KR20240017556A - Electrochromic device and manufacturing method thereof - Google Patents

Abstract

The embodiment includes a first laminate including a first substrate, a first transparent electrode disposed on the first substrate, and a first color change layer disposed on the first transparent electrode; An electrolyte layer disposed on the first discoloration layer; A second laminate including a second discoloring layer disposed on the electrolyte layer, a second transparent electrode disposed on the second discoloring layer, and a second substrate disposed on the second transparent electrode, An electrochromic device in which the light transmission change rate of the first laminate is 0.3 or less is provided.

Description

Electrochromic device and manufacturing method thereof}

Examples relate to electrochromic devices and methods for manufacturing 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.

The embodiment seeks to provide an electrochromic device with improved durability and a method of manufacturing the same.

An electrochromic device according to an embodiment includes a first laminate including a first substrate, a first transparent electrode disposed on the first substrate, and a first color change layer disposed on the first transparent electrode; An electrolyte layer disposed on the first discoloration layer; A second laminate including a second discoloring layer disposed on the electrolyte layer, a second transparent electrode disposed on the second discoloring layer, and a second substrate disposed on the second transparent electrode, In the first laminate, the light transmission change rate measured by the measurement method below is 0.3 or less.

[measurement method]

Quasi-sunlight is irradiated to the first discoloration layer at an intensity of 1000 W/m2 for 10 minutes, the first light transmittance of the first laminate is measured before irradiation of the pseudo-sunlight, and after irradiation of the pseudo-sunlight, the The second light transmittance of the first laminate is measured, and the rate of change in light transmission is the difference between the first light transmittance and the second light transmittance divided by the first light transmittance.

In one embodiment, in the first laminate, the haze change measured by the following measurement method may be 5.5% or less.

[measurement method]

The first haze of the first laminate is measured before the pseudo-solar light irradiation, the second haze of the first laminate is measured after the pseudo-solar light irradiation, and the haze change is from the second haze to the first haze. It is the absolute value of the value minus the haze.

In one embodiment, in the first laminate, the L* change measured by the measurement method below may be 9 or less.

[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 .

In one embodiment, in the first laminate, the a* change measured by the following measurement method may be 5 or less.

[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 .

In one embodiment, in the first laminate, the b* change measured by the following measurement method may be 10 or less.

[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 .

In one embodiment, the first color changing layer may include a first color changing material and an electron accepting material having a lower band gap than the first color changing material.

In one embodiment, the first color changing 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 70% to 90%, 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 first color changing layer may include 0.1 wt% to 1 wt% of the electron accepting material based on the total weight of the first color changing layer.

A method of manufacturing an electrochromic device according to an embodiment includes: a first substrate; and providing a first transparent electrode disposed on the first substrate; forming a first color-changing layer on the first transparent electrode, including a first color-changing material and an electron-accepting material having a lower band gap than the first color-changing material; forming an electrolyte layer on the first discoloration layer; And disposing a second discoloring layer, a second transparent electrode, and a second substrate on the electrolyte layer,

In the first laminate, the light transmission change rate measured by the measurement method below is 0.3 or less.

[measurement method]

Quasi-sunlight is irradiated to the first discoloration layer at an intensity of 1000 W/m2 for 10 minutes, the first light transmittance of the first laminate is measured before irradiation of the pseudo-sunlight, and after irradiation of the pseudo-sunlight, the The second light transmittance of the first laminate is measured, and the rate of change in light transmission is the difference between the first light transmittance and the second light transmittance divided by the first light transmittance.

An electrochromic device according to an embodiment includes a first laminate having a light transmission change rate of 0.3 or less. 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.

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.

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, a first transparent electrode 300, a second transparent electrode 400, and a first color change layer 500. ), a second discoloration layer 600, and an electrolyte layer 700.

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 about 20% or less. 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 about 20% or less. 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, because 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 about 10% or less. The first transparent electrode 300 may have a haze of about 7% or less. The first transparent electrode 300 may have a haze of about 5% or less.

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

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 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. The first color changing layer 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. The first color changing layer 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.

