 may be laminated to the second window 32 by a second polyvinyl butyral sheet. That is, the second polyvinyl butyral sheet may be disposed on the second window 32 and the electrochromic element 10 and laminated on the second window 32 and the electrochromic element 10. .

A space 60 may be formed between the second window 32 and the third window 33. The space may be filled with one or more gases such as argon (Ar), krypton (Kr), or xenon (Xn).

The windows 31, 32, 33 may be any glass pane size for residential or commercial window applications. The size of glass panes can vary widely depending on the specific needs of a home or commercial business. In some embodiments, the windows 31, 32, and 33 may be formed of architectural glass. Architectural glass is commonly used in commercial buildings, but may also be used in residential buildings and typically, although not necessarily, separates the indoor environment from the outdoor environment. In some embodiments, a suitable architectural glass substrate may be at least approximately 20 inches by approximately 20 inches, and may be much larger, for example, approximately 80 inches by approximately 120 inches, or larger. Architectural glass is typically at least about 2 millimeters (mm) thick and can be as thick as 6 mm or more.

In one embodiment, the windows 31, 32, and 33 may have a thickness ranging from approximately 1 mm to approximately 10 mm.

In one embodiment, the windows 31, 32, 33 may be very thin and flexible, such as Gorilla Glass® or WillowTM Glass, each of which is commercially available from Corning, Inc. of Corning, New York. These glasses may be less than 0.3 mm thick or less than about 1 mm thick.

The plug-in component (40) may include a first electrical input (41), a second electrical input (42), a third electrical input (43), a fourth electrical input (44) and a fifth electrical input (45). You can.

Additionally, the power supply unit 50 includes a first power terminal 51 and a second power terminal 52.

The first electrical input 41 is electrically coupled to the first power terminal 51 through one or more wires or other electrical connections, components, or devices.

The first electrical input 41 may include a pin, socket, or other electrical connector or conductor. Additionally, the first electrical input 41 may be electrically connected to the electrochromic element 10 through a first bus bar (not shown). The first bus bar may be electrically connected to the second transparent electrode 400.

The second electrical input 42 is electrically coupled to the second power terminal 52 through one or more wires or other electrical connections, components, or devices.

The second electrical input 42 may include a pin, socket, or other electrical connector or conductor. Additionally, the second electrical input 42 may be electrically connected to the electrochromic element 10 through a second bus bar (not shown). The second bus bar may be electrically connected to the first transparent electrode 300.

The third electrical input 43 may be coupled to device, system, or building ground.

The fourth electrical input 44 and the fifth electrical input 45 can be used individually, for example, for communication between a controller or microcontroller controlling the window device 1 and a network controller.

The power supply unit 50 supplies power to the electrochromic element 10 through the plug-in component 40. In addition, the power supply unit 50 can be controlled by the external controller to supply power of a certain waveform to the electrochromic element 10.

Additionally, the features, structures, effects, etc. described in the embodiments above are included in at least one embodiment of the present invention and are not necessarily limited to only one embodiment. Furthermore, the features, structures, effects, etc. illustrated in each embodiment can be combined or modified and implemented in other embodiments by a person with ordinary knowledge in the field to which the embodiments belong. Therefore, contents related to such combinations and modifications should be construed as being included in the scope of the present invention.

Although the above description focuses on the examples, this is only an example and does not limit the present invention, and those skilled in the art will be able to You will see that various variations and applications are possible. For example, each component specifically shown in the examples can be modified and implemented. And these variations and differences in application should be construed as being included in the scope of the present invention as defined in the appended claims.

Manufacturing example

ITO film: Hansung Industrial Co., Ltd., HI150-ABE-125A-AB

Tungsten oxide powder: Adcro Co., Ltd., ELACO-W

Nickel oxide powder: Adcro Co., Ltd., ELACO-P

Carbon Black: Mitsubishi Chemical Corp, MA-100

Carbon nanotubes: Avention, AV-481436

Gel polymer electrolyte composition

About 39 parts by weight of dipentaerythritol hexaacrylate (DPHA), about 80 parts by weight of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [BMI-TFSI], and about A gel polymer electrolyte composition was prepared by mixing 1 part by weight of diethoxyacetophenone (DEAP) and adding LiBF4 (Li+ concentration: 1 mol/L).

Example 1

About 10 parts by weight of tungsten oxide powder, about 1 part by weight of TEOS, and about 90 parts by weight of ethanol were uniformly mixed to prepare a first color changing material composition. The first color-changing material composition is coated on the first ITO film to a thickness of about 25㎛, and a first color-changing layer with a thickness of about 600nm is formed by a sol-gel reaction at a temperature of about 110°C for about 5 minutes. was formed. Then, about 10 parts by weight of carbon black, about 1 part by weight of TEOS, and about 90 parts by weight of ethanol were mixed uniformly, and an electron accepting material composition was prepared. Thereafter, the electron accepting material composition is coated on the first color change layer to a thickness of about 2.5㎛, and a photoelectron reduction layer having a thickness of about 60nm is obtained by a sol-gel reaction at a temperature of about 110°C for about 5 minutes. A layer was formed. Accordingly, a first laminate including the first discoloration layer and the photoelectron reduction layer was formed.

