Flexible all-solid-state electrochromic device

Abstract

The utility model provides a flexible all-solid-state electrochromic device. The flexible all-solid-state electrochromic device comprises a main body structure, a matching structure and a flexible film, the main body structure comprises a UTG substrate, a first conducting layer, an electrochromic layer, an ion transmission layer, an ion storage layer and a second conducting layer which are sequentially stacked, and the thickness of the UTG substrate is 200 microns or below; the matching structure comprises an electrode, and the electrode is connected with the main body structure; and the flexible film coats the surface of the main body structure and coats at least partial surface of the electrode. The flexible all-solid-state electrochromic device has good flexibility and bending resistance, and can be bent to form a required curvature during use; the flexible film outside the device can reduce oxidation and water absorption of the device on the premise that the high-temperature processing resistance and the bending performance of the device are reserved, and the flexibility and the durability of the device are further improved.

Description

TECHNICAL FIELD

[0001] The utility model belongs to the technical field of electrochromic device, specifically relates to a kind of flexible full solid-state electrochromic device. BACKGROUND

[0002] Electrochromism refers to the phenomenon that the optical properties (such as transmittance, reflectance or color) of a material change reversibly under the action of an applied electric field. Electrochromic devices can be divided into liquid electrolyte devices, gel-type devices and full solid-state devices according to the type of electrolyte. Compared with liquid electrolyte devices and gel-type devices, inorganic full solid-state electrochromic devices have the advantages of higher stability, longer service life and better environmental adaptability, and are therefore widely used in intelligent windows, energy-saving buildings, automobile sunroofs and other fields.

[0003] For example, with the development of new energy electric vehicle technology and the pursuit of green and environmentally friendly buildings, the demand for intelligent color-changing awnings has increased. Due to their unique structure, such intelligent windows require electrochromic devices to be curved instead of flat. However, current industrialized electrochromic inorganic full solid-state devices usually rely on complex processes such as sputtering and high-temperature heating, and are mainly based on traditional glass substrates. Due to the inherent rigidity of traditional glass, these devices are difficult to bend, limiting their application. Therefore, developing electrochromic inorganic full solid-state devices with certain flexibility and bending performance has become a key direction to solve this problem. However, current traditional curved (flexible) electrochromic devices have various limitations. SUMMARY

[0004] To solve all or part of the above technical problems, the utility model provides the following technical solutions:

[0005] The utility model provides a kind of flexible full solid-state electrochromic device, the flexible full solid-state electrochromic device includes main body structure, cooperation structure and flexible film;

[0006] The main body structure includes UTG substrate, first conductive layer, electrochromic layer, ion transport layer, ion storage layer and second conductive layer which are sequentially stacked, wherein the thickness of the UTG substrate is less than or equal to 200 μm;

[0007] The cooperation structure includes electrode, and the electrode is connected with the main body structure;

[0008] The flexible film is coated on the surface of the main body structure and at least part of the surface of the electrode.

[0009] In some embodiments, the UTG substrate is an aluminum-silicon glass substrate.

[0010] In some embodiments, the thickness of the UTG substrate is 30-200 um.

[0011] In some embodiments, the first conductive layer is an FTO conductive layer, an ITO conductive layer, an Ag / ITO / Ag composite conductive layer, or a metal nanowire conductive layer.

[0012] In some embodiments, the second conductive layer is an FTO conductive layer, an ITO conductive layer, an Ag / ITO / Ag composite conductive layer, or a metal nanowire conductive layer.

[0013] In some embodiments, the thickness of the first conductive layer and the second conductive layer is 100-400 nm.

[0014] In some embodiments, the electrochromic layer is a WO3 layer, a TiO2 layer, or a MoO3 layer.

[0015] In some embodiments, the thickness of the electrochromic layer is 100-400 nm.

[0016] In some embodiments, the ion transport layer is a LiNbO3 ion transport layer or a LiTaO3 ion transport layer.

[0017] In some embodiments, the thickness of the ion transport layer is 100-400 nm.

[0018] In some embodiments, the ion storage layer is a CeO2 ion storage layer or a NiO ion storage layer.

[0019] In some embodiments, the thickness of the ion storage layer is 100-200 nm.