Since the first color changing layer includes the first electrochromic material in the average particle diameter and weight range, the first laminate and the electrochromic device according to the embodiment may have improved optical properties 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 may include the binder in an amount of about 1 wt% to 20 wt% based on the total weight of the first discoloring layer. The first discoloring layer may include the binder in an amount of about 5 wt% to 15 wt% based on the total weight of the first discoloring layer. The first discoloring layer may include the binder in an amount of about 7 wt% to 13 wt% based on the total weight of the first discoloring layer.

The first color changing layer 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 changing layer may include the electron accepting material in particle form. 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 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. The first color changing layer 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. The first color changing layer 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.

Since the first color changing layer includes the electron accepting material within the average particle diameter and weight range, the first laminate and 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 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 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 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, 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, etc.

The first substrate, the first transparent electrode, and the first color change layer may be included in a first laminate. That is, the first laminate includes the first substrate, the first transparent electrode, and the first discoloration layer. The first laminate may be composed of the first substrate, the first transparent electrode, and the first discoloration layer.

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

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 is disposed between the first stack and the second stack. The electrolyte layer may be laminated to the first laminate and the second laminate.

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, an electron accepting 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 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 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.

Additionally, the first sol solution may include the electron accepting material in an amount of about 0.05 wt% to about 5 wt% based on the total solid weight. The first sol solution may include the electron accepting material in an amount of about 0.07 wt% to about 3 wt% based on the total solid weight. The electron accepting material is the same as described above.

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.

Accordingly, a first laminate including the first substrate, the first transparent electrode, and the first discoloration layer may be formed.

Referring to FIG. 3, 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.

Afterwards, 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.

Accordingly, a second laminate including the second substrate, the second transparent electrode, and the second discoloration layer is formed.

Referring to FIG. 4, an electrolyte composition for forming an electrolyte layer 700 is formed on the first discoloration layer 500.

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.

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

Thereafter, the coated electrolyte composition is cured by light, and a first laminate including the first substrate 100, the first transparent electrode 300, and the first discoloration layer 500 and the second A second laminate including the 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 70% to about 90%. The light transmittance of the electrochromic device may be about 75% to about 88%. The light transmittance of the electrochromic device may be about 78% to about 86%.

The first laminate 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]

Pseudo-solar light is irradiated to the first color-changing layer at an intensity of about 1000 W/m2 for 10 minutes, the first light transmittance of the electrochromic element is measured before irradiation of the pseudo-solar light, and after irradiation of the pseudo-solar light, the The second light transmittance of the electrochromic device is measured, and the rate of change in light transmission is the difference between the first light transmittance and the second light transmittance divided by the first light transmittance.

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 after the pseudo-sunlight is irradiated to the first color change layer through the first substrate at an intensity of about 1000 W/m2 for 10 minutes, is the light transmittance of the electrochromic device.

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 first laminate may be 0 to about 0.30. The light transmission change rate of the first laminate may be 0 to about 0.25. The light transmittance change rate of the first laminate may be about 0.01 to about 0.20. The light transmission change rate of the first laminate may be about 0.02 to about 0.18. The light transmission change rate of the first laminate may be about 0.03 to about 0.15.

The light transmittance of the first laminate may be about 75% to about 95%. The light transmittance of the first laminate may be about 80% to about 95%. The light transmittance of the first laminate may be about 85% to about 93%.

The light transmittance after the pseudo-sunlight is irradiated to the first laminate may be about 60% to about 85%. Light transmittance after the pseudo-sunlight is irradiated to the first laminate may be about 65% to about 83%. The light transmittance after the pseudo-sunlight is irradiated to the first laminate may be about 70% to about 80%.

The first laminate has the same 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.

The first laminate may have haze.

The haze may mean haze in a state in which the first laminate is not photodiscolored or electrodiscolored.

The haze of the first laminate may be about 5% or less. The haze of the first laminate may be about 4% or less. The haze of the first laminate may be about 3% or less. The haze of the first laminate may be about 2% or less.

The first laminate may have haze changes.

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

[Measurement method 2]

The first haze of the first laminate is measured before the pseudo-solar light irradiation, the second haze of the first laminate is measured after the pseudo-solar light irradiation, and the haze change is from the second haze to the first haze. This is the value minus the haze.