About 11 parts by weight of nickel oxide powder, about 1 part by weight of TEOS, and about 89 parts by weight of ethanol were uniformly mixed to prepare a second color change material composition. The second discoloring material composition is coated on a second ITO film to a thickness of about 40㎛, and includes a second discoloring layer having a thickness of 1200nm by sol-gel reaction at a temperature of about 120°C for about 5 minutes. A second laminate was manufactured. The gel polymer electrolyte composition is coated on the first discoloration layer to a thickness of about 100㎛, and a second ITO film on which the second discoloration layer is formed is laminated on the coated gel polymer electrolyte composition, and is irradiated by UV light. The coated gel polymer electrolyte composition was cured. Afterwards, the laminate was left at room temperature for about 14 hours to age. Accordingly, the electrochromic device according to the example was manufactured.

Examples 2 to 4 and Comparative Examples

As shown in Table 1 below, the electron accepting material composition was prepared, and the photoelectron reduction layer was formed. Additionally, as shown in Table 1 below, the laminate was aged at room temperature.

division electron accepting material,
Photoelectron accepting layer thickness
(㎚) aging time
(hour) Example 1 Carbon Black, 60 14 Example 2 Carbon Black, 50 14 Example 3 Carbon Black, 40 14 Example 4 Carbon Black, 30 10 Example 5 CNT, 50 0 Comparative example - 0

Evaluation example

1. Solar simulator

The electrochromic device according to the example is irradiated with pseudo-sunlight of about 1000 W/m2 for about 10 minutes by a solar simulator (TNE Tech Co., Ltd., UV aging tester).

2. Total light transmittance

In the electrochromic device in the examples and manufacturing examples, the transmittance before irradiation of pseudo-solar light and the transmittance after irradiation of pseudo-solar light were measured by a solar spectrum meter (EDTM company, SS2450) in the wavelength range of about 380 nm to about 780 nm. It is measured as total light transmittance.

3. Haze

In the electrochromic devices manufactured in the examples and production examples, the haze before irradiation of pseudo-solar light and the haze after irradiation of pseudo-solar light were measured by (Konica-Minolta, CM-5).

4. Color values

In the electrochromic devices manufactured in the examples and manufacturing examples, the color values (L*, a*, and b*) before irradiation of the pseudo-sunlight and the color values after irradiation of the pseudo-sunlight were measured using a spectrophotometer (Konica-Minolta). , CM-5).

5. Charge/discharge test

In the electrochromic devices manufactured in Examples and Comparative Examples, placed in a solar simulator and exposed to pseudo-sunlight, the (-) electrode of a charge/discharge tester (Wona Tech, WBCS_D70714K1) was connected to a bus bar attached to tungsten oxide. Connect the (+) electrode to the bus bar attached to nickel oxide. Afterwards, when a predetermined voltage is applied and a sufficiently high decolorization transmittance is reached, each voltage is connected in reverse by internal electrical transformation of the charge/discharge tester, and the (+) voltage is applied to the bus bar connected to the tungsten oxide, (- ) The voltage is adjusted to be applied to the bus bar connected to the nickel oxide, and a sufficiently low color transmittance is reached in one cycle. A charge/discharge test is performed by continuously repeating the cycle and measuring the transmittance and charge/discharge amount, and discoloration occurs after a certain cycle of operation. The number of times the range was not reduced and the charge/discharge amount was maintained above 80% was measured.

As shown in Table 2 below, in the electrochromic devices according to Examples and Comparative Examples, first light transmittance, second light transmittance, first haze, and second haze were measured.

division First light transmittance
(%) Second light transmittance
(%) 1st Haze
(%) 2nd Haze
(%) Example 1 55 51 2.35 5.31 Example 2 59 52 2.44 2.98 Example 3 62 55 1.56 3.82 Example 4 65 57 1.89 3.91 Example 5 56 52 1.08 5.2 Comparative example 69 51 1.98 7.95

As shown in Table 3 below, color values and charge/discharge times were measured in the electrochromic devices according to Examples and Comparative Examples.

division 1st L* 2nd L* 1st a* 2nd a* 1st b* 2nd b* Charge/discharge recovery
Example 1 91.54 89.9 0.51 -4.3 2.37 -0.75 8000 Example 2 91.45 90.02 0.35 -2.8 2.25 0.89 11000 Example 3 84.06 79.8 -1.81 -5.52 1.80 -5.4 20000 Example 4 87.1 78.9 -1.84 -5.63 1.78 -5.2 15000 Example 5 91.34 90.05 -1.85 -1.45 1.95 0.26 20000 Comparative example 93.33 84.19 0.67 -6.47 1.66 -4.41 3000

As shown in Table 2 and Table 3, the electrochromic devices according to the examples had high light resistance characteristics to external sunlight.