[0020] In some embodiments, the flexible film is a CPI film, a PET film, or a TPU film.

[0021] In some embodiments, the thickness of the flexible film is 0.03-1 mm.

[0022] The flexible all-solid-state electrochromic device can be prepared by the following preparation method, comprising:

[0023] A UTG substrate is provided, and a first conductive layer, an electrochromic layer, an ion transport layer, an ion storage layer, and a second conductive layer are sequentially formed on the UTG substrate by physical vapor deposition to obtain a precursor structure;

[0024] The precursor structure is subjected to a first annealing treatment to obtain a main body structure;

[0025] A matching structure is arranged on the main body structure, and the matching structure comprises an electrode.

[0026] Coating a flexible film on the surface of the main body structure and at least a part of the surface of the electrode to obtain a flexible all-solid-state electrochromic device.

[0027] The first annealing process specifically can include: heating to 100-500℃ at a heating rate of 2-10℃ / min in an inert atmosphere or an atmosphere containing a reducing gas and holding for 0.5-2h.

[0028] Further, the inert atmosphere includes argon.

[0029] Further, the atmosphere containing a reducing gas includes an inert gas and hydrogen. The flow rate ratio of the inert gas and hydrogen can be 200:10-200:40.

[0030] The physical vapor deposition method can include one or a combination of magnetic sputtering, thermal evaporation, electron beam evaporation, and atomic layer deposition.

[0031] Further, the physical vapor deposition method preferably includes magnetic sputtering.

[0032] The process conditions for depositing the first conductive layer and the second conductive layer by magnetic sputtering can include: a vacuum degree of 6×10 -3 Pa or less, a sputtering mode of radio frequency mode, an atmosphere of argon with a flow rate of 50-100sccm, a sputtering gas pressure of 0.5-1.5Pa, a power of 50-200W, and a deposition time of 600-4800s.

[0033] The process conditions for depositing the electrochromic layer by magnetic sputtering can include: a vacuum degree of 6×10 -3 Pa or less, a sputtering mode of direct current sputtering, an atmosphere of a mixed atmosphere containing oxygen and argon, wherein the oxygen flow rate is 25-50sccm, the argon flow rate is 80-200sccm, the sputtering gas pressure is 0.5-1.5Pa, the power is 50-200W, and the deposition time is 600-1800s.

[0034] The process conditions for depositing the ion transport layer and the ion storage layer by magnetic sputtering can include: a vacuum degree of 6×10 -3 Pa or less, a sputtering mode of radio frequency mode, an atmosphere of a mixed atmosphere containing oxygen and argon, wherein the oxygen flow rate is 1-10sccm, the argon flow rate is 80-200sccm, the sputtering gas pressure is 0.5-1.5Pa, the power is 50-200W, and the deposition time is 6000-18000s.

[0035] After the first conductive layer is deposited on the UTG substrate by the magnetron sputtering method, a step of performing second annealing on the UTG substrate containing the first conductive layer can be further included, and the second annealing specifically includes: increasing the temperature to 350-550 DEG C at a temperature increasing speed of 2-10 DEG C / min in an inert atmosphere or an atmosphere containing a reducing gas and keeping the temperature for 0.5-2 h.

[0036] Further, the inert atmosphere includes argon.

[0037] Further, the atmosphere containing the reducing gas includes inert gas and hydrogen, and the flow ratio of the inert gas and the hydrogen is 200:10-200:40.

[0038] Compared with the prior art, the flexible all-solid-state electrochromic device has the following technical effects: the flexible all-solid-state electrochromic device has good flexibility and bending resistance, can be bent to the required curvature during use, the flexible film outside the device can reduce oxidation and water absorption of the device under the premise of retaining the high-temperature processing capability and bending performance of the device, and further improve the flexibility and durability of the device. BRIEF DESCRIPTION OF DRAWINGS

[0039] In order to more clearly illustrate the technical solutions in the embodiments or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are only some embodiments described in the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0040] Figure 1 is a structural schematic diagram of the flexible all-solid-state electrochromic device of embodiment 1;

[0041] Figure 2 is an SEM structure diagram of part of the main body structure of the flexible all-solid-state electrochromic device of embodiment 1.

