CN210742648U - Composite conductive substrate, all-solid-state electrochromic device and electrochromic glass - Google Patents

Abstract

The utility model provides a compound conductive substrate, full solid-state electrochromic device and electrochromic glass, including transparent substrate, ion barrier layer, first transparent conductive oxide layer, transparent metal level, the transparent conductive oxide layer of second and the high resistant protective layer of superpose in proper order. The all-solid-state electrochromic device comprises a composite conductive substrate, an EC stack layer and a second composite conductive layer which are sequentially stacked. Electrochromic glazing comprising a glass substrate for laminating, a film and the use of an all-solid-state electrochromic device according to claim 8 or 9. The utility model discloses a set up the high resistance protective layer, reduce the current value to reduce the voltage drop of the production of potential distribution in-process on the conducting layer, effectively eliminate the chromatic halo phenomenon.

Description

Composite conductive substrate, all-solid-state electrochromic device and electrochromic glass

Technical Field

The utility model relates to a glass technical field that discolours, concretely relates to compound conductive substrate, full solid state electrochromic device and electrochromic glass.

Background

Most of transparent conductive oxide glass produced by the prior art adopts a magnetron sputtering method to sputter metal oxide on the surface of the glass to form a transparent conductive film. Currently this technique faces the following problems: if the conductivity of the film is to be improved, the film thickness needs to be increased, and as a result, the light transmittance of the film is remarkably reduced; conversely, in order to increase the transmittance of the film, the film thickness is decreased, but the conductivity of the film is decreased. To solve this problem, utility model 201720589137.4 discloses a composite transparent conductive layer including two conductive layers, i.e., a transparent conductive oxide layer and a metal layer. However, the application of such composite conductive layer on electrochromic devices still has some non-negligible disadvantages:

1. the conductive substrate needs to be transported, stored and cleaned before the EC film is plated because only one transparent conductive oxide layer is formed on the metal layer, resulting in the metal layer being easily reacted with moisture and oxygen during transportation, storage and cleaning, resulting in corrosion.

2. The EC device prepared by coating the composite conductive layer is easy to generate local short circuit and is represented as a white point.

SUMMERY OF THE UTILITY MODEL

In order to solve the technical problem, the utility model provides a compound conductive substrate, full solid state electrochromic device and electrochromic glass can overcome the contradiction problem of low sheet resistance and high transmittance well, and concrete technical scheme is as follows:

a composite conductive substrate comprises a transparent substrate, an ion barrier layer, a first transparent conductive oxide layer, a transparent metal layer, a second transparent conductive oxide layer and a high-resistance protective layer which are sequentially stacked.

Preferably, the transparent substrate is a glass substrate or a transparent polymer flexible substrate.

Preferably, the material of the ion barrier layer adopts oxide or nitride of silicon, aluminum and titanium.

Preferably, the first transparent conductive oxide layer and the second transparent conductive oxide layer are made of any one of indium tin oxide, fluorine-doped tin oxide, gallium zinc oxide, gallium indium tin oxide and aluminum-doped zinc oxide.

Preferably, the composition of the transparent metal layer is gold, silver, copper or alloy.

Preferably, the high-resistance protective layer is made of transition metal oxide or nitride and has a resistivity of 1000 Ω · M to 10⁸omega.M, the thickness is 10nm to 1000 nm.

Preferably, the high-resistance protective layer is any one of indium tin oxide, silicon nitride, aluminum oxide, titanium oxide, magnesium oxide, vanadium oxide, nickel oxide, and molybdenum oxide.

An all-solid-state electrochromic device comprises the composite conductive substrate, an EC stack layer and a second composite conductive layer which are sequentially stacked.

Further, a second resistance layer is arranged between the second composite conductive layer and the EC stacking layer.

An electrochromic glass comprises a glass substrate for laminating, a film and the all-solid-state electrochromic device.

The utility model discloses in, the electric current passes through perpendicularly the high resistant protective layer, this high resistant protective layer has following characteristic:

1. the resistance of the glass has little influence on large-size electrochromic glass devices, and the color change time is hardly influenced;

2. the high-resistance layer has a good inhibiting effect on local short circuits.

Drawings

Fig. 1 is a schematic structural view of the present invention;

Detailed Description

The present invention will be described in detail with reference to the drawings and specific embodiments, wherein prior to describing the technical aspects of the embodiments of the present invention in detail, the terms and the like are explained, and in the present specification, the components with the same names or the same reference numbers represent the similar or the same structures and are only used for illustrative purposes.

As shown in fig. 1, the composite conductive substrate includes a transparent substrate 1, an ion blocking layer 2, a first transparent conductive oxide layer 3, a transparent metal layer 4, a second transparent conductive oxide layer 5, and a high-resistance protective layer 6, which are sequentially stacked.

The transparent substrate 1 is a glass substrate or a transparent polymer flexible substrate, and the material of the ion barrier layer 2 is an oxide or nitride of silicon, aluminum, titanium, such as silicon dioxide (SiO)₂) Aluminum oxide (Al)₂O₃) Titanium dioxide (TiO)₂) Or silicon nitride (Si)₃N₄) The thickness of the film is 5 to 100 nm.

The first transparent conductive oxide layer 3 and the second transparent conductive oxide layer 5 are made of any one of indium tin oxide, fluorine-doped tin oxide, gallium zinc oxide, gallium indium tin oxide and aluminum-doped zinc oxide. The thickness is 5 to 500nm, preferably 50 to 300 nm.