First substrate (100)
Second substrate (200)
First transparent electrode (300)
Second transparent electrode (400)
First discoloration layer (500)
Second color change layer (600)
Electrolyte layer (700)

Claims (11)

first substrate;
a second substrate disposed on the first substrate; and
Comprising an electrochromic portion disposed between the first substrate and the second substrate,
An electrochromic element having a light transmission change rate of less than 0.25, as measured by the following measurement method.
[measurement method]
Through the first substrate, pseudo-solar light is irradiated to the electrochromic portion at an intensity of 1000 W/m2 for 10 minutes, and the first light transmittance of the electrochromic element is measured before irradiation of the pseudo-solar light, and the pseudo-solar light is measured. After irradiation of sunlight, the second light transmittance of the electrochromic element is measured, and the light transmission change rate is the difference between the first light transmittance and the second light transmittance divided by the first light transmittance. The electrochromic device according to claim 1, wherein the haze change measured by the following measurement method is less than 5.5%.
[measurement method]
The first haze of the electrochromic device according to the embodiment is measured before irradiation of the pseudo-solar light, and the second haze of the electrochromic device according to the embodiment is measured after irradiation of the pseudo-solar light, and the haze change is determined by the second haze. It is a value obtained by subtracting the first haze from . The electrochromic device according to claim 2, wherein the L* change measured by the measurement method described below is less than 9.
[measurement method]
The first L* of the first discoloration layer is measured before irradiation of the pseudo-solar light, and the second L* of the first discoloration layer is measured after the irradiation of the pseudo-solar light, and the L* change is the second L* It is the absolute value of the value obtained by subtracting the first L* from . The electrochromic device according to claim 3, wherein the a* change measured by the following measurement method is less than 5.
[measurement method]
The first a* of the first discoloration layer is measured before irradiation of the pseudo-solar light, and the second a* of the first discoloration layer is measured after the irradiation of the pseudo-solar light, and the a* change is the second a* It is the absolute value of the value obtained by subtracting the first a* from . The electrochromic element according to claim 4, wherein the b* change measured by the following measurement method is less than 10.
[measurement method]
The first b* of the first discoloration layer is measured before irradiation of the pseudo-solar light, the 2nd b* of the first discoloration layer is measured after the irradiation of the pseudo-solar light, and the b* change is the second b* It is the absolute value of the value obtained by subtracting the first b* from . According to claim 1,
The electrochromic part
a first transparent electrode disposed on the first substrate;
a first discoloring layer disposed on the first transparent electrode;
an optoelectronic reduction layer disposed on the first discoloration layer;
An electrolyte layer disposed on the photoelectron reduction layer;
a second discoloration layer disposed on the electrolyte layer; and
It includes a second transparent electrode disposed on the second color change layer,
The first color-changing layer includes an electrochromic color-changing material,
The photoelectron reduction layer is an electrochromic device comprising an electron accepting material having a lower band gap than the electrochromic material. 7. The method of claim 6, wherein the first color changing material comprises tungsten oxide,
An electrochromic device wherein the electron accepting material includes at least one from the group consisting of carbon black, carbon nanotubes, or graphene. The electrochromic device of claim 2, wherein the first light transmittance is 50% to 85%, and the first haze is 0.1% to 5%. The electrochromic device of claim 5, wherein the first L* is 80 to 100, the first a* is -2 to 1.5, and the first b* is 0.5 to 4. The electrochromic device of claim 6, wherein the photoelectron reduction layer includes the electron accepting material and a binder. frame;
a window mounted on the frame; and
Comprising an electrochromic element disposed in the window,
The electrochromic element is
first substrate;
a second substrate disposed on the first substrate; and
Comprising an electrochromic portion disposed between the first substrate and the second substrate,
A window device whose light transmission change rate is less than 0.25 as measured by the measurement method below.
[measurement method]
Through the first substrate, pseudo-solar light is irradiated to the electrochromic portion at an intensity of 1000 W/m2 for 10 minutes, and the first light transmittance of the electrochromic element is measured before irradiation of the pseudo-solar light, and the pseudo-solar light is measured. After irradiation of sunlight, the second light transmittance of the electrochromic element is measured, and the light transmission change rate is the difference between the first light transmittance and the second light transmittance divided by the first light transmittance.