[0042] 1-UTG ultra-thin aluminum-silicon glass, 2-first ITO conductive layer, 3-WO3 layer, 4-LiNbO3 layer, 5-CeO2 layer, 6-second ITO conductive layer, 7-CPI film, 8-electrode. DETAILED DESCRIPTION

[0043] The technical solutions of the present application will be described in detail below in combination with specific embodiments, so that those skilled in the art can better understand and implement the technical solutions of the present application. The specific functional details disclosed in this paper should not be interpreted as being limited, but only as being the basis of the claims and being used to teach those skilled in the art to use the representative basis of the present application in different ways in practically any appropriate detailed embodiment.

[0044] In addition, unless otherwise specified, the various raw materials used in the following examples can be obtained from the market or the like, and the various production and testing equipment used is known in the art, and the testing methods used are conventional methods in the art.

[0045] Example 1

[0046] The present embodiment provides a flexible all-solid-state electrochromic device and a preparation method thereof. Figure 1 is a structural schematic diagram of the flexible all-solid-state electrochromic device of the present embodiment, as shown in Figure 1 the flexible all-solid-state electrochromic device includes a main structure, a matching structure, and a flexible film 7; the main structure includes a UTG ultra-thin aluminum-silicon glass substrate 1, a first ITO conductive layer 2, a WO3 layer 3, a LiNbO3 layer 4, a CeO2 layer 5, and a second ITO conductive layer 6 which are sequentially stacked, the matching structure includes a copper electrode 8, and the copper electrode 8 is in contact with the main structure; the flexible film 7 is a CPI film, and the CPI film is coated on the surface of the main structure and the electrode.

[0047] The thickness of the UTG ultra-thin aluminum-silicon glass substrate 1 is 30 μm, the thickness of the first ITO conductive layer 2 is 200 nm, the thickness of the WO3 layer 3 is 320 nm, the thickness of the LiNbO3 layer 4 is 270 nm, the thickness of the CeO2 layer 5 is 160 nm, and the thickness of the second ITO conductive layer 6 is 200 nm; the thickness of the CPI film 7 is 0.03 mm, and the CPI film can reduce the oxidation and water absorption of the device and enhance the toughness of the device.

[0048] The preparation method of the flexible all-solid-state electrochromic device specifically includes the following steps:

[0049] (1) The UTG ultra-thin aluminum-silicon glass (thickness 30 μm, size 20 mm x 30 mm x 0.03 mm) is ultrasonically cleaned in ethanol for 10 min and dried in a vacuum oven.

[0050] (2) The cleaned and dried UTG ultra-thin aluminum-silicon glass is transferred to the vacuum chamber of a magnetron sputtering system, the gas pressure is pumped to 6 x 10 -3 Pa, a 200 nm thick ITO conductive layer is sputtered using an ITO target, the sputtering mode is radio frequency mode, the deposition parameters are argon 60 sccm, the sputtering gas pressure is 0.8 Pa, the power is 100 W, the deposition time is 1200 s, and a UTG / ITO composite structure is prepared.

[0051] (3) The UTG / ITO composite structure is placed in a tube furnace, annealed at 400℃ for 0.5 h in an argon atmosphere (argon flow rate 1200 sccm) at a heating rate of 5℃ / min, and naturally cooled to room temperature after annealing.

[0052] (4) The UTG / ITO composite structure after annealing in step (3) is transferred to a magnetron sputtering vacuum chamber, and the gas pressure is extracted to 6x10 -3 Pa, and then a W target is used to sputter a WO3 film, the sputtering mode is direct current sputtering, the specific deposition parameters are O2: Ar of 27 sccm: 81 sccm, the sputtering gas pressure is 1.2 Pa, the power is 100 W, the deposition time is 1200 s, and the UTG / ITO / WO3 composite structure is prepared.

[0053] (5) Then, the ion transport layer is deposited on the UTG / ITO / WO3 composite structure using a magnetron sputtering device, the vacuum degree is extracted to 4x10 -4 Pa, the radio frequency mode and the LiNbO3 target are selected, the power is set to 100 W, the gas pressure is 1.1 Pa, the oxygen and argon gas flow rate ratio is set to 5 sccm: 95 sccm, the deposition time is 12000 s, and the UTG / ITO / WO3 / LiNbO3 composite structure is prepared.