The transparent metal layer 4 is made of gold, silver, copper or alloy.

The high-resistance protective layer 6 is made of transition metal oxide or nitride and has a resistivity of 1000 omega-M to 10⁸omega.M, the thickness is 10nm to 1000 nm. The high-resistance protective layer is any one of indium tin oxide, silicon nitride, aluminum oxide, titanium oxide, magnesium oxide, vanadium oxide, nickel oxide and molybdenum oxide.

The electrical performance of the electrochromic device is abstracted, and the electrochromic device can be abstracted into a series circuit of a resistor and a capacitor. The current passing between the conductive layers can be regarded as a process of passing current through the resistor, while the ion conductive layer in the EC stack is an insulator of an ion conductor and basically an electron, so the EC stack can be regarded as a capacitor.

Suppose the power voltage is Vo, the resistance of the resistor is R, the capacitance of the capacitor is C, the voltage on the two sides of the capacitor is U, and the time is t.

Since the currents through the resistor and the capacitor are equal in the series circuit, there are:

voltage across the capacitor:

the time constant τ of the RC series circuit is RC, and when the time t is 3RC, U is 95% Vo, which can be equivalent to the discoloration time.

The short circuit white point of the electrochromic device is generated by the principle that conductive impurities in the film layer locally enable conductive layers on two sides of the EC stack layer to be electrically connected. The ion conducting layer in the EC stack is inherently ion conducting and electronically insulating, but once the conductive impurities cause a short circuit locally in the device, the current increases at the conductive impurities, and the nearby regions do not have sufficient potential to cause lithium ion movement, so the nearby regions no longer participate in the coloration. And with the repeated circulation of the device, the size of a short-circuit point is larger and larger near the conductive impurities due to the repeated burning of the current, and the size of a white point which does not participate in color change visually is also larger and larger.

If the resistance layer exists, a film layer for preventing conductive impurities from causing short circuit is additionally arranged between the upper conductive layer and the lower conductive layer. In addition, the high resistance of the resistance layer can limit the magnitude of short-circuit current caused by conductive impurities, and prevent the short-circuit white point from further expanding. It is worth mentioning that the resistive layer is different from the conductive layer. The current of the conducting layer is transmitted transversely, the current of the resistance layer is transmitted vertically, and R is (rho L)/S according to a resistance calculation formula, wherein rho is the resistivity of the material; l is equal to the length of the conductor in the direction of current flow; s is the cross-sectional area of the conductor perpendicular to the current direction. If the resistivity of the resistive layer is 10⁶And Ω · M, assuming that the device size is 1M × 1M and the resistive layer thickness is 100nm, when the current is transmitted vertically, the resistance R is 0.1 ohm by substituting the formula, and according to the above relationship t of the electrochromic device discoloration time and the series resistance being 3RC, the increase of the resistive layer does not have an obvious influence on the discoloration time.

If the film structure of the device is locally poor, 1mm is caused²When the local current increases, the resistance of the high-resistance protective layer at the local position becomes 10⁵Ohm can locally inhibit the increase of current and prevent the further sintering of the film layer, thereby avoiding short circuitThe road area is further enlarged.

The utility model also provides an all-solid-state electrochromic device, pile up layer and the compound conducting layer of second including foretell compound conducting substrate, EC of superpose in proper order. In order to further improve the effect, a second resistance layer is arranged between the second composite conductive layer and the EC stacked layer.

Also provides electrochromic glass, which comprises a glass substrate for laminating, a film and the all-solid-state electrochromic device using the glass substrate.

The above-mentioned embodiments are only to describe the preferred embodiments of the present invention, but not to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art without departing from the design spirit of the present invention should fall into the protection scope defined by the claims of the present invention.

Claims (10)

1. The composite conductive substrate is characterized by comprising a transparent substrate, an ion blocking layer, a first transparent conductive oxide layer, a transparent metal layer, a second transparent conductive oxide layer and a high-resistance protective layer which are sequentially stacked.

2. The composite conductive substrate of claim 1, wherein the transparent substrate is a glass substrate or a transparent polymer flexible substrate.

3. The composite conductive substrate as claimed in claim 1, wherein the material of the ion blocking layer is an oxide or nitride of silicon, aluminum, titanium.

4. The composite conductive substrate of claim 1, wherein the first and second transparent conductive oxide layers are each any one of indium tin oxide, fluorine-doped tin oxide, gallium zinc oxide, gallium indium tin oxide, and aluminum-doped zinc oxide.

5. The composite conductive substrate of claim 1, wherein the transparent metal layer is formed of gold, silver, copper or an alloy.

6. The composite conductive substrate as claimed in claim 1, wherein the high-resistance protective layer is made of transition metal oxide or nitride and has a resistivity of 1000 Ω -M to 10⁸Omega, M, the thickness is 10 nm-1000 nm.

7. The composite conductive substrate according to claim 1, wherein the high-resistance protective layer is any one of indium tin oxide, silicon nitride, aluminum oxide, titanium oxide, magnesium oxide, vanadium oxide, nickel oxide, and molybdenum oxide.

8. An all-solid electrochromic device comprising the composite conductive substrate according to any one of claims 1 to 7, an EC stack, and a second composite conductive layer, which are stacked in this order.

9. The all-solid-state electrochromic device according to claim 8, wherein a second resistive layer is disposed between the second composite conductive layer and the EC stack.

10. An electrochromic glass comprising a glass substrate for laminating, a prepreg and an all-solid electrochromic device according to claim 8 or 9.

Images