The haze change of the first laminate may be 5.5% or less. The haze change of the first laminate may be 5% or less. The haze change of the first laminate may be 4% or less. The haze change of the first laminate may be 3% or less. The haze change of the first laminate may be 2% or less.

In the first laminate, haze after irradiation with the pseudo-solar light may be about 6% or less. In the first laminate, haze after irradiation with the pseudo-solar light may be about 5% or less. In the first laminate, the haze after being irradiated with the pseudo-solar light may be about 4% or less. In the first laminate, haze after irradiation with the pseudo-solar light may be about 3% or less.

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.

The first color change layer may have L*, a*, and b*.

L* of the first discoloration layer may be about 70 to about 100. L* of the first discoloration layer may be about 80 to about 100. L* of the first discoloration layer may be about 91 to about 100. The L* can be measured in a state in which the first color change layer does not photo-discolor and/or electro-discolor.

The first color change layer may have an L* change.

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

[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 .

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

[Formula 2]

L*change = │2nd L* - 1st L*│

The L* change of the first discoloration layer may be 7 or less. The L* change of the electrochromic device may be 6 or less. The L* change of the first discoloration layer may be 5 or less. The L* change of the first discoloration layer may be 4 or less.

L* after the pseudo-solar light is irradiated to the first discoloration layer may be about 70 to about 95. L* after the pseudo-solar light is irradiated to the first color change layer may be about 76 to about 94.

a* of the first discoloration layer may be -3 to 2. a* of the first discoloration layer may be -2.5 to 1.5. a* of the first discoloration layer may be -2 to 1. The a* can be measured in a state in which the first color changing layer does not photochromic and/or electrochromic.

The first color change layer may have a* change.

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

[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 a value obtained by subtracting the first a* from .

The a* change of the first discoloration layer can be expressed by Equation 3 below.

[Formula 3]

a*change = │2nd a* - 1st a*│

The a* change of the first discoloration layer may be 6 or less. The a* change of the first discoloration layer may be 5 or less. The a* change of the first discoloration layer may be 2 or less. The a* change of the first discoloration layer may be 3 or less. The a* change of the first discoloration layer may be 1.8 or less. The a* change of the first discoloration layer may be 1.6 or less. The a* change of the first discoloration layer may be 1.5 or less.

a* after the pseudo-sunlight is irradiated to the first color change layer may be about -5 to about 0. a* after the pseudo-sunlight is irradiated to the first discoloration layer may be about -4.5 to about 0.

b* of the first discoloration layer may be 0 to 4. b* of the first discoloration layer may be 0.1 to 3.5. b* of the first discoloration layer may be 0.5 to 3. The b* can be measured in a state in which the first color changing layer does not photodiscolor and/or electrodiscolor.

The first color change layer may have a b* change.

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

[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 a value obtained by subtracting the first b* from .

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

[Formula 4]

b* change = │2nd b* - 1st b*│

The b*change of the first discoloration layer may be 10 or less. The b*change of the first discoloration layer may be 8 or less. The b*change of the first discoloration layer may be 7 or less. The b*change of the first discoloration layer may be 2.8 or less. The b*change of the first discoloration layer may be 2.6 or less. The b*change of the first discoloration layer may be 2.5 or less.

b* after the pseudo-solar light is irradiated to the first discoloration layer may be about -5 to about 3. b* after the first discoloration layer is irradiated with the pseudo-solar light may be about -4.5 to about 2.

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

The first laminate may have the same haze change as described above. Additionally, the first discoloration layer 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.

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, about 90 parts by weight of ethanol, and about 0.1 part by weight of carbon black 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 having a thickness of about 600nm is formed by a sol-gel reaction at a temperature of about 110°C for about 5 minutes. A first laminate comprising: 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 a 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 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 first discoloration material composition was prepared, and the first discoloration layer was formed. Additionally, as shown in Table 1 below, the laminate was aged at room temperature.

division tungsten oxide
(part by weight) ethanol
(part by weight) TEOS
(part by weight) electron accepting material
(part by weight) aging time
(hour) Example 1 10 90 One Carbon black, 0.01 14 Example 2 10 90 One Carbon black, 0.05 14 Example 3 10 90 One Carbon black, 0.1 14 Example 4 10 90 One Carbon black, 0.1 10 Example 5 10 90 One CNT, 0.01 0 Comparative example 10 90 One 0 0

Evaluation example

1. Solar simulator

In the first laminate, pseudo-sunlight of about 1000 W/m2 is irradiated to the first discoloration layer by a solar simulator (TNI Tech Co., Ltd., UV aging tester) for about 10 minutes.