[0054] (6) The ion storage layer is deposited on the LiNbO3 layer of the UTG / ITO / WO3 / LiNbO3 composite structure using a magnetron sputtering device, the vacuum degree is extracted to 4x10 -4 Pa, the radio frequency mode and the CeO2 target are selected, the power is 100 W, the gas pressure is 1.1 Pa, the oxygen and argon gas flow rate ratio is set to 5 sccm: 95 sccm, the deposition time is 6000 s, and the UTG / ITO / WO3 / LiNbO3 / CeO2 composite structure is prepared.

[0055] (7) Finally, the bottom ITO conductive layer is deposited using a magnetron sputtering device, the vacuum degree is extracted to 4x10 -4 Pa, the radio frequency mode and the ITO target are selected, the power is 100 W, the gas pressure is 0.8 Pa, the argon flow rate is 60 sccm, the deposition time is 1200 s, and the UTG / ITO / WO3 / LiNbO3 / CeO2 / ITO structure is prepared, which is denoted as the precursor structure;

[0056] (8) The precursor structure prepared in step (7) is annealed in a tube furnace, the atmosphere is argon atmosphere and the argon flow rate is 1200 sccm, the temperature is raised to 150℃ at a rate of 5℃ / min and kept for 0.5 h, and the main body structure is obtained.

[0057] (9) After the annealing is completed, the temperature is naturally lowered to room temperature, then the copper electrode is assembled, and a layer of CPI film with a thickness of 0.03 mm is covered on the surface, and the flexible all-solid-state electrochromic device is obtained.

[0058] Figure 2 It is a SEM structure diagram of part of the main body structure of the flexible all-solid-state electrochromic device of the embodiment.

[0059] The flexibility of the device prepared in Example 1 was tested. After 500 times of bending with a bending radius of 1 cm, the modulation amplitude of the device did not decrease by more than 10%.

[0060] The durability of the device prepared in Example 1 was tested. It was found that the device still had a modulation amplitude of 40% at 630 nm after 1000 times of cycling (±3V voltage).

[0061] Bending to the required curvature: the device prepared in this embodiment can be applied to the sky screen of a new energy vehicle, and the ideal bending radius of the device is 1 mm.

[0062] The coloring and fading times of Example 1 were tested: the coloring time was 15 s, the fading time was 25 s, and the color change response speed was relatively fast.

[0063] Example 2

[0064] Example 2 provides a flexible all-solid-state electrochromic device, which comprises a main body structure, a matching structure and a flexible film; the main body structure comprises a UTG ultra-thin aluminum-silicon glass substrate, a first FTO conductive layer, a TiO2 layer, a LiTaO3 layer, a NiO layer and a second FTO conductive layer which are sequentially stacked, the matching structure comprises a copper electrode, and the copper electrode is in contact with the main body structure; the flexible film is a PET film, and the PET film is coated on the surface of the main body structure.

[0065] The thickness of the UTG ultra-thin aluminum-silicon glass substrate is 30 μm, the thickness of the first FTO conductive layer is 100 nm, the thickness of the TiO2 layer is 100 nm, the thickness of the LiTaO3 layer is 100 nm, the thickness of the NiO layer is 100 nm, and the thickness of the second FTO conductive layer is 100 nm. The thickness of the PET film is 0.1 mm. The PET film can reduce the oxidation and water absorption of the device and enhance the toughness of the device.

[0066] Example 3

[0067] Example 3 provides a flexible all-solid-state electrochromic device, which comprises a main body structure, a matching structure and a flexible film; the main body structure comprises a UTG ultra-thin aluminum-silicon glass substrate, a first ITO conductive layer, a MoO3 layer, a LiTaO3 layer, a CeO2 layer and a second ITO conductive layer which are sequentially stacked, the matching structure comprises a copper electrode, and the copper electrode is in contact with the main body structure; the flexible film is a TPU film, and the TPU film is coated on the surface of the main body structure.

[0068] The thickness of the UTG ultra-thin aluminum-silicon glass substrate is 200 microns, the thickness of the first ITO conductive layer is 400 nm, the thickness of the WO3 layer is 400 nm, the thickness of the LiTaO3 layer is 400 nm, the thickness of the CeO2 layer is 200 nm, and the thickness of the second ITO conductive layer is 400 nm. The thickness of the TPU film is 1 mm, and the TPU film can reduce the oxidation and water absorption of the device and enhance the toughness of the device.

[0069] Comparative Example 1

[0070] The difference between Comparative Example 1 and Example 1 is that the flexible all-solid-state electrochromic device of Comparative Example 1 does not have a CPI film.

[0071] Comparing Comparative Example 1 and Example 1, it is found that the shearing force resistance of the device with the CPI film is improved by about 50% compared with the device without the CPI film, indicating that the film can improve the flexibility and durability of the device.

[0072] The aspects, embodiments, features, and examples of the present application should be considered in all respects as illustrative only and not restrictive in any manner. The scope of the present application is defined only by the claims. Other embodiments, modifications, and uses can be apparent to those skilled in the art, which do not depart from the spirit and scope of the application as claimed.

[0073] In addition, the present application has also been tested by referring to the foregoing examples, using other raw materials, process operations, and process conditions described in the specification, and ideal results have been obtained.

[0074] Although the present application has been described with reference to the illustrative embodiments, those skilled in the art will appreciate that various other changes, omissions, and / or additions can be made thereto without departing from the spirit and scope of the application as claimed. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the application without departing from the scope of the application. Therefore, the present application is not intended to be limited to the disclosed embodiments for carrying out the application, but rather is intended to cover all alternatives, modifications, and equivalents falling within the scope of the appended claims. Furthermore, unless specifically stated otherwise, any use of the terms first, second, etc., does not indicate any order or importance, but rather the terms first, second, etc., are used to distinguish one element from another.

Claims

1. A flexible all-solid-state electrochromic device, characterized by, The main body structure, the matching structure and the flexible film are included. The main body structure includes a UTG substrate, a first conductive layer, an electrochromic layer, an ion transmission layer, an ion storage layer and a second conductive layer which are sequentially stacked, wherein the thickness of the UTG substrate is below 200 μm. The matching structure includes an electrode which is connected with the main body structure. The flexible film is wrapped on the surface of the main body structure and the surface of the electrode at least partially.

2. The flexible all-solid-state electrochromic device according to claim 1, characterized in that: The UTG substrate is an aluminum-silicon glass substrate, and the thickness of the UTG substrate is 30-200 μm.

3. The flexible all-solid-state electrochromic device according to claim 1, characterized in that: The first conductive layer is an FTO conductive layer, an ITO conductive layer, an Ag / ITO / Ag composite conductive layer or a metal nanowire conductive layer, and the thickness of the first conductive layer is 100-400 nm.

4. The flexible all-solid-state electrochromic device according to claim 1, characterized in that: The second conductive layer is an FTO conductive layer, an ITO conductive layer, an Ag / ITO / Ag composite conductive layer or a metal nanowire conductive layer, and the thickness of the second conductive layer is 100-400 nm.

5. The flexible all-solid-state electrochromic device according to claim 1, characterized in that: The electrochromic layer is a WO3 layer, a TiO2 layer or a MoO3 layer, and the thickness of the electrochromic layer is 100-400 nm.

6. The flexible all-solid-state electrochromic device according to claim 1, characterized in that: The ion transmission layer is a LiNbO3 ion transmission layer or a LiTaO3 ion transmission layer, and the thickness of the ion transmission layer is 100-400 nm.

7. The flexible all-solid-state electrochromic device according to claim 1, characterized in that: The ion storage layer is a CeO2 ion storage layer or a NiO ion storage layer, and the thickness of the ion storage layer is 100-200 nm.

8. The flexible all-solid-state electrochromic device according to claim 1, characterized in that: The flexible film is a CPI film, a PET film or a TPU film.

9. The flexible all-solid-state electrochromic device according to claim 1, characterized in that: The thickness of the flexible film is 0.03-1 mm.

10. The flexible all-solid-state electrochromic device according to claim 1, characterized in that: The electrode is a copper electrode.

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