2. Total light transmittance

In the first laminate in the examples and manufacturing examples, the transmittance before irradiation of the pseudo-solar light and the transmittance after irradiation of the 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 first laminate 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 first discoloration layer prepared in the examples and production 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- It is measured by 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 81 68 1.19 6.31 Example 2 77 69 1.25 1.98 Example 3 71 66 2.19 2.82 Example 4 71 68 2.17 2.91 Example 5 80 67 1.08 5.32 Comparative example 83 55 0.98 7.19

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 92.44 89.92 0.51 -4.13 2.27 -071 7000 Example 2 92.44 89.92 0.35 -2.28 2.28 0.79 10000 Example 3 83.05 74.87 -1.61 -5.59 1.89 -5.44 20000 Example 4 83.19 74.95 -1.68 -5.64 1.99 -5.32 15000 Example 5 92.39 90.05 -1.68 -1.43 1.87 0.23 20000 Comparative example 94.33 84.19 0.56 -6.47 1.66 -4.40 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 discoloration layer (600)
Electrolyte layer (700)

Claims (11)

A first laminate including a first substrate, a first transparent electrode disposed on the first substrate, and a first color change layer disposed on the first transparent electrode;
An electrolyte layer disposed on the first discoloration layer;
Comprising a second laminate including a second discoloring layer disposed on the electrolyte layer, a second transparent electrode disposed on the second discoloring layer, and a second substrate disposed on the second transparent electrode,
In the first laminate, an electrochromic element having a light transmission change rate of 0.3 or less as measured by the following measurement method.
[measurement method]
Quasi-sunlight is irradiated to the first discoloration layer at an intensity of 1000 W/m2 for 10 minutes, the first light transmittance of the first laminate is measured before irradiation of the pseudo-sunlight, and after irradiation of the pseudo-sunlight, the The second light transmittance of the first laminate is measured, and the rate of change in light transmission is the difference between the first light transmittance and the second light transmittance divided by the first light transmittance. The electrochromic element according to claim 1, wherein, in the first laminate, a haze change measured by the following measurement method is 5.5% or less.
[measurement method]
The first haze of the first laminate is measured before the pseudo-solar light irradiation, the second haze of the first laminate is measured after the pseudo-solar light irradiation, and the haze change is from the second haze to the first haze. This is the value minus the haze. The electrochromic element according to claim 2, wherein in the first laminate, the L* change measured by the measurement method below is 9 or less.
[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 element according to claim 3, wherein in the first laminate, a* change measured by the following measurement method is 5 or less.
[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 in the first laminate, the b* change measured by the following measurement method is 10 or less.
[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 . The method of claim 1, wherein the first discoloration layer is
a first discoloring material; and
An electrochromic device comprising an electron accepting material having a lower band gap than the first color changing 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 70% to 95%, 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 first color changing layer includes the electron accepting material in an amount of 0.1 wt% to 1 wt% based on the total weight of the first color changing layer. first substrate; and providing a first transparent electrode disposed on the first substrate;
forming a first color-changing layer on the first transparent electrode, including a first color-changing material and an electron-accepting material having a lower band gap than the first color-changing material;
forming an electrolyte layer on the first discoloration layer; and
Comprising the step of disposing a second discoloring layer, a second transparent electrode, and a second substrate on the electrolyte layer,
A method of manufacturing an electrochromic element in which, in the first laminate, the light transmission change rate is 0.3 or less, as measured by the following measurement method.
[measurement method]
Quasi-sunlight is irradiated to the first discoloration layer at an intensity of 1000 W/m2 for 10 minutes, the first light transmittance of the first laminate is measured before irradiation of the pseudo-sunlight, and after irradiation of the pseudo-sunlight, the The second light transmittance of the first laminate is measured, and the rate of change in light transmission is the difference between the first light transmittance and the second light transmittance divided by the first light transmittance.